An organic polymer support, an ethylene oligomerization catalyst system, and a method for preparing and using the same

Abstract

The application provides an organic polymer carrier, an ethylene oligomerization catalyst system and a preparation method and application thereof. The organic polymer carrier is obtained by copolymerization of monomers including divinylbenzene and a monomer containing a PNP ligand; wherein the monomer containing the PNP ligand has a structure shown in formula I: in formula I, R1 and R2 are each independently selected from H, halogen, C1-C7 alkyl and derivatives thereof, C6-C10 aryl and derivatives thereof; and x is 0-3. The catalyst system has good ethylene oligomerization activity, C6 and C8 olefin selectivity and alpha-olefin selectivity.

Description

Technical Field

[0001] This invention belongs to the field of ethylene oligomerization catalysts, specifically relating to an organic polymer support, an ethylene oligomerization catalyst system, 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 a specific number of carbon atoms. 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-order 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. Industrially, single components or several mixed components can be separated for use as needed. Highly selective ethylene catalysis provides an important pathway for producing single α-olefins with a specific number of carbon atoms, which is of positive significance to both academia and industry. Patents US3444263, US3510539, and US3789081 use the Ziegler-Natta process with triethylaluminum as a catalyst to produce linear α-olefins; however, the use of a large amount of alkylaluminum as a catalyst makes the reaction difficult to control. Subsequently, patent US3644563 used a phosphine-oxygen bidentate nickel complex as a catalyst, which is the well-known SHOP catalyst system, and successfully achieved the industrialization of ethylene oligomerization. This catalyst system represents a major breakthrough in the field of ethylene oligomerization. While the SHOP method offers high activity and good product quality, the multiple isomerization and disproportionation processes result in a lengthy process and high investment. Patents EP241596 and EP320571 used a catalyst system composed of zirconium tetrachloride and alkylaluminum to achieve ethylene oligomerization in a one-step process. This process offers mild reaction conditions and good selectivity for α-olefins in the product. This method further promoted the application of transition metal complexes in ethylene oligomerization. Furthermore, 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. Patent CN1552525A, which uses a tridentate nickel-based complex based on a salicylaldehyde-imine framework, also exhibits high ethylene oligomerization activity.

[0003] Selective trimerization of ethylene was first discovered by Union Carbide during their research on ethylene polymerization. The catalyst consisted of partially hydrolyzed triisobutylaluminum and tri(2-ethylhexanoic acid)chromium. In the catalytic reaction, some ethylene trimerized to form 1-hexene, which then copolymerized with ethylene to form a polymer containing butyl side chains. Phillips Corporation further developed this by introducing pyrrole ligands and modifying the auxiliaries, forming a catalyst system composed of chromium 2-ethylhexanoate, 2,5-dimethylpyrrole, triethylaluminum, and diethylaluminum chloride. This system exhibited high selectivity in catalyzing ethylene trimerization in cyclohexane solvent at 115°C and 10 MPa pressure, producing up to 93% 1-hexene. Carter, A. and Cohen, SA et al. (Chem. Commun. 2002, pp. 858-859) reported that a system composed of chromium trichloride, phosphorus nitrogen phosphorus (PNP) ligand, and methylaluminoxane also exhibited high selectivity in catalyzing the trimerization of ethylene in toluene solvent at 80 °C and 2.0 MPa pressure, producing nearly 90% 1-hexene, with an activity reaching 1.0 × 10⁻⁶. 6 The reaction conditions are relatively mild, with a yield of g / (g Cr·h). Researchers at Sasol Technologies replaced the aryl substituents on the phosphorus atoms of the phosphorus-nitrogen-phosphorus ligands with methoxy groups or hydrogen or alkyl groups. The resulting system, composed of chromium trichloride and methylaluminoxane, selectively catalyzes the tetramerization of ethylene in toluene at 65°C and 3.0 MPa pressure or 45°C and 4.5 MPa pressure, yielding up to 67.5% 1-octene.

[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] Xu et al. (Guo CY, Xu H et al., Immobilization of bis(imino)pyridine iron complexes onto mesoporous molecular sieves and their catalytic performance in ethylene oligomerization. Catalysis Communications, 2009, Vol. 10, No. 10, pp. 1467-1471.) immobilized bis(imino)pyridine iron complexes onto a mesoporous molecular sieve support treated with MAO. The supported catalyst exhibited good ethylene oligomerization activity and α-olefin selectivity. Although its oligomerization activity was lower than that of the homogeneous catalyst at lower reaction temperatures, it still reached 3.2 × 10⁻⁶. 6 g / (molFe·h); When the reaction temperature is high, the thermal stability of the supported catalyst is much better than that of the homogeneous catalyst, and its activity is higher than that of the homogeneous catalyst. In addition, due to the introduction of molecular sieves, there is a "nano confinement effect", so the carbon number distribution of the generated products shifts towards the lower carbon number direction. Moreover, since the pore size of MCM-41 is smaller than that of SBA-15, the confinement effect on macromolecules is stronger. Therefore, when MCM-41 is used as a support, there are more low molecular weight α-olefins in the oligomerization products than when SBA-15 is used as a support, and the distribution range of α-olefins is also narrower. However, its selectivity for C4-C8 olefins is not high, and the content of C10 and above olefins is too high, exceeding 20%. Braca et al. (Braca G. et al., Organometallic nickel catalysts anchored on polymeric matrices in the oligomerization and / or polymerization of olefins. Part II. Effect and role of the components of the catalytic system. Journal of Molecular Catalysis A: Chemical, 1995, Vol. 96, No. 3, pp. 203-213.) prepared a series of supported ethylene oligomerization catalysts by anchoring organometallic nickel bidentate PO chelates on polystyrene resin via ligand carbon atoms. The supported ethylene oligomerization catalysts achieved high ethylene oligomerization activity and good α-olefin selectivity.

[0006] Patent CN200510025276.6 describes a novel diimine nickel or palladium complex for ethylene oligomerization, exhibiting high catalytic activity and selectivity for terminal olefins, with a catalytic activity reaching 2.3 × 10⁻⁶. 6 The yield is g / (molNi·h), and the product is mainly C4-C8 olefins, with α-olefin content greater than 80%, reaching up to 92%. This technology uses unsupported catalysts, and the catalyst system is homogeneous during polymerization. The catalyst and product cannot be separated or reused.

[0007] Carter, A.; Cohen, SA et al. (Chem. Commun. 2002, pp. 858-859) disclosed a system composed of chromium trichloride, phosphorus nitrogen phosphorus (PNP) ligand, and methylaluminoxane, which also exhibited highly selective catalytic catalysis of ethylene trimerization in toluene solvent at 80 °C and 2.0 MPa pressure, yielding nearly 90% 1-hexene, with an activity reaching 1.0 × 10⁻⁶. 6 The reaction conditions are relatively mild, with a yield of g / (g Cr.h). However, this unsupported catalyst results in a homogeneous catalyst system during polymerization, meaning the catalyst and product cannot be separated. Summary of the Invention

[0008] To address the aforementioned problems, the present invention aims to provide an organic polymer support, an ethylene oligomerization catalyst system, its preparation method, and its applications. This catalyst system exhibits good ethylene oligomerization activity, C6 and C8 olefin selectivity, and α-olefin selectivity.

[0009] To achieve the above objectives, the present invention provides an organic polymer carrier obtained by copolymerization of a monomer comprising divinylbenzene and a monomer containing a PNP ligand; wherein the monomer containing the PNP ligand has the structure shown in Formula I:

[0010]

[0011] In Formula I, R1 and R2 are each independently selected from H, halogens, C1-C7 alkyl groups and their derivatives, and C6-C10 aryl groups and their derivatives; x is 0-3.

[0012] According to a specific embodiment of the present invention, preferably, in Formula I, R1 and R2 are each independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl, trifluoromethyl, ethyl, isopropyl, tert-butyl, phenyl, benzyl; x is 0-3.

[0013] According to a specific embodiment of the present invention, preferably, in Formula I, R1 and R2 are each independently selected from hydrogen atoms, methyl groups, and isopropyl groups; x is 0 or 1.

[0014] According to a specific embodiment of the present invention, preferably, the monomer containing the PNP ligand is selected from N,N-diphenylphosphino-4-allylaniline, N,N-diphenylphosphino-4-allyl-2-methylaniline, N,N-diphenylphosphino-4-allyl-2-ethylaniline, N,N-diphenylphosphino-4-allyl-2-isopropylaniline, N,N-diphenylphosphino-4-allyl-2-tert-butylaniline, N,N-diphenylphosphino-4-allyl-2-trifluoromethylaniline, N,N-diphenylphosphino-4-allyl-2,6-dimethylaniline, N,N-diphenylphosphino-4-allyl-2,6-diethylaniline, N,N-diphenylphosphino-4-allyl-2,6-diisopropylaniline, ... N,N-Diphenylphosphino-4-allyl-2,6-dichloroaniline, N,N-Diphenylphosphino-4-allyl-2,6-dibromoaniline, N,N-Diphenylphosphino-4-allyl-2,6-ditert-butylaniline, N,N-Diphenylphosphino-4-allyl-2,6-trifluoromethylaniline, N,N-Diphenylphosphino-4-vinylaniline, N,N-Diphenylphosphino-4-vinyl-2-methylaniline, N,N-Diphenylphosphino-4-vinyl-2-ethylaniline, N,N-Diphenylphosphino-4-vinyl-2-isopropylaniline, N,N-Diphenylphosphino-4-vinyl-2-tert-butylaniline, N,N-Diphenylphosphino-4-vinyl-2-trifluoromethylaniline, N,N-di ...trifluoromethylaniline, N,N-diphenylphosphino-4-vinyl-2-dichloroaniline, N,N-diphenylphosphino-4-vinyl-2-tert-butylaniline, N,N-diphenylphosphino-4-vinyl-2-trifluoromethylaniline, N,N-diphenylphosphino-4-vinyl-2-trifluoromethylaniline, N,N-diphenylphosphino-4-vinyl-2-dichloroaniline, N,N-diphenylphosphino-4-vinyl-2-trifluoromethylaniline, N,N-diphenylphos N,N-diphenylphosphino-4-vinyl-2,6-dimethylaniline, N,N-diphenylphosphino-4-vinyl-2,6-diethylaniline, N,N-diphenylphosphino-4-vinyl-2,6-diisopropylaniline, N,N-diphenylphosphino-4-vinyl-2,6-dichloroaniline, N,N-diphenylphosphino-4-vinyl-2,6-dibromoaniline, N,N-diphenylphosphino-4-vinyl-2,6-ditert-butylaniline, N,N-diphenylphosphino-4-vinyl-2,6-trifluoromethylaniline, N,N-diphenylphosphino-4-allylaniline, N,N-diphenylphosphino-4-allyl-2-ethylaniline, N,N-diphenylphosphino-4-allyl-2-isopropylaniline, N,N-di... Phenylenylphosphino-4-enbutyl-2-tert-butylaniline, N,N-diphenylphosphino-4-enbutyl-2-trifluoromethylaniline, N,N-diphenylphosphino-4-enbutyl-2,6-dimethylaniline, N,N-diphenylphosphino-4-enbutyl-2,6-diethylaniline, N,N-diphenylphosphino-4-enbutyl-2,6-diisopropylaniline, N,N-diphenylphosphino-4-enbutyl-2,6-dichloroaniline, N,N-diphenylphosphino-4-enbutyl-2,6-dibromoaniline, N,N-diphenylphosphino-4-enbutyl-2,6-ditert-butylaniline, N,N-diphenylphosphino-4-enbutyl-2,6-trifluoromethylaniline, N,N-diphenylphosphino-4-enpentylaniline, N,One or a combination of two or more of N-diphenylphosphino-4-enpentyl-2,6-dimethylaniline, N,N-diphenylphosphino-4-enpentyl-2,6-diethylaniline, and N,N-diphenylphosphino-4-enpentyl-2,6-diisopropylaniline.

[0015] According to a specific embodiment of the present invention, preferably, the mass fraction of the monomer containing the PNP ligand is 20-60% when the mass of the organic polymer carrier is 100%; the content of functional monomer in the carrier is determined by the amount of divinylbenzene and the monomer containing the PNP ligand added.

[0016] According to a specific embodiment of the present invention, preferably, the monomer containing the PNP ligand can be prepared by dehydrochlorination in the presence of an organic base using an unsaturated substituted aniline compound (L2) of Formula II as the nitrogen source and a disubstituted diphenylphosphine chloride as the phosphorus source, wherein the molar ratio of the phosphorus source to the nitrogen source compound is 2:1.

[0017]

[0018] L2 can be prepared by referring to existing literature (Kitagawa, Kazuya; Inoue, Atsushi; Shinokubo, Hiroshi; Oshima, Koichiro Angewandte Chemie-International Edition, 2000, vol.39, #14p.2481-2483; Furayama, Taniyuki; Yonehara, Mitsuhiro; Arimoto, Sho; Kobayashi, Minoru; Matsumoto, Yotaro; Uchiyama, Masanobu Chemistry-A European Journal, 2008, vol.14, #33p.10348-10356, etc.), for example, L2 is prepared by reacting 4-bromo-2,6-methylaniline (CAS: 24596-19-8) with a brominated unsaturated alkene; the synthesis of monomers containing PNP ligands can be carried out by existing literature (Zhaofu Fei, Rosario Scopelliti and Paul J. Dyson, Dalton). (Trans., 2003, 2772–2779.) Preparation, for example, using L2 monomer and monochlorodiphenylphosphine PPh2Cl in triethylamine at a molar ratio of 1:2:2 with dichloromethane as solvent to prepare monomer containing PNP ligand at room temperature.

[0019] The present invention also provides a method for preparing the above-mentioned organic polymer carrier, which includes the following steps: using a monomer including the divinylbenzene and the monomer containing the PNP ligand as raw materials, the organic polymer carrier is obtained by copolymerization; the mass ratio of the monomer containing the PNP ligand to the divinylbenzene is 0.2-2:1.

[0020] According to a specific embodiment of the present invention, preferably, the organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization; the dispersion polymerization includes the following steps: adding divinylbenzene and a monomer containing PNP ligands to a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, reacting at 50-80°C for 5-12 hours, washing, filtering and drying to obtain the organic polymer carrier, denoted as POP carrier.

[0021] According to a specific embodiment of the present invention, preferably, the dispersing solvent includes one or more of alcohol solvents, fatty acid ester solvents, and tetrahydrofuran.

[0022] According to a specific embodiment of the present invention, preferably, the alcohol solvent includes one or a combination of two or more of ethanol, propanol, isopropanol, and isobutanol.

[0023] According to a specific embodiment of the present invention, preferably, the fatty acid ester solvent includes 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.

[0024] According to a specific embodiment of the present invention, preferably, the mass ratio of the total amount of monomer added to the dispersing solvent is 1:5-20.

[0025] According to a specific embodiment of the present invention, preferably, the stabilizer is polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer.

[0026] According to a specific embodiment of the present invention, preferably, the weight-average molecular weight of the stabilizer is 1000-100000.

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

[0028] According to a specific embodiment of the present invention, preferably, the initiator is azobisisobutyronitrile (AIBN) and / or benzoyl peroxide (BPO).

[0029] According to a specific embodiment of the present invention, preferably, the mass ratio of the amount of initiator added to the total amount of monomer added is 0.5-3:100.

[0030] According to a specific embodiment of the present invention, preferably, the divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor.

[0031] The present invention can also employ dispersion polymerization, first preparing an organic polymer carrier POP-1 containing substituted aniline functional groups by copolymerizing divinylbenzene with unsaturated substituted aniline monomer L2 free radical, and then reacting POP-1 with diphenylphosphine chloride to prepare an organic polymer carrier containing PNP groups.

[0032] This invention provides an ethylene oligomerization catalyst system (POP-PNP-Cr / (M)MAO), which comprises a main catalyst and a co-catalyst; wherein the main catalyst is prepared by supporting metal Cr on the above-mentioned organic polymer support.

[0033] According to a specific embodiment of the present invention, preferably, the cocatalyst comprises an alkylaluminoxane compound and / or an alkylaluminum.

[0034] According to a specific embodiment of the present invention, preferably, the co-catalyst is methylaluminoxane and / or modified methylaluminoxane.

[0035] According to a specific embodiment of the present invention, preferably, the molar ratio of aluminum in the co-catalyst to Cr in the main catalyst is 30-300, more preferably 50-200.

[0036] According to a specific embodiment of the present invention, preferably, the ratio of aluminum in the co-catalyst to the organic polymer support is from 1 mmol / g support to 15 mmol / g support, more preferably from 3 mmol / g support to 10 mmol / g support.

[0037] According to a specific embodiment of the present invention, preferably, the Cr content in the main catalyst is from 5 micromoles Cr / g support to 100 micromoles Cr / g support, more preferably from 20 micromoles Cr / g support to 50 micromoles Cr / g support.

[0038] The present invention also provides a method for preparing the above-mentioned ethylene oligomerization catalyst system, which includes the following steps: adding the organic polymer support to toluene, then adding a chromium precursor compound, reacting at 20℃-70℃ for 1-5 hours, and obtaining the main catalyst after filtration, washing, and drying; mixing the main catalyst and the co-catalyst in an inert solvent, reacting at 0℃-50℃ for 30-180 minutes, and obtaining the ethylene oligomerization catalyst system after filtration, washing, and drying.

[0039] According to a specific embodiment of the present invention, preferably, the chromium precursor compound includes one or more of the following: chromium trichlorotritetrahydrofuran CrCl3(THF)3, chromium triacetylacetone Cr(acac)3, chromium dichlorotoluene CrCl2(tolyl)(THF)3, chromium dichloride CrCl2, chromium dichloroditetrahydrofuran CrCl2(THF)2, chromium hexacarbonyl Cr(CO)6, chromium dichloromethyltritetrahydrofuran CrCl2Me(THF)3, and chromium triphenyltritetrahydrofuran Cr(Ph)3(THF)3.

[0040] According to a specific embodiment of the present invention, the above preparation method includes the following specific steps:

[0041] A POP support containing a PNP group was added to toluene, followed by the addition of a chromium precursor compound, such as CrCl3(THF)3. The reaction was carried out at 20℃-70℃ for 1-5 hours. After the reaction was complete, the unreacted metal halide reagent was filtered, washed, and dried to obtain an organically supported chromium-containing metal compound POP-PNP-Cr main catalyst system. Then, the dried POP-PNP-Cr main catalyst system and alkylaluminoxane MAO or modified alkylaluminoxane MMAO were added to an inert solvent such as toluene. The temperature was adjusted to 0℃-50℃, and the reaction was carried out for 30-180 minutes. After the reaction was complete, the mixture was filtered, and the product was washed with an inert solvent and dried to obtain the supported POP-PNP-Cr / (M)MAO catalyst system.

[0042] The present invention also provides the application of the above-mentioned ethylene oligomerization catalyst system in ethylene oligomerization.

[0043] According to a specific embodiment of the present invention, preferably, the reaction temperature of the ethylene oligomerization is 20-80°C and the partial pressure of ethylene is 1-10 MPa.

[0044] According to a specific embodiment of the present invention, preferably, the solvent used in the slurry polymerization of ethylene oligomerization is C5-C. 10 Alkanes, such as hexane, cyclohexane, toluene, and methylcyclohexane, more preferably methylcyclohexane. In ethylene oligomerization, a small amount of alkyl aluminum, such as triethylaluminum, can be added to remove trace amounts of water from the solvent.

[0045] The organically supported ethylene oligomerization catalyst system POP-PNP-Cr / (M)MAO of this invention is obtained by copolymerizing divinylbenzene with functional monomers containing [PNP] ligand groups to obtain a porous POP support containing multiple [PNP] ligand groups. Based on the [PNP] ligands on the POP support, the Cr metal active center is fixed on the POP support. Then, through reaction with methylaluminoxane MAO or modified methylaluminoxane MMAO co-catalyst, the organically supported POP-PNP-Cr / (M)MAO catalyst solid component is prepared. The total C6 and C8 olefin content of the organic polymer supported ethylene oligomerization catalyst system POP-PNP-Cr / (M)MAO of this invention can reach more than 85%, and the selectivity of linear α-olefins for both 1-C6 and 1-C8 can reach more than 80%. This invention has the following beneficial effects:

[0046] 1. This invention designs and prepares a POP-PNP-Cr / (M)MAO catalyst solid catalyst component supported on a POP support containing a [PNP] ligand group. The catalyst system exhibits good catalytic activity and selectivity for C6 and C8 olefins in ethylene oligomerization.

[0047] 2. The ethylene oligomerization catalyst system POP-PNP-Cr / (M)MAO supported on the organic polymer support of the present invention can achieve an olefin content of more than 85% for C6 and C8 after ethylene oligomerization, wherein the linear α-olefin selectivity of 1-C6 and 1-C8 can reach more than 80%. Attached Figure Description

[0048] Figure 1 The 1H NMR spectrum of compound L1-1;

[0049] Figure 2 The 1H NMR spectrum of compound L1-2;

[0050] Figure 3 The image shows the 1H NMR spectrum of compound L1-4. Detailed Implementation

[0051] 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.

[0052] The monomer used in the carrier preparation process of this invention is a commercially available monomer, divinylbenzene (DVB), 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 follow existing techniques, such as washing with sodium hydroxide solution and distilled water, followed by drying with anhydrous magnesium sulfate before use.

[0053] 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 testing.

[0054] Example 1

[0055] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0056] 1. Preparation of the functional monomer of N,N-diphenylphosphino-4-allylaniline (L1-1, structure shown below) [PNP]:

[0057]

[0058] (1) Preparation of 4-allyl aniline (L2-1) compound:

[0059] References (Furayama, Taniyuki; Yonehara, Mitsuhiro; Arimoto, Sho; Kobayashi, Minoru; Matsumoto, Yotaro; Uchiyama, Masanobu) 4-Allylaniline (L2-1) was prepared by the reaction of 4-bromoaniline with allyl bromide: In a 250 ml reaction flask, 100 ml of dried tetrahydrofuran (THF), 30 mmol of 4-bromoaniline (CAS: 106-40-1), and then 33 mmol of lithium tert-butylzinc (tBu4ZnLi2 in THF solution) reagent were added. [At -78 °C, in a 500 ml flask, 100 ml of THF and 0.1 mol of ZnCl2 (THF solution) were added, followed by the addition of 0.4 mol of...] [tBuLi (n-pentane solution), reacted for 60 min, filtered at 0 °C to obtain 0.1 mol pale yellow tBu4ZnLi2THF solution], reacted at room temperature for 2 h to prepare 4-(ZntBu3Li2)-aniline intermediate, then a slightly excess of 32 mmol allyl bromide (CAS: 106-95-6) was added, stirred at room temperature for 24 h, filtered, recrystallized to prepare 4-allyl aniline (L2-1) compound, yield 78%;

[0060] (2) Preparation of N,N-diphenylphosphino-4-allylaniline [PNP] functional monomer (L1-1):

[0061] In a 250 ml reaction flask, 100 ml of dried dichloromethane was added, followed by 20 mmol of 4-allylaniline (L2-1) reagent, then 40 mmol of dichlorodiphenylphosphine (CAS: 1079-66-9) and 40 mmol of triethylamine. The reaction was carried out at room temperature for 12 hours. After filtration, N,N-diphenylphosphino-4-allylaniline (L1-1) was prepared by recrystallization with dichloromethane, with a yield of 83%. Its 1H NMR spectrum is shown below. Figure 1 As shown;

[0062] 2. Preparation of porous organic polymer supports containing [PNP] ligands:

[0063] In a 250 ml reactor, 130 ml of anhydrous ethanol and 10 ml of tetrahydrofuran were added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 3.0 g of N,N-diphenylphosphino-4-allyl aniline (L1-1). The mixture was stirred at room temperature for 5 min, and then 2% of the monomer 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% of the monomer mass 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 4.5 g of free-flowing porous carrier POP-1 containing [PNP] ligand.

[0064] 3. Preparation of POP-PNP-Cr / MAO catalyst:

[0065] In a 250 ml reactor, 2 g of dried porous POP-1 support containing [PNP] ligands was added, along with 0.05 g of chromium acetylacetone (III)Cr(acac)3 (CAS: 21679-31-2) and 100 ml of toluene. The mixture was stirred for 3 hours, filtered, and washed twice with toluene to obtain the POP-PNP-Cr main catalyst containing [PNP] ligands. In another 250 ml reactor, the obtained POP-PNP-Cr solid catalyst and 100 ml of toluene were added. The mixture was then heated to 30 °C, and 0.80 g of methylaluminoxane (MAO) solid (obtained as white MAO powder after drying from a 10% MAO toluene solution) was added. The mixture was reacted at room temperature (25 °C) for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing brownish-red catalyst particles, designated Cat-1. The catalyst contained 28.7 μmol / g of chromium and 8.3 mmol / g of aluminum.

[0066] Example 2

[0067] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0068] In a 250 ml reactor, 2 g of POP-1 support was added, followed by 100 ml of toluene. The mixture was stirred, then heated to 50 °C, and 0.06 g of chromium tetrahydrofuran chloride CrCl3(THF)3 (CAS: 10170-68-0) was added. The mixture was stirred for 2 hours, filtered, and washed twice with toluene to obtain the POP-PNP-Cr main catalyst containing the [PNP] ligand. In a 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, along with 100 ml of toluene and 0.65 g of methylaluminoxane (MAO) solid. The reaction was carried out at room temperature for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-2. The catalyst contained 29.5 μmol / g of chromium and 7.2 mmol / g of aluminum.

[0069] Example 3

[0070] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0071] 1. Preparation of porous organic polymer supports containing [PNP] ligands:

[0072] In a 250 ml reactor, 130 ml of anhydrous ethanol was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.0 g of N,N-diphenylphosphino-4-allyl aniline (L1-1). The mixture was stirred at room temperature for 5 min, then 2% of the monomer mass of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added. The mixture was stirred at 45 °C for 1 h, then 2.0% of the monomer mass 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 8 h. After filtration, the mixture was washed three times with anhydrous ethanol, filtered, and dried to obtain 4.7 g of free-flowing porous carrier POP-2 containing [PNP] ligands.

[0073] 2. Preparation of POP-PNP-Cr / MAO catalyst:

[0074] In a 250 ml reactor, 2 g of dried porous POP-2 support was added, followed by 100 ml of toluene. The mixture was stirred, and then 0.06 g of chromium tetrahydrofuran chloride CrCl3(THF)3 (CAS: 10170-68-0) was added. The mixture was then heated to 50 °C and stirred for 3 hours. After filtration, the mixture was washed three times with toluene to obtain POP-PNP-Cr solid catalyst particles containing [PNP] ligands. In another 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, along with 100 ml of toluene and 0.65 g of methylaluminoxane (MAO) solid. The reaction was carried out at room temperature (25 °C) for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and then dried to obtain free-flowing catalyst particles, designated Cat-3. The catalyst contained 27.8 μmol / g of chromium and 5.4 mmol / g of aluminum.

[0075] Example 4

[0076] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0077] 1. Preparation of functional monomers of N,N-diphenylphosphino-4-allyl-2,6-dimethylaniline (L1-2, structure shown below):

[0078]

[0079] (1) Preparation of 4-allyl-2,6-dimethylaniline (L2-2) compound:

[0080] In a 250 ml reaction flask, add 100 ml of dried tetrahydrofuran (THF) and 30 mmol of... 4-Bromo-2,6-methylaniline (CAS: 24596-19-8) was reacted with 33 mmol of lithium tert-butylzinc (tBu4ZnLi2 in THF solution) reagent. [At -78°C, 100 mL of THF and 0.1 mol of ZnCl2 (THF solution) were added to a 500 mL flask, followed by the addition of 0.4 mol of tBuLi (n-pentane solution). The reaction was carried out for 60 min, and the mixture was filtered at 0°C to obtain 0.1 mol of pale yellow tBu4ZnLi2THF solution]. The reaction was continued at room temperature for 2 hours to prepare 4-(ZntBu3Li2)-aniline intermediate. Then, a slightly excess of 32 mmol of allyl bromide (CAS: 106-95-6) was added, and the mixture was stirred at room temperature for 24 hours. After filtration and recrystallization, 4-allyl-2,6-dimethylaniline (L2-2) compound was obtained with a yield of 73%.

[0081] (2) Preparation of N,N-diphenylphosphino-4-allyl-2,6-dimethylaniline (L1-2) functional monomer:

[0082] In a 250 mL reaction flask, 100 mL of dried dichloromethane was added, followed by 20 mmol of 4-allyl-2,6-dimethylaniline (L2-2) reagent, then 40 mmol of dichlorophosphine (CAS: 1079-66-9) and 40 mmol of triethylamine. The reaction was carried out at room temperature for 12 hours. After filtration, the mixture was recrystallized from dichloromethane to prepare N,N-diphenylphosphino-4-allyl-2,6-dimethylaniline (L1-2) with a yield of 92%. Its 1H NMR spectrum is shown below. Figure 2 As shown;

[0083] 2. Preparation of porous organic polymer supports containing [PNP] ligands:

[0084] In a 250 ml reactor, 130 ml of anhydrous ethanol was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.5 g of N,N-diphenylphosphino-4-allyl-2,6-dimethylaniline (L1-2) compound. The mixture was stirred at room temperature for 5 min, and then 2% of monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of monomer mass of AIBN was added. The temperature was raised to 80 °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 4.9 g of free-flowing porous carrier POP-3 containing [PNP] ligand.

[0085] 3. Preparation of POP-PNP-Cr / MAO catalyst:

[0086] In a 250 ml reactor, 2 g of POP-3 support was added, followed by 100 ml of toluene. The mixture was stirred, and then 0.05 g of chromium acetylacetone (III)Cr(acac)3 was added. The temperature was then raised to 65 °C, and the mixture was stirred for 3 hours. After filtration, the catalyst was washed three times with toluene to obtain the POP-PNP-Cr main catalyst containing the [PNP] ligand. In another 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, along with 100 ml of toluene and 0.70 g of methylaluminoxane (MAO) solid. The reaction was carried out at room temperature for 2 hours. After the reaction was complete, the catalyst was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-4. The catalyst contained 27.1 μmol / g of chromium and 7.2 mmol / g of aluminum.

[0087] Example 5

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

[0089] 1. Preparation of porous organic polymer supports containing [PNP] ligands:

[0090] In a 250 ml reactor, 130 ml of anhydrous ethanol was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 55%) and 2.5 g of N,N-diphenylphosphino-4-allyl-2,6-dimethylaniline (L1-2) compound. The mixture was stirred at room temperature for 5 min, and then 2% of monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of monomer mass of AIBN was added. The temperature was raised to 80 °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 5 h. After filtration, the mixture was washed three times with anhydrous ethanol, filtered, and dried to obtain 4.3 g of free-flowing porous carrier POP-4 containing [PNP] ligand.

[0091] 2. Preparation of POP-PNP-Cr / MMAO catalyst:

[0092] In a 250 ml reactor, 2 g of POP-4 support was added, followed by 100 ml of toluene. The mixture was stirred, then heated to 50 °C, and 0.05 g of chromium(II)dichlorotetrahydrofuran(II)CrCl2(THF)2 (CAS: 13931-94-7) was added. The mixture was stirred for 3 hours, filtered, and washed three times with toluene to obtain the POP-PNP-Cr main catalyst containing the [PNP] ligand. In a 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, along with 100 ml of toluene and 0.70 g of modified methylaluminoxane (MMAO) (CAS: 206451-54-9). The reaction was carried out at room temperature for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-5. The catalyst contained 26.7 μmol / g of chromium and 7.5 mmol / g of aluminum.

[0093] Example 6

[0094] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0095] 1. Preparation of functional monomers of N,N-diphenylphosphino-4-allyl-2,6-diisopropylaniline (L1-3, structure shown below):

[0096]

[0097] (1) Preparation of 4-allyl-2,6-diisopropylaniline (L2-3) compound:

[0098] In a 250 ml reaction flask, add 100 ml of dried tetrahydrofuran (THF) and 30 mmol of... 4-Bromo-2,6-diisopropylaniline (CAS: 80058-84-0) was reacted with 33 mmol of lithium tert-butylzinc (tBu4ZnLi2 in THF solution) reagent. [At -78°C, 100 ml of THF and 0.1 mol of ZnCl2 (THF solution) were added to a 500 ml flask, followed by the addition of 0.4 mol of tBuLi (n-pentane solution). The reaction was carried out for 60 min, and the mixture was filtered at 0°C to obtain 0.1 mol of pale yellow tBu4ZnLi2THF solution]. The reaction was continued at room temperature for 2 hours to prepare 4-(ZntBu3Li2)-aniline intermediate. Then, a slightly excess of 32 mmol of allyl bromide (CAS: 106-95-6) was added, and the mixture was stirred at room temperature for 24 hours. After filtration and recrystallization, 4-allyl-2,6-diisopropylaniline (L2-3) compound was obtained with a yield of 68%.

[0099] (2) Preparation of N,N-diphenylphosphino-4-allyl-2,6-diisopropylaniline (L1-3) functional monomer:

[0100] In a 250 ml reaction flask, 100 ml of dried dichloromethane was added, followed by 20 mmol of 4-allyl-2,6-diisopropylaniline (L2-3) reagent, then 40 mmol of dichlorophenylphosphine (CAS: 1079-66-9) and 40 mmol of triethylamine. The reaction was carried out at room temperature for 12 hours, filtered, and recrystallized from dichloromethane to prepare N,N-diphenylphosphino-4-allyl-2,6-diisopropylaniline (L1-3) with a yield of 85%.

[0101] 2. Preparation of porous organic polymer supports containing [PNP] ligands:

[0102] In a 250 ml reactor, 130 ml of isobutanol was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.0 g of N,N-diphenylphosphino-4-allyl-2,6-diisopropylaniline (L1-3) compound. The mixture was stirred at room temperature for 5 min, and then 2% of monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of monomer mass of AIBN was added. The temperature was raised to 80 °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 5.8 g of free-flowing porous carrier POP-5 containing [PNP] ligands.

[0103] 3. Preparation of POP-PNP-Cr / MAO catalyst:

[0104] In a 250 ml reactor, 2 g of POP-5 support was added, followed by 100 ml of toluene. The mixture was stirred, and 0.065 g of CrCl3(THF)3 was added at room temperature. The mixture was stirred for 5 hours, filtered, and washed twice with toluene to obtain the POP-PNP-Cr main catalyst containing the [PNP] ligand. In another 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, along with 100 ml of toluene and 0.70 g of methylaluminoxane (MAO) solid. The reaction was carried out at room temperature for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-6. The catalyst contained 28.9 μmol / g of chromium and 6.5 mmol / g of aluminum.

[0105] Example 7

[0106] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0107] In a 250 ml reactor, 2 g of POP-5 support was added, followed by 100 ml of toluene. The mixture was stirred, and then 0.05 g of CrCl3(THF)3 was added at 60 °C. The mixture was stirred for 2 hours, filtered, washed three times with toluene, and dried to obtain a POP-PNP-Cr solid catalyst containing [PNP] ligands. In another 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, and the temperature was raised to 40 °C. 100 ml of toluene and 0.60 g of methylaluminoxane (MAO) solid were added, and the reaction was carried out for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-7. The catalyst contained 27.1 μmol / g of chromium and 5.7 mmol / g of aluminum.

[0108] Example 8

[0109] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0110] 1. Preparation of functional monomers of N,N-diphenylphosphino-4-vinylaniline (L1-4, structure shown below):

[0111]

[0112] (1) Preparation of 4-vinylaniline (L2-4) compound:

[0113] In a 250 ml reaction flask, 100 ml of dried tetrahydrofuran (THF) and 30 mmol of 4-bromoaniline (CAS: 697-88-1) were added, followed by 33 mmol of lithium tert-butylzinc (THF solution of tBu4ZnLi2). [At -78 °C, in a 500 ml flask, 100 ml of THF and 0.1 mol of ZnCl2 (THF solution) were added, followed by the dropwise addition of 0.4 mol of tBuLi (n-pentane solution). The reaction was carried out for 60 min, and the solution was filtered at 0 °C to obtain 0.1 mol of pale yellow tBu4ZnLi2THF solution]. The reaction was continued at room temperature for 2 hours to prepare the 4-(ZntBu3Li2)-aniline intermediate. Then, a slightly excess of 32 mmol of vinyl bromide (CAS: 593-60-2) was added, and the reaction was stirred at room temperature for 24 hours. After filtration and recrystallization, the 4-vinylaniline (L2-4) compound was obtained with a yield of 73%.

[0114] (2) Preparation of N,N-diphenylphosphino-4-vinylaniline (L1-4) functional monomer:

[0115] In a 250 ml reaction flask, 100 ml of dried dichloromethane was added, followed by 20 mmol of 4-vinylaniline (L2-4) reagent, then 40 mmol of dichlorophenylphosphine (CAS: 1079-66-9) and 40 mmol of triethylamine. The reaction was carried out at room temperature for 12 hours. After filtration, N,N-diphenylphosphino-4-vinylaniline (L1-4) was prepared by recrystallization with dichloromethane, with a yield of 78%. Its 1H NMR spectrum is shown below. Figure 3 As shown;

[0116] 2. Preparation of porous organic polymer supports containing [PNP] ligands:

[0117] In a 250 ml reactor, 120 ml of anhydrous ethanol and 20 ml of THF were added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 3.0 g of N,N-diphenylphosphino-4-vinylaniline (L1-4) compound. The mixture was stirred at room temperature for 5 min, and then 2% of monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of monomer mass of AIBN was added. The temperature was raised to 80 °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 6.1 g of free-flowing porous carrier POP-6 containing [PNP] ligand.

[0118] 3. Preparation of POP-PNP-Cr / MAO catalyst:

[0119] In a 250 ml reactor, 2 g of POP-6 support was added, followed by 100 ml of toluene. The mixture was stirred, and 0.060 g of chromium acetylacetone (III)Cr(acac)3 was added at room temperature. The mixture was stirred for 5 hours, filtered, and washed three times with toluene alcohol to obtain the POP-PNP-Cr main catalyst containing the [PNP] ligand. In another 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, along with 100 ml of toluene and 0.70 g of methylaluminoxane (MAO) solid. The reaction was carried out at room temperature for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-8. The catalyst contained 31.2 μmol / g of chromium and 6.8 mmol / g of aluminum.

[0120] Example 9

[0121] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0122] 1. Preparation of porous organic polymer supports containing [PNP] ligands:

[0123] In a 250 ml reactor, 130 ml of anhydrous ethanol was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.5 g of N,N-diphenylphosphino-4-vinylaniline (L1-4) compound. The mixture was stirred at room temperature for 5 min, and then 2% of monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of monomer mass of AIBN was added. The temperature was raised to 78 °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 4 h. After filtration, the mixture was washed three times with anhydrous ethanol, filtered, and dried to obtain 4.9 g of free-flowing porous carrier POP-7 containing [PNP] ligand.

[0124] 2. Preparation of POP-PNP-Cr / MAO catalyst:

[0125] In a 250 ml reactor, 2 g of dried POP-7 support was added, followed by 100 ml of toluene. The mixture was stirred, and 0.065 g of CrCl3(THF)3 was added at room temperature. The mixture was stirred for 5 hours, filtered, and washed three times with toluene to obtain the POP-PNP-Cr main catalyst containing the [PNP] ligand. In another 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, along with 100 ml of toluene and 0.70 g of methylaluminoxane (MAO) solid. The reaction was carried out at room temperature for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-9. The catalyst contained 32.7 μmol / g of chromium and 7.2 mmol / g of aluminum.

[0126] Example 10

[0127] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0128] In a 250 ml reactor, 2 g of dried POP-7 support was added, followed by 100 ml of toluene. The mixture was stirred, and then 0.05 g of CrCl3(THF)3 was added at 60 °C. The mixture was stirred for 3 hours, filtered, and washed three times with toluene to obtain the POP-PNP-Cr main catalyst containing the [PNP] ligand. In another 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, and the temperature was raised to 40 °C. 100 ml of toluene and 0.60 g of methylaluminoxane (MAO) solid were added, and the reaction was carried out for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-10. The catalyst contained 25.3 μmol / g of chromium and 5.9 mmol / g of aluminum.

[0129] Example 11

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

[0131] 1. Preparation of N,N-diphenylphosphino-4-vinyl-2,6-diisopropylaniline (L1-5) functional monomer:

[0132]

[0133] (1) Preparation of 4-vinyl-2,6-diisopropylaniline (L2-5) compound:

[0134] In a 250 ml reaction flask, add 100 ml of dried tetrahydrofuran (THF) and 30 mmol of... 4-Bromo-2,6-diisopropylaniline (CAS: 80058-84-0) was reacted with 33 mmol of lithium tert-butylzinc (tBu4ZnLi2 in THF solution) reagent. [At -78°C, 100 mL of THF and 0.1 mol of ZnCl2 (THF solution) were added to a 500 mL flask, followed by the addition of 0.4 mol of tBuLi (n-pentane solution). The reaction was carried out for 60 min, and the mixture was filtered at 0°C to obtain 0.1 mol of pale yellow tBu4ZnLi2THF solution]. The reaction was continued at room temperature for 2 hours to prepare 4-(ZntBu3Li2)-aniline intermediate. Then, a slightly excess of 32 mmol of vinyl bromide (CAS: 593-60-2) was added, and the mixture was stirred at room temperature for 24 hours. After filtration and recrystallization, 4-vinyl-2,6-diisopropylaniline (L2-5) compound was obtained with a yield of 73%.

[0135] (2) Preparation of N,N-diphenylphosphino-4-vinyl-2,6-diisopropylaniline (L1-5) functional monomer:

[0136] In a 250 ml reaction flask, 100 ml of dried dichloromethane was added, followed by 20 mmol of 4-vinyl-2,6-diisopropylaniline (L2-5) reagent, then 40 mmol of dichlorophenylphosphine (CAS: 1079-66-9) and 40 mmol of triethylamine. The reaction was carried out at room temperature for 12 hours, filtered, and recrystallized from dichloromethane to prepare N,N-diphenylphosphino-4-vinyl-2,6-diisopropylaniline (L1-5) with a yield of 89%.

[0137] 2. Preparation of porous organic polymer supports containing [PNP] ligands:

[0138] In a 250 ml reactor, 120 ml of anhydrous ethanol and 20 ml of THF were added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 80%) and 2.5 g of N,N-diphenylphosphino-4-vinyl-2,6-diisopropylaniline (L1-5) compound. The mixture was stirred at room temperature for 5 min, and then 2% of monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of monomer mass of AIBN was added. The temperature was raised to 80 °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 4.8 g of free-flowing porous carrier POP-8 containing [PNP] ligand.

[0139] 3. Preparation of POP-PNP-Cr / MAO catalyst:

[0140] In a 250 ml reactor, 2 g of dried POP-8 support was added, followed by 100 ml of toluene. The mixture was stirred, heated to 60 °C, and 0.050 g of chromium acetylacetone (III)Cr(acac)3 was added. The mixture was stirred for 2 hours, filtered, and washed three times with toluene to obtain the POP-PNP-Cr main catalyst with [PNP] ligand. In a 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, along with 100 ml of toluene and 0.70 g of methylaluminoxane (MAO) solid. The reaction was carried out at room temperature for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-11. The catalyst contained 27.6 μmol / g of chromium and 7.1 mmol / g of aluminum.

[0141] Example 12

[0142] This embodiment provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0143] 1. Preparation of porous organic polymer supports containing [PNP] ligands:

[0144] In a 250 ml reactor, 130 ml of anhydrous ethanol was added, followed by 5.0 g of divinylbenzene (Aladdin reagent, 55%) and 2.5 g of N,N-diphenylphosphino-4-vinyl-2,6-diisopropylaniline (L1-5) compound. The mixture was stirred at room temperature for 5 min, and then 2% of monomer mass of polypropylene oxide-ethylene oxide copolymer F127 (BASF, molecular weight 12000) was added. The mixture was stirred at 45 °C for 1 h, and then 2.0% of monomer mass of AIBN was added. The temperature was raised to 80 °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 5 h. After filtration, the mixture was washed three times with anhydrous ethanol, filtered, and dried to obtain 4.3 g of free-flowing porous carrier POP-9 containing [PNP] ligand.

[0145] 2. Preparation of POP-PNP-Cr / MAO catalyst:

[0146] In a 250 ml reactor, 2 g of dried porous POP-9 support containing [PNP] ligands was added, along with 100 ml of toluene. The mixture was stirred, and 0.065 g of CrCl3(THF)3 was added at room temperature. The mixture was stirred for 3 hours, filtered, and washed three times with toluene to obtain the POP-PNP-Cr main catalyst containing [PNP] ligands. In another 250 ml reactor, the obtained POP-PNP-Cr solid catalyst was added, along with 100 ml of toluene and 0.70 g of methylaluminoxane (MAO) solid. The reaction was carried out at room temperature for 2 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-12. The catalyst contained 35.7 μmol / g of chromium and 6.7 mmol / g of aluminum.

[0147] Comparative Example 1

[0148] This comparative example provides an ethylene oligomerization catalyst, which is prepared by the following steps:

[0149] (1) Synthesis of N,N-diphenylphosphinoaniline [PNP] compounds:

[0150] In a 250 ml reaction flask, 100 ml of dried dichloromethane was added, followed by 20 mmol of aniline (CAS: 62-53-3, Aladdin reagent), then 40 mmol of dichlorophosphine (CAS: 1079-66-9) and 40 mmol of triethylamine. The reaction was carried out at room temperature for 12 hours, filtered, and N,N-diphenylphosphine-aniline was prepared by recrystallization after adding dichloromethane, with a yield of 89%.

[0151] (2) In a 250 ml reactor, 1.0 g of N,N-diphenylphosphinoaniline [PNP] compound was added, 100 ml of toluene was added and stirred, then the temperature was raised to 70 °C, 0.065 g of chromium acetylacetone (III)Cr(acac)3 (CAS: 21679-31-2) was added, and the mixture was stirred for 3 hours to obtain a toluene solution of the metal compound PNP-Cr of the polydentate pyridine imine ligand.

[0152] (3) Preparation of silica-supported PNP-Cr / MAO catalyst:

[0153] In a 250 ml reactor, 2 g of dried Grace 955 silica gel support (treated at 600 °C for 6 hours) was added, along with 100 ml of toluene and 0.70 g of solid methylaluminoxane (MAO). The mixture was reacted at room temperature for 2 hours, then heated to 70 °C, and the above PNP-Cr toluene solution was added. The mixture was stirred for 3 hours. After the reaction was complete, the mixture was filtered, washed three times each with toluene and hexane, and dried to obtain free-flowing catalyst particles, designated Cat-13. The catalyst contained 31.2 μmol / g of chromium and 7.3 mmol / g of aluminum.

[0154] Test Example 1-12: Ethylene Oligomerization Performance Test

[0155] Test Example 1: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried methylcyclohexane and 5ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.10g of Cat-1 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 50°C, and ethylene was introduced. The reaction was maintained at a pressure of 4.5 MPa and stirred at 600 rpm for 1 hour. After the reaction was complete, the mixture was cooled to obtain 45.2g of product. The ethylene oligomerization activity was 15.7 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0156] Test Example 2: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried methylcyclohexane (CAS: 108-87-2) and 5ml of triethylaluminum TEA (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.10g of Cat-2 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 45°C, and ethylene was introduced. The reaction was carried out at a pressure of 5 MPa and a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the mixture was cooled to obtain 65.8g of product. The ethylene oligomerization activity was 22.3 × 10⁻⁶. 6 g / molCr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0157] Test Example 3: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried cyclohexane and 5ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.10g of Cat-3 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 60°C, and ethylene was introduced. The reaction was carried out at a pressure of 5.0 MPa and a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the temperature was lowered to obtain 37.5g of product. The ethylene oligomerization activity was 13.5 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0158] Test Example 4: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried cyclohexane and 5ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.20g of Cat-4 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 50°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 completed, the temperature was lowered to obtain 42.8g of product. The ethylene oligomerization activity was 7.9 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0159] Test Example 5: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried toluene and 5ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.20g of Cat-5 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 60°C, and ethylene was introduced. The reaction was maintained at a pressure of 6.0 MPa and stirred at 600 rpm for 2 hours. After the reaction was completed, the temperature was lowered to obtain 45.7g of product. The ethylene oligomerization activity was 8.6 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0160] Test Example 6: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried methylcyclohexane and 5ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.10g of Cat-6 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 60°C, and ethylene was introduced. The reaction was carried out at a pressure of 5.0 MPa and a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the temperature was lowered to obtain 56.2g of product. The ethylene oligomerization activity was 19.4 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0161] Test Example 7: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried methylcyclohexane and 10ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.10g of Cat-7 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 60°C, and ethylene was introduced. The reaction was carried out at a pressure of 5.0 MPa and a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the temperature was lowered to obtain 65.8g of product. The ethylene oligomerization activity was 24.2 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0162] Test Example 8: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried toluene and 5ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.20g of Cat-8 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 50°C, and ethylene was introduced. The reaction was carried out at a pressure of 1.0 MPa and a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the temperature was lowered to obtain 22.5g of product. The ethylene oligomerization activity was 3.6 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC, and the main components were C4-C8 olefins. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0163] Test Example 9: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried toluene and 5ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.10g of Cat-9 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 45°C, and ethylene was introduced. The reaction was maintained at 7.0 MPa pressure and stirred at 600 rpm for 1 hour. After the reaction was complete, the mixture was cooled to obtain 38.6g of product. The ethylene oligomerization activity was 11.8 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0164] Test Example 10: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried toluene and 5ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.10g of Cat-10 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 60°C, and ethylene was introduced. The reaction was carried out at a pressure of 6.0 MPa and a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the temperature was lowered to obtain 22.5g of product. The ethylene oligomerization activity was 8.9 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0165] Test Example 11: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried methylcyclohexane and 10ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.10g of Cat-11 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 60°C, and ethylene was introduced. The reaction was carried out at a pressure of 4.5 MPa and a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the mixture was cooled to obtain 70.9g of product. The ethylene oligomerization activity was 25.7 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0166] Test Example 12: In a 2.0L dried ethylene oligomerization reactor, 800ml of dried cyclohexane and 10ml of triethylaluminum (TEA) (1.0 mol / L) were added. The stirring speed was 600 rpm, followed by the addition of 0.10g of Cat-12 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 50°C, and ethylene was introduced. The reaction was carried out at a pressure of 6.0 MPa and a stirring speed of 600 rpm for 1 hour. After the reaction was completed, the temperature was lowered to obtain 24.1g of product. The ethylene oligomerization activity was 6.8 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0167] Comparative Test Example 1:

[0168] In a 2.0L dried ethylene oligomerization reactor, 800ml of dried methylcyclohexane and 5ml of triethylaluminum (TEA) (1.0 mol / L) were added. The mixture was stirred at 600 rpm, followed by the addition of 0.20g of Cat-13 ethylene oligomerization catalyst. The mixture was stirred for 3-5 minutes, heated to 50°C, and ethylene was introduced. The reaction was maintained at 4.5 MPa pressure and stirred at 600 rpm for 1 hour. After the reaction was complete, the mixture was cooled to obtain 13.1g of product with an ethylene oligomerization activity of 2.1 × 10⁻⁶. 6 g / mol Cr.h. The oligomer composition was determined by GC. 1 The α-olefin content in the oligomer was determined by HNMR, and the results are shown in Table 1.

[0169] Table 1 Results of ethylene oligomerization

[0170]

[0171] The polymerization results above show that the organically supported ethylene oligomerization POP-PNP-Cr / MAO catalyst system of this invention exhibits good ethylene oligomerization activity, reaching 25.7 × 10⁻⁶. 6 The ethylene oligomers exhibit good selectivity at g / mol Cr.h, with total C6 and C8 olefin content reaching over 85%, and linear α-olefin selectivity for both 1-C6 and 1-C8 reaching over 80%.

Claims

1. An organic polymer carrier obtained by copolymerization of a monomer comprising divinylbenzene and a PNP-containing ligand; in, The monomer containing the PNP ligand has the structure shown in Formula I: Formula I, In Formula I, R1 and R2 are each independently selected from hydrogen atoms, methyl groups, and isopropyl groups; x is 0 or 1.

2. The organic polymer carrier according to claim 1, wherein, The monomer containing the PNP ligand is selected from one or more combinations of N,N-diphenylphosphino-4-allylaniline, N,N-diphenylphosphino-4-allyl-2-methylaniline, N,N-diphenylphosphino-4-allyl-2-isopropylaniline, N,N-diphenylphosphino-4-allyl-2,6-dimethylaniline, N,N-diphenylphosphino-4-allyl-2,6-diisopropylaniline, N,N-diphenylphosphino-4-vinylaniline, N,N-diphenylphosphino-4-vinyl-2-methylaniline, N,N-diphenylphosphino-4-vinyl-2-isopropylaniline, N,N-diphenylphosphino-4-vinyl-2,6-dimethylaniline, and N,N-diphenylphosphino-4-vinyl-2,6-diisopropylaniline.

3. The organic polymer carrier according to claim 1, wherein, Based on the organic polymer carrier mass being 100%, the mass fraction of the monomer containing the PNP ligand is 20-60%.

4. A method for preparing the organic polymer carrier according to any one of claims 1-3, comprising the following steps: The organic polymer carrier is prepared by copolymerization using the divinylbenzene and the monomer containing the PNP ligand as raw materials. The mass ratio of the monomer containing the PNP ligand to divinylbenzene is 0.2-2:

1.

5. The preparation method according to claim 4, wherein, The organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization. The dispersion polymerization method includes the following steps: adding divinylbenzene and a monomer containing PNP ligands to a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, and reacting at 50-80℃ for 5-12 hours to obtain the organic polymer carrier.

6. The preparation method according to claim 5, wherein, The dispersion solvent includes one or more of alcohol solvents, fatty acid ester solvents, and tetrahydrofuran.

7. The preparation method according to claim 6, wherein, The alcohol solvents include one or more of ethanol, propanol, isopropanol, and isobutanol; The fatty acid ester solvents include one or more of the following: 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.

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

9. The preparation method according to claim 5, wherein, The stabilizer is polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer.

10. The preparation method according to claim 5, wherein, The weight-average molecular weight of the stabilizer is 1,000-100,000.

11. The preparation method according to claim 5, wherein, The mass ratio of the amount of stabilizer added to the total amount of monomer added is 0.5-3:

100.

12. The preparation method according to claim 5, wherein, The initiator is azobisisobutyronitrile and / or benzoyl peroxide.

13. The preparation method according to claim 5, wherein, The mass ratio of the amount of initiator added to the total amount of monomer added is 0.5-3:

100.

14. The preparation method according to claim 5, wherein, The divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor.

15. An ethylene oligomerization catalyst system, comprising a main catalyst and a co-catalyst; in, The main catalyst is prepared by supporting metallic Cr on an organic polymer support as described in any one of claims 1-3.

16. The ethylene oligomerization catalyst system according to claim 15, wherein, The cocatalyst includes alkylaluminoxane compounds and / or alkylaluminum.

17. The ethylene oligomerization catalyst system according to claim 16, wherein, The cocatalyst is methylaluminoxane and / or modified methylaluminoxane.

18. The ethylene oligomerization catalyst system according to claim 16, wherein, The molar ratio of aluminum in the co-catalyst to Cr in the main catalyst is 30-300.

19. The ethylene oligomerization catalyst system according to claim 18, wherein, The molar ratio of aluminum in the co-catalyst to Cr in the main catalyst is 50-200.

20. The ethylene oligomerization catalyst system according to claim 16, wherein, The ratio of aluminum in the co-catalyst to the organic polymer support is from 1 mmol / g aluminum / g support to 15 mmol / g support.

21. The ethylene oligomerization catalyst system according to claim 20, wherein, The ratio of aluminum in the co-catalyst to the organic polymer support is from 3 mmol / g aluminum / g support to 10 mmol / g support.

22. The ethylene oligomerization catalyst system according to claim 15, wherein, The Cr content in the main catalyst is from 5 micromoles Cr / g support to 100 micromoles Cr / g support.

23. The ethylene oligomerization catalyst system according to claim 22, wherein, The Cr content in the main catalyst is from 20 micromoles Cr / g support to 50 micromoles Cr / g support.

24. A method for preparing the ethylene oligomerization catalyst system according to any one of claims 15-23, comprising the following steps: The organic polymer support is added to toluene, followed by the addition of a chromium precursor compound. The reaction is carried out at 20°C-70°C for 1-5 hours. After filtration, washing, and drying, the main catalyst is obtained. The main catalyst and the co-catalyst are mixed in an inert solvent and reacted at 0°C-50°C for 30-180 minutes. After filtration, washing, and drying, the ethylene oligomerization catalyst system is obtained.

25. The preparation method according to claim 24, wherein, The chromium precursor compound includes one or more of the following: chromium trichlorotritetrahydrofuran, chromium triacetylacetone, chromium dichlorotoluenetritetrahydrofuran, chromium dichloride, chromium dichloroditetrahydrofuran, chromium hexacarbonyl, chromium dichloromethyltritetrahydrofuran, and chromium triphenyltritetrahydrofuran.

26. The use of the ethylene oligomerization catalyst system according to any one of claims 15-23 in ethylene oligomerization.

27. The application according to claim 26, wherein, The reaction temperature for ethylene oligomerization is 20-80℃, and the partial pressure of ethylene is 1-10MPa.

28. The application according to claim 26, wherein, The solvent used in the slurry polymerization of ethylene oligomerization is C5-C. 10 Alkanes.

29. The application according to claim 28, wherein, The solvent used in the slurry polymerization of ethylene oligomerization is methylcyclohexane.

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