Supported nickel catalysts, methods for their preparation and use

Abstract

The present disclosure provides a supported nickel catalyst and its preparation method and application, and belongs to the technical field of catalyst synthesis. The supported nickel catalyst contains a structure shown in formula (I), wherein R1 is selected from C1-C 20 hydrocarbon group, nitro group, hydroxyl group, substituted silicon group, C1-C 20 substituted hydrocarbon group; R2 and R3 are independently selected from hydrogen, C1-C 20 hydrocarbon group, fluorine, chlorine, bromine, iodine, nitro group, hydroxyl group, substituted silicon group, C1-C 20 substituted hydrocarbon group, R2 and R3 can be bonded to each other to form a ring; R4 and R5 are independently selected from C1-C 20 hydrocarbon group, C1-C 20 substituted hydrocarbon group, C5-C 20 aliphatic or aromatic hydrocarbon group, R4 and R5 can be bonded to each other to form a ring; R6 and R7 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C 20 hydrocarbon group, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, silicon-containing group or tin-containing group, R6 and R7 can be bonded to each other to form a ring; wherein the surface of the carrier exists a hydroxyl group, which forms a hydrogen bond with the oxygen in the benzoquinone structure.

Description

Technical Field

[0001] This disclosure belongs to the field of catalyst synthesis technology, and in particular relates to a supported nickel catalyst, its preparation method and application. Background Technology

[0002] Currently, academic research on polyolefin catalysis mainly focuses on homogeneous systems due to their inherent advantages, such as well-defined molecular structures and the ability to be rationally modified, making them suitable for mechanistic studies. In contrast, the polyolefin industry primarily utilizes heterogeneous systems because they allow for control over product morphology, enabling continuous polymerization processes and preventing reactor fouling. This difference poses a significant challenge to the practical application of high-performance polyolefin catalysts in industrialization research. One possible solution is the heterogeneous formation of homogeneous metal complexes on solid supports through surface organometallic (coordination) chemistry. This method has been extensively studied for organic conversion and has yielded many excellent catalytic systems. This is of great significance for polyolefin research and its industrial development because, in addition to combining the advantages of both types of catalysts, it provides new ideas and solutions for existing technologies. Many heterogeneous polymerization systems based on transition metal catalysts have been successfully industrialized. However, these transition metal catalysts exhibit low catalytic activity and thermal stability in polyolefin catalysis, and the reaction between olefins and polar monomers easily leads to catalyst poisoning and deactivation. Summary of the Invention

[0003] In view of this, the present disclosure provides a supported nickel catalyst, its preparation method and application, in order to at least partially solve the above-mentioned technical problems.

[0004] To address the aforementioned technical problems, as one aspect of this disclosure, the following technical solution is provided:

[0005] A supported nickel catalyst, characterized in that the supported nickel catalyst contains the structure shown in formula (I),

[0006]

[0007] Among them, R1 is selected from C1 to C2. 20 Hydrocarbon group, nitro group, hydroxyl group, substituted silicon group, C1-C 20 The substituted hydrocarbon groups; R2 and R3 are independently selected from hydrogen, C1 to C3. 20 Hydrocarbon groups, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon groups, C1-C 20 The substituted hydrocarbon groups, R2 and R3 can bond to each other to form a ring; R4 and R5 are independently selected from C1 to C5. 20 hydrocarbon groups, C1-C 20 Substituted hydrocarbon groups, C5-C 20The alicyclic or aromatic hydrocarbon groups, R4 and R5 can bond to each other to form a ring; R6 and R7 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6. 20 The groups R6 and R7 can form rings with each other, including hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups, phosphorus-containing groups, silicon-containing groups, or tin-containing groups.

[0008] The carrier surface contains hydroxyl groups, which form hydrogen bonds with oxygen in the benzoquinone structure.

[0009] In one embodiment, the carrier includes one or more of the following: silicon dioxide, magnesium oxide, titanium dioxide, zinc oxide, aluminum oxide, glass fiber, magnesium chloride, graphene, expanded graphite, ammonium polyphosphate, and carbon black.

[0010] In one embodiment, the structure shown in formula (I) above includes at least one of the following:

[0011]

[0012]

[0013] In another aspect of this disclosure, a method for preparing a supported nickel catalyst is provided, the method comprising:

[0014] Under an inert atmosphere, the ligand with the structure shown in formula (II) and the nickel source were dissolved in a good solvent. The ligand solution was added dropwise to the nickel source solution. After reacting for 1-12 hours, the solution was filtered and the solvent was removed to obtain the complex with the structure of formula (IM).

[0015] The complex (IM) was added to the organic solvent of the dispersed support, stirred for 1-120 minutes, filtered and washed to obtain the supported nickel catalyst shown in formula (I);

[0016] Among them, the above formula (II) represents: The above formula (IM) is: R1, R2, R3, R4, R5, R6 and R7 are as defined in the supported nickel catalysts of the above embodiments.

[0017] In one embodiment, the ligand represented by formula (II) above is obtained by the following steps:

[0018] In an inert atmosphere, The product is obtained by reacting with the hydroxyl protecting group. treat After reacting with butyllithium, (b) Adding to the reaction system to obtain the protected structure of the ligand. Removing the protecting group yields After oxidation, the ligand shown in formula (II) is obtained.

[0019] In one embodiment, the structure shown in formula (II) above includes at least one of the following:

[0020]

[0021] In one embodiment, the aforementioned nickel source includes at least one of the following:

[0022] Bis(1,5-cyclooctadiene)nickel, bis(allyl)dichloronickel, dimethyl dipyridinium nickel, nickel bromide (ethylene glycol dimethyl ether);

[0023] The aforementioned good solvents and organic solvents include at least one of the following: dichloromethane, toluene, tetrahydrofuran, benzene, carbon tetrachloride, 1,4-dioxane, and 1,2-dichloroethane.

[0024] In one embodiment, the mass ratio of the complex (IM) to the carrier is 1:20-50000.

[0025] As another aspect of this disclosure, an application for catalytic olefin polymerization is also provided, including...

[0026] The supported nickel catalyst is used to catalyze the homopolymerization of olefins and / or the copolymerization of olefins with polar monomers, wherein the supported nickel catalyst is the supported nickel catalyst in the above embodiments.

[0027] In another embodiment, the olefin comprises ethylene or an α-olefin;

[0028] The aforementioned polar monomers include C2 to C4 groups containing polar groups. 20 1-olefin derivatives and cyclic olefin derivatives containing polar groups;

[0029] Among them, the polar groups mentioned above include organic functional groups containing oxygen, nitrogen, sulfur, or selenium, and the organic functional groups mentioned above include hydroxyl, carboxyl, ester, alkoxy, amino, amide, thioether, silyl ether, or selenyl ether.

[0030] Based on the above technical solution, the supported nickel catalyst, its preparation method, and its application provided in this disclosure have at least one of the following beneficial effects:

[0031] (1) According to the embodiments of this disclosure, a phosphine-benzoquinone structure is introduced into the structure of the supported nickel catalyst. The oxygen-containing group in benzoquinone can form hydrogen bonds with the hydroxyl groups on the support surface, so that the complex containing benzoquinone can be firmly supported on the support surface, thereby increasing the loading of the nickel metal source and enhancing the structural stability of the supported nickel catalyst.

[0032] (2) The supported nickel catalyst provided in this disclosure has a large number of functional groups and the functional groups have large steric hindrance. The ligand with large steric hindrance can increase the thermal stability and polymerization activity of the catalyst during the catalytic reaction process, as well as increase the comonomer insertion ratio and the molecular weight of the catalytic polymer.

[0033] (3) The supported nickel catalyst provided in this disclosure can achieve an activity of 1.82 × 10⁻⁶ for the copolymerization of ethylene with polar monomers to prepare polar polyolefins. 4 g·mol -1 ·h -1 .

[0034] (4) In this embodiment, benzoquinone ligands are prepared from phenolic compounds, and then supported nickel catalysts are prepared from benzoquinone ligands. This preparation route is relatively simple, the process is relatively easy, and the yield and purity of the prepared catalyst products are high. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of this disclosure clearer, the following detailed description is provided in conjunction with specific embodiments.

[0036] Polyolefins are among the most common and important synthetic materials, accounting for more than half of global plastic production. This stems from their excellent properties, including high strength, high chemical stability, and corrosion resistance, while also being inexpensive, making them widely used in packaging, electronics, textiles, and foaming industries. The advent of the Ziegler-Natta catalyst in the 1950s allowed for the polymerization of olefins under milder conditions. The 1964 Nobel Prize awarded to Ziegler and Natta brought attention to olefin polymerization catalysts, accelerating their continuous development. In 1996, Brookhart's group developed the classic α-diimide catalyst, which can catalyze the copolymerization of methyl acrylate (MA) or other special monomers with ethylene, marking a milestone breakthrough in the field of olefin coordination polymerization. In 1968, Shell developed an advanced olefin process using... Transition metal catalysts, exhibiting high catalytic activity in ethylene copolymerization and good tolerance to polar solvents, were quickly adopted industrially for the production of α-olefins and remain relevant even decades later. Their discovery was a significant breakthrough in the field of ethylene oligomerization. By making structural modifications, these catalysts could potentially be used to produce higher molecular weight polyethylene. However, transition metal catalysts suffer from lower catalytic activity, thermal stability, and susceptibility to deactivation in polyolefin catalysis.

[0037] Given the importance and pressing issues of supported transition metals in the heterogeneous polymerization of olefins, this disclosure adds oxygen-containing groups to the ligand structure, enabling it to interact strongly with the support surface, thereby increasing the loading rate of the supported catalyst and improving the stability of its bond with the support. This results in the supported nickel catalyst exhibiting high thermal stability and catalytic activity in olefin homopolymerization or olefin / polar monomer copolymerization reactions.

[0038] This disclosure provides a supported nickel catalyst having the structure shown in formula (I):

[0039]

[0040] Among them, R1 is selected from C1 to C2. 20 Hydrocarbon group, nitro group, hydroxyl group, substituted silicon group, C1-C 20 The substituted hydrocarbon groups; R2 and R3 are independently selected from hydrogen, C1 to C3. 20 Hydrocarbon groups, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silicon groups, C1-C 20 The substituted hydrocarbon groups, R2 and R3 can bond to each other to form a ring; R4 and R5 are independently selected from C1 to C5. 20 hydrocarbon groups, C1-C 20 Substituted hydrocarbon groups, C5-C 20 The alicyclic or aromatic hydrocarbon groups, R4 and R5 can bond to each other to form a ring; R6 and R7 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6. 20 The groups R6 and R7 can form rings with each other, including hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups, phosphorus-containing groups, silicon-containing groups, or tin-containing groups.

[0041] The carrier surface contains hydroxyl groups, which form hydrogen bonds with oxygen in the benzoquinone structure.

[0042] According to embodiments of this disclosure, R1 can be selected from C1-C6 hydrocarbon groups, hydroxyl groups, substituted silyl groups, and substituted hydrocarbon groups of C1-C6; R2 and R3 can be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6 hydrocarbon groups, hydroxyl groups, and substituted hydrocarbon groups of C1-C6, wherein R2 and R3 can form a ring with each other; R4 and R5 can be independently selected from C1-C6 hydrocarbon groups, substituted hydrocarbon groups of C1-C6, and C5-C6... 20 The alicyclic or aromatic hydrocarbon groups, wherein R4 and R5 can bond to each other to form a ring; R6 and R7 can be independently selected from hydrogen, chlorine, bromine, C1-C6 hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, aluminum-containing groups, phosphorus-containing groups or silicon-containing groups, wherein R6 and R7 can bond to each other to form a ring.

[0043] According to embodiments of this disclosure, the hydrocarbon group includes alkyl, substituted alkyl, phenyl, or substituted phenyl, wherein the alkyl group includes C1 to C2. 20 Alkyl groups, including halogenated, nitro-substituted, and hydroxyl-substituted alkyl groups; substituted phenyl groups include alkyl (such as methyl, ethyl) substituted groups, halogen substituted groups such as pentafluorophenyl and difluorophenyl, nitro-substituted groups, sulfur-containing group substituted groups, or hydroxyl-substituted groups such as dihydroxyphenyl (hydroquinone), etc.; silicon-based substituents include alkoxy groups, C1-C1 substituents, etc. 12 Hydrocarbon groups, fluorine, chlorine, bromine, iodine, nitro, hydroxyl-substituted silicon groups, such as oxymethyl groups.

[0044] According to embodiments of this disclosure, the bonds formed between R2 and R3, R4 and R5, and R6 and R7 can be single bonds, double bonds, or triple bonds; the rings formed are not limited to ternary rings, quaternary rings, or pentagonal rings.

[0045] According to embodiments of this disclosure, the carrier includes one or more of the following: silicon dioxide, magnesium oxide, titanium dioxide, zinc oxide, aluminum oxide, glass fiber, magnesium chloride, graphene, expanded graphite, ammonium polyphosphate, and carbon black.

[0046] In the embodiments of this disclosure, a support with a high specific surface area and hydroxyl functional groups on its surface is preferred. This support can form hydrogen bonds with the oxygen-containing groups in the phosphine-benzoquinone structure, allowing the phosphine-benzoquinone complex to be firmly loaded onto the support surface, thereby increasing the loading of the nickel-based complex and the structural stability between the complex and the support. Furthermore, because the supported nickel catalyst has a large number of functional groups with significant steric hindrance, it can effectively increase the catalyst's thermal stability and polymerization activity during the catalytic reaction, as well as improve the comonomer insertion ratio and the molecular weight of the catalytic polymer.

[0047] According to embodiments of this disclosure, the structure shown in formula (I) includes at least one of the following:

[0048]

[0049]

[0050] Another aspect of this disclosure provides a method for preparing a supported nickel catalyst, comprising:

[0051] Under an inert atmosphere, the ligand with the structure shown in formula (II) and the nickel source were dissolved in a good solvent. The ligand solution was added dropwise to the nickel source solution. After reacting for 1-12 hours, the nickel black was filtered off and the solvent was removed to obtain the complex with the structure shown in formula (IM). The complex (IM) was added to the organic solvent of the dispersed support, stirred for 1-120 minutes, filtered and washed to obtain the supported nickel catalyst shown in formula (I). The structure of formula (II) is as follows: The structure of formula (IM) is as follows It should be noted that, given the instability of the nickel source, some nickel source will generate insoluble nickel black during the reaction process. Therefore, more than 0.1 equivalents of nickel source needs to be added during the reaction of the ligand and the metallic nickel source to ensure that the ligand can react completely. Excess nickel source and nickel black in the reaction system can be removed by recrystallization, filtration, etc. In the embodiments of this disclosure, R1, R2, R3, R4, R5, R6 and R7 have been defined in the supported nickel catalyst, and will not be defined in more specific ways here.

[0052] The supported nickel catalyst in this embodiment can be obtained through the following steps:

[0053] According to embodiments of this disclosure, the ligand with the structure shown in formula (II) is obtained by the following steps:

[0054] Will The product is obtained by reacting with a hydroxyl protecting group (PG). treat After reacting with butyllithium, Adding it to the reaction system yields an intermediate product with a ligand-protected structure. After removing the protecting group (PG), it was obtained After oxidation, the ligand shown in formula (II) is obtained.

[0055] According to embodiments of this disclosure, the protecting group (PG) can be dihydropyran; the method of removing the protecting group is not limited to hydrochloric acid treatment, and the oxidant for oxidizing the phenolic structure (a-3) to the quinone structure (II) is not limited to iodophenyl diacetic acid. Using the phenolic structure as the starting material for ligand synthesis, the hydroxyl group protection can prevent its destruction during the reaction. After deprotection and oxidation treatment, the phenolic structure is converted to the quinone structure. This technical route is relatively simple, and the prepared ligands have high content and purity.

[0056] The ligand (II) in the embodiments of this disclosure can be obtained through the following steps:

[0057]

[0058] According to embodiments of this disclosure, the structure shown in formula (II) includes at least one of the following:

[0059]

[0060] According to embodiments of this disclosure, the nickel source includes at least one of the following:

[0061] Bis(1,5-cyclooctadiene)nickel (Ni(COD)2), bis(allyl)dichloronickel ([Ni(ally)Cl]2), dimethyl dipyridinium nickel (Py2NiMe2), and nickel bromide (ethylene glycol dimethyl ether) ((DME)NiBr2), wherein bis(allyl)dichloronickel ([Ni(ally)Cl]2) requires reaction with sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (NaBArF4, C 32 H 12 BF 24 Na (abbreviated NaBAF, CAS: 79060-88-1) is used together. Among them, the bis(1,5-cyclooctadiene) nickel source (Ni(COD)2) can cyclically form R2 and R3, R4 and R5, and R6 and R7.

[0062] According to embodiments of this disclosure, the good solvent and organic solvent include at least one of the following: dichloromethane, toluene, tetrahydrofuran, benzene, tetrachloromethane, 1,4-dioxane, and 1,2-dichloroethane.

[0063] According to embodiments of this disclosure, the mass ratio of the complex (IM) to the carrier includes 1:20-50000. Within this range, the complex (IM) can be uniformly loaded onto the carrier and achieve a high loading capacity.

[0064] As another aspect of this disclosure, an application for catalytic olefin polymerization is also provided, including the use of a supported nickel catalyst for catalytic homopolymerization of olefins and / or copolymerization of olefins with polar monomers, wherein the supported nickel catalyst can be prepared by the preparation method described in the above embodiments.

[0065] According to embodiments of this disclosure, the olefins catalyzed by the supported nickel catalyst include ethylene or α-olefins, wherein α-olefins refer to C3-C4 olefins. 18 Terminal olefins, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 1-decene, 1-dodecene, and 1-octadecene.

[0066] According to embodiments of this disclosure, the polar monomers in the copolymerization reaction of olefins and polar monomers catalyzed by a supported nickel catalyst include: C2-C6 groups containing polar groups. 20 1-olefin derivatives and cyclic olefin derivatives containing polar groups; wherein the polar groups include oxygen-containing, nitrogen-containing, sulfur-containing, and selenium-containing organic functional groups, wherein the organic functional groups include hydroxyl, carboxyl, ester, alkoxy, amino, amide, thioether, silyl ether, or selenium ether.

[0067] According to embodiments of this disclosure, the polymerization employs slurry polymerization, loop polymerization, gas-phase polymerization, or other forms of polymerization processes.

[0068] According to embodiments of this disclosure, the polymerization reaction is generally carried out in an organic solvent, which can be a hydrocarbon, cyclic hydrocarbon, or aromatic hydrocarbon. To facilitate reactor operation and polymerization products, the organic solvent can be a hydrocarbon with fewer than 12 carbon atoms, wherein one or more of hexane, toluene, and chlorobenzene may be selected; the polymerization temperature is 0–200°C, for example, 80°C; and the polymerization pressure for olefins is 0.1–50 MPa, for example, 20 MPa.

[0069] The supported nickel catalyst, its preparation method, and its application are further illustrated below through specific embodiments. It should be noted that the specific embodiments described below are merely illustrative examples, and the scope of protection of this disclosure is not limited thereto.

[0070] The following examples illustrate the specific content of this disclosure. The data provided include the synthesis of ligands, the synthesis of catalysts, and applications in ethylene polymerization or copolymerization. Catalyst synthesis and polymerization processes are carried out under anhydrous and oxygen-free conditions. All sensitive substances are stored in glove boxes, all solvents are rigorously dried and dehydrated, ethylene gas is purified using a dehydration and deoxygenation column, and methyl acrylate is purified by dehydration, deoxygenation, and vacuum distillation. Unless otherwise specified, all raw materials are commercially available.

[0071] Silica gel columns were made of 200-300 mesh silica gel, and NMR was performed using a Bruker 400MHz NMR instrument. Elemental analysis was conducted by the Physics and Chemistry Center of the University of Science and Technology of China. Molecular weight and molecular weight distribution were determined by GPC (polystyrene column, trichlorobenzene mobile phase, flow rate 1.0 mL / min, using polydisperse polystyrene as the standard). Mass spectrometry was performed using a Thermo LTQ Orbitrap XL (ESI+) or P-SIMS-Gly of Bruker Daltonics Inc (EI+). Single-crystal X-ray diffraction analysis was performed using an Oxford Diffraction Gemini S Ultra CCD single-crystal diffractometer, Cu Kα. Room temperature radiation.

[0072] Example 1

[0073] The specific process for preparing 2-(tert-butyl)-6-((2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)(phenyl)phosphino)benzoquinone is as follows, and the structure of the ligand is shown in formula (II1):

[0074]

[0075] 50 mmol of tert-butylhydroquinone was reacted with dihydropyran at room temperature for 12 h to obtain a product with a tetrahydropyran protecting group. This product was dissolved in 200 mL of tetrahydrofuran and placed at 0 °C. 55 mmol of n-butyllithium (n-BuLi) was added dropwise, and the reaction was continued for 2 h. Then, 50 mmol of chloro(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)(phenyl)phosphine was added, and the mixture was slowly heated to room temperature and the reaction continued for 12 h. The reaction was then quenched with water. The organic phase was then extracted with diethyl ether, concentrated to 100 mL, and deoxygenated by refrigeration. 15 mL of concentrated hydrochloric acid was added under a nitrogen atmosphere, and the reaction was continued for 6 h. The mixture was neutralized with NaHCO3 aqueous solution, quenched with water, and the organic phase was extracted with diethyl ether. The mixture was dried over anhydrous MgSO4, filtered, concentrated, and subjected to rapid column chromatography to obtain a white solid, namely 2-(bis(2-methoxyphenyl)phosphono)-6-(tert-butyl)phenyl-1,4-diol.

[0076] Then, 10 mmol of 2-(tert-butyl)-6-((2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)(phenyl)phosphino)benzene-1,4-diol was dissolved in 20 mL of methanol, and 10 mmol of iodophenyldiacetic acid methanol solution was slowly added dropwise for oxidation. After reacting for 20 min, the mixture was concentrated at low temperature and subjected to rapid column chromatography to obtain a dark red solid, which is 2-(tert-butyl)-6-((2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)(phenyl)phosphino)benzoquinone with the structure of formula (II1).

[0077] The proton NMR spectrum data of equation (II1) are as follows:

[0078] 1 H NMR (400MHz, Benzene-d6) δ7.40–7.28(m,3H),7.21–7.18(m,1H),7.16–6.98(m,6H),6.52(dd,J=2.7,1.0 Hz,1H),6.43–6.36(m,2H),6.30(d,J=8.4Hz,1H),3.48(s,3H),3.06(s,3H),0.96(s,9H).ESI-MS(m / z):[M + H] + Calcd for C 30 H 30 O4P,484.18; Found:485.18.

[0079] Example 2

[0080] The specific process for preparing 2-(tert-butyl)-6-((2',6'-difluoro-[1,1'-biphenyl]-2-yl)(phenyl)phosphino)benzoquinone is as follows, and the structure of the ligand is shown in formula (II2):

[0081]

[0082] The synthesis method of 2-(tert-butyl)-6-((2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)(phenyl)phosphino)benzene-1,4-diol is the same as that in Example 1, except that 50 mmol of chloro(2',6'-difluoro-[1,1'-biphenyl]-2-yl)(phenyl)phosphino was used instead of chloro(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)(phenyl)phosphino to obtain 2-(tert-butyl)-6-((2',6'-difluoro-[1,1'-biphenyl]-2-yl)(phenyl)phosphino)benzoquinone having formula (II2).

[0083] The proton NMR spectrum data of equation (II2) are as follows:

[0084] 1 H NMR (400MHz, Benzene-d6) δ7.29–7.21(m,2H),7.12(m,2H),7.07–6.91(m,5H),6.68–6.55(m,2H ),6.54–6.47(m,1H),6.42(d,J=2.5Hz,1H),6.38(d,J=2.5Hz,1H),0.93(s,9H).ESI-MS(m / z):[M + H] + Calcd for C 28 H 24 F2O2P, 460.14; Found: 461.14.

[0085] Example 3

[0086] The catalyst shown in formula (I1) is prepared by the following specific method:

[0087]

[0088] In a nitrogen atmosphere, ligand (II2) (1.0 mmol) and nickel source [Ni(ally)Cl]2+NaBArF4 (1.1 mmol) were dissolved in toluene. The solution of ligand (II2) was added dropwise to the solution of nickel source ([Ni(ally)Cl]2+NaBArF4), stirred, and reacted at room temperature for 1 h. The solution was filtered to obtain a brownish-yellow solution. After removing the solvent under vacuum, a solid intermediate product was obtained. 10 mg of the solid intermediate product was added to a toluene solution containing 1 g of silica (SiO2) support. The mixture was stirred for 30 minutes, filtered, the solid was washed, and dried to obtain the supported catalyst (I1).

[0089] Example 4

[0090] The catalyst shown in formula (I2) is prepared by the following method:

[0091]

[0092] In a nitrogen atmosphere, ligand (II2) (1.0 mmol) and nickel source ([Ni(ally)Cl]2+NaBArF4) (1.1 mmol) were dissolved in toluene. The solution of ligand (II2) was added dropwise to the solution of nickel source ([Ni(ally)Cl]2+NaBArF4), stirred, and reacted at room temperature for 1 h. The solution was filtered to obtain a brownish-yellow solution. After removing the solvent under vacuum, a solid intermediate product was obtained. 10 mg of the solid intermediate product was added to a toluene solution containing 1 g of alumina (Al2O3) support. The mixture was stirred for 30 minutes, filtered, the solid was washed, and dried to obtain the supported catalyst (I2).

[0093] Example 5

[0094] The catalyst shown in formula (I3) is prepared by the following method:

[0095]

[0096] In a nitrogen atmosphere, ligand (II2) (1.0 mmol) and nickel source ([Ni(ally)Cl]2+NaBArF4) (1.1 mmol) were dissolved in toluene. The solution of ligand (II2) was added dropwise to the solution of nickel source ([Ni(ally)Cl]2+NaBArF4), stirred, and reacted at room temperature for 1 h. The solution was filtered to obtain a brownish-yellow solution. After removing the solvent under vacuum, a solid intermediate product was obtained. 10 mg of the solid intermediate product was added to a toluene solution containing 1 g of titanium dioxide (TiO2) support, stirred for 30 min, filtered, washed with the solid, and dried to obtain the supported catalyst (I3).

[0097] Example 6

[0098] The catalyst shown in formula (I4) is prepared by the following method:

[0099]

[0100] In a nitrogen atmosphere, ligand (II2) (1.0 mmol) and nickel source ([Ni(ally)Cl]2+NaBArF4) (1.1 mmol) were dissolved in toluene. The solution of ligand (II2) was added dropwise to the solution of nickel source ([Ni(ally)Cl]2+NaBArF4), stirred, and reacted at room temperature for 1 h. The solution was filtered to obtain a brownish-yellow solution. After removing the solvent under vacuum, a solid intermediate product was obtained. 10 mg of the solid intermediate product was added to a toluene solution containing 1 g of magnesium oxide (MgO) support. The mixture was stirred for 30 minutes, filtered, the solid was washed, and dried to obtain the supported catalyst (I4).

[0101] Example 7

[0102] The catalyst shown in formula (I5) is prepared by the following method:

[0103]

[0104] In a nitrogen atmosphere, ligand (1.0 mmol) of formula (II1) and nickel source ([Ni(ally)Cl]2+NaBArF4) (1.1 mmol) were dissolved in toluene. The ligand solution was added dropwise to the nickel source ([Ni(ally)Cl]2+NaBArF4) solution, stirred, and reacted at room temperature for 1 h. The solution was filtered to obtain a brownish-yellow solution. The solvent was removed under vacuum to obtain a solid intermediate product. 10 mg of the solid intermediate product was added to a toluene solution containing 1 g of silica (SiO2) support. The mixture was stirred for 30 minutes, filtered, the solid was washed, and dried to obtain the supported catalyst (I5).

[0105] Example 8

[0106] The catalyst shown in formula (I6) is prepared by the following method:

[0107]

[0108] In a nitrogen atmosphere, ligand (II1) (1.0 mmol) and nickel source ([Ni(ally)Cl]2+NaBArF4) (1.1 mmol) were dissolved in toluene. The solution of ligand (II1) was added dropwise to the solution of nickel source ([Ni(ally)Cl]2+NaBArF4), stirred, and reacted at room temperature for 1 h. The solution was filtered to obtain a brownish-yellow solution. After removing the solvent under vacuum, a solid intermediate product was obtained. 10 mg of the solid intermediate product was added to a toluene solution containing 1 g of magnesium oxide (MgO) support. The mixture was stirred for 30 minutes, filtered, the solid was washed, and dried to obtain the supported catalyst (I6).

[0109] Application Example 1

[0110] The ethylene polymerization reaction was carried out using the catalysts prepared in Examples 3-5. The specific polymerization methods are as follows:

[0111] In a glove box under a nitrogen atmosphere, 20 mL of toluene and the supported catalyst (containing 5 μmol of nickel) prepared in Examples 3-5 were added to a 350 mL autoclave (equipped with a magnetic stirrer, oil bath heating device, and thermometer). The container was then connected to a high-pressure pipeline, and the pipeline was evacuated. The container temperature was set to 80 °C and maintained for 5 minutes. Afterward, the ethylene valve was opened, and ethylene was introduced into the autoclave. The ethylene pressure was adjusted to 20 atm, and the reaction was allowed to proceed for 30 minutes. The reaction was then stopped, the autoclave was opened, and ethanol was added to precipitate the solid. The mixture was filtered under reduced pressure and dried in a vacuum drying oven to obtain a white solid. The experimental results of the catalysts prepared in Examples 3-5 catalyzing the polymerization of ethylene are shown in Table 1.

[0112] Table 1. Experimental results of ethylene polymerization catalyzed by different catalysts

[0113]

[0114] in, a Polymerization conditions: catalyst 5 μmol, toluene = 18 mL, dichloromethane = 2 mL, time = 30 min, polymerization temperature 80 degrees Celsius; b Activity=10 6 g·mol -1 ·h -1 ; c Melting point was determined using a differential scanning calorimeter. d Weight-average molecular weight = 10 4 gmol -1 The molecular weight was determined by gel permeation chromatography (GPC) at 150°C using polystyrene as the standard and trichlorobenzene as the solvent.

[0115] Table 1 shows that different supports have different loading capacities for complexes (IM) and different effects on the electron density of nickel centers in the complexes, which results in different effects of complexes supported on the catalytic reaction under the same reaction conditions.

[0116] Application Example 2

[0117] The catalyst prepared in Example 3 was used for the copolymerization of ethylene with polar monomers. The specific polymerization method is as follows:

[0118] In a glove box under a nitrogen atmosphere, 15 mL of toluene and the supported catalyst (containing 20 μmol of nickel) prepared in Examples 3-5 were added to a 350 mL autoclave (equipped with a magnetic stirrer, oil bath heating device, and thermometer). The container was then connected to a high-pressure pipeline and the pipeline was evacuated. The container temperature was set to 80 °C and maintained for 5 minutes. Polar monomers (methyl 10-undecenoate, 10-undecenol, 6-chloro-1-hexene, etc.) were prepared to a concentration of 0.5 mol / L, dissolved in 5 mL of toluene, and injected into the autoclave using a syringe. The ethylene valve was opened, ethylene was introduced into the autoclave, and the ethylene pressure was adjusted to 20 atm. The reaction was allowed to proceed for 60 minutes. The reaction was then stopped, the autoclave was opened, ethanol was added to precipitate the solid, the mixture was filtered under reduced pressure, and dried in a vacuum drying oven to obtain a white solid.

[0119] The results of the polymerization of ethylene with polar monomers catalyzed by the catalyst prepared in Example 3 are shown in Table 2:

[0120] Table 2. Catalytic effect of catalysts on the polymerization of ethylene with monomers of different polarities in Example 3

[0121]

[0122] in, a Polymerization conditions: catalyst 20 μmol, toluene = 20 mL, ethylene = 20 atm, time = 60 minutes, polymerization temperature 80 degrees Celsius; b Activity=10 4 g·mol -1 ·h -1 ; c Melting point was determined using a differential scanning calorimeter. d The polar monomer insertion ratio was measured by 1H NMR spectroscopy. e Weight-average molecular weight = 10 4 g mol -1 The molecular weight was determined by GPC using polystyrene as the standard and trichlorobenzene as the solvent at 150°C.

[0123] As shown in Table 2, the catalyst disclosed in this invention can catalyze the copolymerization of ethylene with polar monomers to prepare polar polyolefins under certain conditions, with the highest activity reaching 1.82 × 10⁻⁶. 4 g·mol -1 ·h -1 Melting point: 124.5–126.1℃; Weight-average molecular weight: up to 15.7 × 10⁻⁶. 4 g / mol.

[0124] The specific embodiments described above further illustrate the purpose, technical solutions, and beneficial effects of this disclosure. It should be understood that the above descriptions are merely specific embodiments of this disclosure and are not intended to limit this disclosure. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this disclosure should be included within the protection scope of this disclosure.

Claims

1. A supported nickel catalyst characterized in that, The supported nickel catalyst contains a structure shown in formula (I), Formula (I); wherein R1is selected from the group consisting of C1-C20hydrocarbyl, nitro, hydroxyl, substituted silyl, C1-C20substituted hydrocarbyl; R2and R3are independently selected from the group consisting of hydrogen, C1-C20hydrocarbyl, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silyl, C1-C20substituted hydrocarbyl, R2and R3may be bonded to each other to form a ring; R4and R5are independently selected from the group consisting of C1-C20hydrocarbyl, C1-C20substituted hydrocarbyl, R4and R5may be bonded to each other to form a ring; R6and R7are independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, C1-C20hydrocarbyl, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, silicon-containing group, or tin-containing group, R6and R7may be bonded to each other to form a ring. 20 20 20 20 20 20 20 wherein R1is selected from the group consisting of C1-C20hydrocarbyl, nitro, hydroxyl, substituted silyl, C1-C20substituted hydrocarbyl; R2and R3are independently selected from the group consisting of hydrogen, C1-C20hydrocarbyl, fluorine, chlorine, bromine, iodine, nitro, hydroxyl, substituted silyl, C1-C20substituted hydrocarbyl, R2and R3may be bonded to each other to form a ring; R4and R5are independently selected from the group consisting of C1-C20hydrocarbyl, C1-C20substituted hydrocarbyl, R4and R5may be bonded to each other to form a ring; R6and R7are independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, C1-C20hydrocarbyl, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, silicon-containing group, or tin-containing group, R6and R7may be bonded to each other to form a ring.​​​​​​ wherein, the hydroxyl group on the surface of the carrier forms a hydrogen bond with the oxygen in the quinone structure.

2. The catalyst according to claim 1, characterized in that, The carrier includes one or more of silica, magnesium oxide, titanium dioxide, zinc oxide, aluminum oxide, glass fiber, magnesium chloride, graphene, expanded graphite, ammonium polyphosphate, carbon black.

3. The catalyst of claim 2, wherein The structure shown in formula (I) includes at least one of the following: Formula (I1), Formula (I2), Formula (I3), Formula (I4), Formula (I5), Formula (I6).

4. The catalyst of claim 1, wherein R4and R5are independently selected from C5-C 20 alicyclic or aromatic hydrocarbon groups.

5. A process for preparing the catalyst of claim 1, characterized by, The method includes: under an inert atmosphere, the ligand shown in formula (II) and the metal nickel source are dissolved in a good solvent respectively, the ligand solution is added dropwise into the metal nickel source solution, after reaction for 1-12 hours, filtration and removal of the solvent to obtain a complex of structure shown in formula (I-M); The complex (I-M) is added to the organic solvent in which the carrier is dispersed, stirred for 1-120 minutes, filtered and washed to obtain the supported nickel catalyst shown in formula (I); wherein the structure of formula (II) is: formula (II); The structure of formula (I-M) is: Formula (I-M); wherein R1, R2, R3, R4, R5, R6, and R7 are as defined in claim 1.

6. The method of claim 5, wherein, The ligand shown in formula (II) is obtained by the following steps: In an inert atmosphere, the compound of formula (I) is reacted with a hydroxyl protecting group to obtain the compound of formula (II) (a) reacting with a hydroxyl protecting group to obtain the compound of formula (II) (a-1); the compound of formula (II) is obtained by reacting (a-1) with butyl lithium, and then (b) adding to the reaction system to obtain the protected structure of the ligand (a-2), and removing the protecting group to obtain (a-3), and then oxidizing to obtain the ligand of formula (II) 7. The method according to claim 5 or 6, characterized in that, The structure shown in formula (II) includes at least one of the following: Formula (III1), Formula (III2).

8. The method of claim 5, wherein, The metal nickel source includes at least one of the following: bis(1,5-cyclooctadiene)nickel, bis(allyl)nickel dichloride, dimethyl nickel dipyridine, nickel bromide (glycol dimethyl ether); The good solvent and the organic solvent include at least one of the following: dichloromethane, toluene, tetrahydrofuran, benzene, carbon tetrachloride, 1,4-dioxane, 1,2-dichloroethane.

9. The method of claim 5, wherein, The mass ratio of the complex (I-M) to the carrier includes 1:20-50000.

10. Use of a catalyst for the polymerization of olefins, characterized in that, The application includes using the supported nickel catalyst for catalyzing olefin homopolymerization and / or copolymerization of olefin and polar monomer, wherein the supported nickel catalyst is the supported nickel catalyst according to any one of claims 1-4.

11. The application according to claim 10, characterized in that, The olefin includes ethylene or a-olefin; The polar monomers include C2to C1o olefin derivatives containing polar groups and cyclic olefin derivatives containing polar groups. 20 The polar monomers include C2to C1o olefin derivatives containing polar groups and cyclic olefin derivatives containing polar groups. wherein, the polar group includes oxygen-containing, nitrogen-containing, sulfur-containing, selenium-containing organic functional groups, the organic functional groups include hydroxyl, carboxyl, ester, alkoxy, amine, amide, sulfide, silyl ether or selenide ether.

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