A novel 2,4,8-triarylnaphthylpyridine imine palladium (II) catalyst, its preparation method and application

Abstract

The present invention provides a novel 2,4,8-triarylnaphthylpyrimidine palladium (II) catalyst and its preparation method and application, belonging to the technical field of olefin polymerization catalysis; using 2-acetylpyridine as the catalyst skeleton, a series of amine compounds containing 2,4,8-triarylnaphthalene structures are introduced on the skeleton, and the substituents at the 8th position of the naphthyl group are exactly located at the axial position of the metal center, which effectively hinders the synergistic chain transfer during the polymerization process and improves the thermal stability, so that high molecular weight polyethylene can be synthesized. The distal substituents on the 2,4-diaryl of the catalyst can moderately adjust the activity and molecular weight of polymerization and copolymerization, as well as the insertion ratio of acrylate esters in copolymerization. The products of ethylene (co) polymerization all have ultra-high degrees of branching. The homopolymer exhibits liquid flow characteristics at room temperature and has the potential to be used as a base oil for lubricants; while the copolymer has good low-temperature fluidity and can be applied to polar additives and special lubricants.

Description

Technical Field

[0001] The invention belongs to the technical field of olefin polymerization catalysis, and specifically relates to a novel 2,4,8-triarylnaphthylpyridineimine palladium (II) catalyst and a preparation method and application thereof. Background Art

[0002] Since the rapid development of the polyolefin industry driven by Ziegler-Natta catalysts, the limited application of non-polar polyolefins has gradually become prominent. The introduction of a small amount of polar functional groups (even 0.5 mol%) can effectively alleviate the shortcomings of most polyethylene (PE), such as poor surface properties and difficulty in adhesion of polar materials, thereby improving and adjusting product properties such as adhesion, barrier and surface properties, dyeability, printability and polymer miscibility, and increasing its commercial value. In the past 20 years, reports and application studies on the introduction of polar monomers into polyolefins have continued to appear, showing the urgent market demand for polar functionalized polyolefin materials. The introduction of polar functional groups into non-polar polyolefins can effectively improve their adhesion, toughness, surface properties, compatibility, dyeability and barrier properties, which is of great significance for expanding the application of polyolefin materials in different fields.

[0003] A variety of polymerization techniques have been developed to prepare functionalized polyolefins. Among these techniques, coordination insertion polymerization promoted by late transition metal catalysts is considered to be a powerful tool to achieve this goal. Pyridine imine catalysts, as a diimine catalyst with a unilateral stereostructure, have received attention and development. Due to their chain walking effect, copolymers with different polymer structures and topological structures can be produced, so that the polar groups are usually located at the end of the branch. However, they can usually only catalyze the polymerization of ethylene or copolymerization with polar monomers to produce low molecular weight polyethylene or polar copolymers. At the same time, due to the presence of polar monomers, it is easy to form polar group chelation and accelerate chain transfer reactions, resulting in low copolymerization activity, low polar monomer insertion rate, and low polymer molecular weight. These are also problems that need to be solved in the field of olefin polymerization. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a novel 2,4,8-triarylnaphthylpyridine imine palladium (II) catalyst and its preparation method and application, which improves the molecular weight of the produced polyolefin by changing the steric hindrance of the axial position of the catalyst metal center, and adjusts the activity in the polymerization process and the insertion ratio of the polar monomer by regulating the remote substituents at the 2,4-diaryl position of the catalyst. In the present invention, all polymers obtained by the pyridine imine palladium (II) catalyst have the characteristics of hyperbranching.

[0005] To achieve the above object, this solution first provides a novel 2,4,8-triarylnaphthylpyrimidine imine palladium (II) catalyst. The catalyst contains a pyrimidine imine ligand of 2,4,8-triarylnaphthyl, and the structure of the catalyst is shown in the following formula 1:

[0006]

[0007] Wherein, R is selected from H, Ph or alkyl; Ar is selected from 4-substituted aryl, H, thienyl, pyrrolyl, furyl.

[0008] Based on a general inventive concept, this solution also provides a preparation method of a catalyst, including the following steps:

[0009] S1. Prepare a pyrimidine imine ligand containing 2,4,8-triarylnaphthyl: Heat and stir aniline solid containing triarylnaphthyl, 2-acetylpyridine and p-toluenesulfonic acid in a toluene solution at 90 °C until a main spot appears on the thin layer chromatography plate. Evaporate the solvent and concentrate it to 5 ml under vacuum. Dilute the remaining solution with methanol and recrystallize to form a solid. Wash it with ethanol after filtration and dry it under vacuum to obtain a solid powder of pyrimidine imine palladium (II) ligand containing 2,4,8-triarylnaphthyl;

[0010] S2. Prepare a novel 2,4,8-triarylnaphthylpyrimidine imine palladium (II) catalyst: Under the atmosphere of a protective gas, using dichloromethane as a solvent, mix the pyrimidine imine ligand containing 2,4,8-triarylnaphthyl prepared in step S1 with (COD)PdMeCl, stir and react at room temperature, filter the suspension, and after removing the solvent from the mother liquor under vacuum conditions, wash it with ether and dry it under vacuum to obtain a solid complex, namely the novel 2,4,8-triarylnaphthylpyrimidine imine palladium (II) catalyst.

[0011] Preferably, the stirring reaction time in step S1 is 24 h.

[0012] Preferably, the molar ratio of the pyrimidine imine ligand containing 2,4,8-triarylnaphthyl to (COD)PdMeCl in step S2 is 1:1.

[0013] Preferably, the heating and stirring time in step S2 is 12 h, and the protective gas is air or nitrogen.

[0014] Based on a general inventive concept, this solution also provides an application of the novel 2,4,8-triarylnaphthylpyrimidine imine palladium (II) catalyst in the catalytic ethylene polymerization reaction.

[0015] Preferably, the temperature of the catalytic ethylene polymerization reaction is 30-70 °C, and the time is 180-360 minutes.

[0016] Based on a general inventive concept, the present solution also provides an application of a novel 2,4,8-triarylnaphthylpyridineimine palladium (II) catalyst in the copolymerization reaction of ethylene and acrylate compounds.

[0017] Preferably, the acrylate compound includes any one of methyl acrylate, ethyl acrylate, and n-butyl acrylate.

[0018] Preferably, the application is carried out in a composite catalytic system composed of a novel 2,4,8-triarylnaphthylpyridineimine palladium catalyst and a cocatalyst sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and the molar ratio of the novel 2,4,8-triarylnaphthylpyridineimine palladium catalyst to the cocatalyst sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is 1:2.

[0019] The preparation mechanism of the novel 2,4,8-triarylnaphthylpyridineimine palladium (II) catalyst prepared in the present solution is as follows:

[0020] The synthesis general formula of the novel 2,4,8-triarylnaphthylpyridineimine palladium (II) catalyst prepared in the present solution is as follows:

[0021]

[0022] In the pyridineimine palladium (II) ligand containing 2,4,8-triarylnaphthyl, 2-acetylpyridine is used as the catalyst skeleton, and a series of amine compounds containing 2,4,8-triarylnaphthalene structures are introduced on the skeleton. The substituent at the 8-position of the naphthyl group is exactly located at the axial position of the metal center, which effectively hinders the synergistic chain transfer during the polymerization process and improves the thermal stability, so that high molecular weight polyethylene can be synthesized. The distal substituents on the 2,4-diaryl of the catalyst can moderately adjust the activity and molecular weight of polymerization and copolymerization, as well as the insertion ratio of acrylate in the copolymerization.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) The catalyst prepared in the present solution utilizes the substituent at the 8-position of the naphthyl group, which is exactly located at the axial position of the metal center, which effectively hinders the synergistic chain transfer during the polymerization process and improves the thermal stability, so that high molecular weight polyethylene can be synthesized. The distal substituents on the 2,4-diaryl of the catalyst can moderately adjust the activity and molecular weight of polymerization and copolymerization, as well as the insertion ratio of acrylate in the copolymerization. Compared with the classical pyridineimine palladium catalyst, the novel pyridineimine palladium catalyst of the present solution not only increases the molecular weight of polyolefins, but also greatly increases the insertion ratio of polar monomers.

[0025] (2) A series of hyperbranched polyethylene oils with high molecular weights (16.8 - 60.8 kg / mol) (90 - 96 / 1000C) and hyperbranched polar copolymers with high insertion ratios (9.21 - 21.00 mol%) (96 - 120 / 1000C) can be obtained through the catalytic reaction of this solution. The products of this ethylene polymerization exhibit liquid flow characteristics at room temperature and have the potential to be used as base oils for lubricants, while the copolymers have good low-temperature fluidity and can be applied to polar additives and special lubricants. Description of the Drawings

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or in the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0027] Figure 1 1H NMR spectrum of the catalyst prepared in Example 1;

[0028] Figure 2 1H NMR spectrum of the catalyst prepared in Example 2;

[0029] Figure 3 1H NMR spectrum of the catalyst prepared in Example 3;

[0030] Figure 4 1H NMR spectrum of the catalyst prepared in Example 4;

[0031] Figure 5 Single crystal diagram of the catalyst prepared in Example 3;

[0032] Figure 6 Detailed carbon spectrum analysis diagram of the hyperbranched polyethylene product in Experimental Example 1;

[0033] Figure 7 Detailed carbon spectrum analysis diagram of the hyperbranched polar functionalized polyethylene product in Experimental Example 2. Detailed Description of the Invention

[0034] To make the technical problems, technical solutions, and advantages to be solved by the present invention clearer, the following will be described in detail with reference to the drawings and specific embodiments.

[0035] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention. Without departing from the spirit and essence of the present invention, any modification or replacement of the methods, steps, or conditions of the present invention belongs to the scope of the present invention.

[0036] Unless otherwise specified, the technical means used in the examples are conventional means well-known to those skilled in the art; unless otherwise specified, the reagents used in the examples are all commercially available.

[0037] Reagents and raw materials used in the examples: Except for the reactions involving removing (COD)PdMeCl, all metal-organic reactions were carried out under nitrogen protection, and all solvents were dried and deoxygenated. Anhydrous methanol and ethanol were of analytical grade and used directly. Toluene was dehydrated by molecular sieve, refluxed with metallic sodium under nitrogen protection, and distilled before use.

[0038] The reactants in the examples of this solution are selected from:

[0039]

[0040] Example 1

[0041] Preparation of a novel 2,4,8-triarylnaphthylpyridine imine palladium catalyst

[0042] S1. 2,4,8-Triarylnaphthylpyridine imine ligand: Preparation A solution of A1 (1.0 mmol, 1.0 equivalent), 2-acetylpyridine (1.0 mmol, 1.0 equivalent) and p-toluenesulfonic acid (20 mg) in toluene (20 mL) was stirred at 90 °C for 24 hours. During the stirring, samples were taken every 6 hours and observed on a thin-layer chromatography plate until a main spot appeared on the thin-layer chromatography plate. The solvent was evaporated and concentrated to 5 mL under vacuum. The remaining solution was diluted with methanol (20 mL) to form a solid. After filtration, it was washed with 10 mL of ethanol and dried under vacuum to obtain a solid powder (L1) with a yield of 83%. The preparation reaction formula is as follows:

[0043]

[0044] The mass spectrometry analysis result was: ACPI-MS: calcd for C 36 H 29 N2 + : 489.2326, Found, 489.2317, [M + H] +

[0045] S2. Preparation of a novel 2,4,8-triarylnaphthylpyridine imine palladium catalyst

[0046] Dissolve 0.4 mmol of the pyridine-imine ligand prepared in S1 and (COD)PdMeCl (106 mg, 0.4 mmol) in 20 mL of dichloromethane, and stir the reaction at room temperature for 12 h; during the stirring process, the color of the solution deepens. After the reaction, most of the dichloromethane is evaporated under reduced pressure, the solution is concentrated to 2 mL, the product is precipitated with 20 mL of ether, and washed with 3×5 mL of ether to obtain the pure compound as a solid for standby, with a yield of 80%. The NMR analysis and elemental analysis of the pyridine-imine palladium complex prepared in this example are as follows:

[0047] The 1H NMR spectrum is as shown in Figure 1 Figure;

[0048] NMR analysis: 1 H NMR (400 MHz, CDCl3) δ 9.01, 8.93 (d, d, J = 5.3, 1.5 Hz, 1H, Ar-H), 8.56, 8.24 (d, d, J = 7.8, 1.9 Hz, 1H, Ar-H), 7.92–7.72 (m, 4H, Ar-H), 7.50–7.26 (m, 10H, Ar-H), 7.20–7.03 (m, 4H, Ar-H), 6.66 (dd, J = 7.7, 1.9 Hz, 1H, Ar-H), 6.37 (dd, J = 7.7, 1.8 Hz, 1H, Ar-H), 1.95, 1.85, 1.80 (s, s, s, 3H, Ar-CH3), 1.76, 1.72, 1.68 (s, s, s, 3H, -CH3), 1.18, 0.90, 0.17 (s, s, s, 3H, Pd-CH3). 13 C NMR (101 MHz, CDCl3) δ 172.27 (C=N), 152.76, 148.62, 141.24, 140.39, 140.37, 140.08, 139.39, 139.33, 137.61, 135.96, 132.48, 131.39, 131.36, 130.40, 130.08, 129.71, 129.47, 129.35, 128.51, 127.97, 127.76, 127.55, 127.35, 126.83, 126.68, 125.78, 124.82, 123.89, 20.87 (Ar-CH3), 20.12 (-CH3), -1.77 (Pd-CH3).

[0049] Elemental analysis: calc. for C 37 H 31 C lN2Pd:C, 68.84; H, 4.84; N, 4.34. Found: C, 68.74; H, 4.69; N, 4.28.

[0050] Example 2

[0051] Preparation of a novel 2,4,8-triarylnaphthylpyridine imine palladium catalyst

[0052] S1. 2,4,8-Triarylnaphthylpyridine imine ligand: Preparation: A solution of A2 (1.0 mmol, 1.0 equivalent), 2-acetylpyridine (1.0 mmol, 1.0 equivalent) and p-toluenesulfonic acid (20 mg) in toluene (20 mL) was stirred at 90 °C for 24 h. During the stirring, samples were taken every 6 h and observed on a thin-layer chromatography plate until a main spot appeared on the thin-layer chromatography plate. The solvent was evaporated and concentrated to 5 mL under vacuum. The remaining solution was diluted with methanol (20 mL) to form a solid. After filtration, it was washed with 10 mL of ethanol and dried under vacuum to obtain a solid powder (L2) with a yield of 80%.

[0053] Mass spectrometry analysis: ACPI-MS (m / z): calcd for C 38 H 33 N2 + : 517.2639, Found, 517.2637, [M + H] +

[0054] S2. Preparation of a novel 2,4,8-triarylnaphthylpyridine imine palladium catalyst

[0055] 0.4 mmol of the pyridine imine ligand prepared in S1 and (COD)PdMeCl (106 mg, 0.4 mmol) were dissolved in 20 mL of dichloromethane and stirred at room temperature for 12 h; during the stirring, the color of the solution deepened. After the reaction, most of the dichloromethane was evaporated under reduced pressure, the solution was concentrated to 2 mL, the product was precipitated with 20 ml of ether, and washed with 3 × 5 ml of ether to obtain a pure compound as a solid for standby, with a yield of 83%. The nuclear magnetic resonance analysis and elemental analysis of the pyridine imine palladium complex prepared in this example are as follows:

[0056] The single crystal diagram of the novel 2,4,8-triarylnaphthylpyridine imine palladium catalyst prepared in this example is as Figure 5 described;

[0057] The nuclear magnetic resonance hydrogen spectrum is as Figure 2 shown;

[0058] Nuclear magnetic resonance analysis: 11H NMR (400 MHz, CDCl3) δ 9.00 (d, J = 5.1 Hz, 1H, Ar-H), 8.31 (dd, J = 7.7, 1.9 Hz, 1H, Ar-H), 7.99 (d, J = 8.5 Hz, 1H, Ar-H), 7.83–7.79 (m, 1H, Ar-H), 7.71 (d, J = 7.8 Hz, 2H, Ar-H), 7.50–7.40 (m, 5H, Ar-H), 7.36–7.32 (m, 4H, Ar-H), 7.08 (dd, J = 17.2, 7.8 Hz, 3H, Ar-H), 6.70 (dd, J = 7.6, 1.8 Hz, 1H, Ar-H), 6.42 (d, J = 7.6 Hz, 1H, Ar-H), 2.47 (s, 3H, Ar-CH3), 2.23 (s, 3H, Ar-CH3), 2.01, 1.92 (s, 3H, Ar-CH3), 1.76, 1.61 (s, 3H, Ar-CH3), 0.24, 0.02 (s, 3H, Pd-CH3). 13 13C NMR (101 MHz, CDCl3) δ 172.06 (C=N), 152.70, 148.46, 141.20, 140.13, 139.69, 139.13, 137.40, 137.35, 137.32, 136.86, 136.23, 135.71, 132.31, 131.22, 131.15, 130.15, 130.02, 129.37, 129.31, 129.09, 129.03, 127.81, 127.34, 126.72, 126.49, 125.39, 124.68, 123.75, 21.23 (Ar-CH3), 21.11 (Ar-CH3), 20.73 (Ar-CH3), 19.91 (Ar-CH3), -1.87 (Pd-CH3).

[0059] Elemental analysis: calc. for C 39 H 35 C l N2Pd: C, 69.54; H, 5.24; N, 4.16. Found: C, 69.36; H, 5.33; N, 4.25.

[0060] Example 3

[0061] Preparation of a novel 2,4,8-triarylnaphthylpyridine imine palladium catalyst

[0062] S1, 2,4,8-Triarylnaphthylpyridine Imine Ligand: Preparation Dissolve a solution of A3 (1.0 mmol, 1.0 equiv), 2-acetylpyridine (1.0 mmol, 1.0 equiv), and p-toluenesulfonic acid (20 mg) in toluene (20 mL) and stir at 90 °C for 24 h. During the stirring process, samples are taken every 6 h and observed on a thin-layer chromatography plate until a main spot appears on the thin-layer chromatography plate. Evaporate the solvent and concentrate it to 5 mL under vacuum. Dilute the remaining solution with methanol (20 mL) to form a solid. Wash it with 10 mL of ethanol after filtration and dry it under vacuum to obtain a solid powder (L3) with a yield of 85%.

[0063] Mass Spectrometry Analysis: ACPI-MS (m / z): calcd for C 36 H 27 F2N2 + : 525.2137, Found, 525.2134, [M+H] +

[0064] S2、Preparation of Novel 2,4,8-Triarylnaphthylpyridine Imine Palladium Catalyst

[0065] Dissolve 0.4 mmol of the pyridine imine ligand prepared in S1 and (COD)PdMeCl (106 mg, 0.4 mmol) in 20 mL of dichloromethane and stir at room temperature for 12 h; during the stirring process, the color of the solution deepens. After the reaction is completed, most of the dichloromethane is evaporated under reduced pressure, the solution is concentrated to 2 mL, the product is precipitated with 20 ml of ether, and washed with 3 × 5 ml of ether to obtain a pure compound as a solid for standby with a yield of 78%. The NMR analysis and elemental analysis of the pyridine imine palladium complex prepared in this example are as follows:

[0066] The nuclear magnetic resonance hydrogen spectrum is as Figure 3 shown;

[0067] NMR Analysis: 11H NMR (400 MHz, CDCl3) δ 9.12, 8.95 (d, d, J = 5.1 Hz, 1H, Ar-H), 8.34, 8.23 (d, d, J = 7.8, 1.9 Hz, 1H, Ar-H), 7.87–7.76 (m, 4H, Ar-H), 7.48–7.31 (m, 6H, Ar-H), 7.20–6.90 (m, 6H, Ar-H), 6.65 (dd, J = 7.6, 1.9 Hz, 1H, Ar-H), 6.38 (d, J = 7.7 Hz, 1H, Ar-H), 1.98, 1.87, 1.83 (s, s, s, 3H, Ar-CH3), 1.78, 1.75, 1.70 (s, s, s, 3H, -CH3), 1.20, 0.92, 0.17 (s, s, s, 3H, Pd-CH3). 13 13C NMR (101 MHz, CDCl3) δ 172.32 (C=N), 163.87, 160.69, 148.73, 139.46, 139.41, 137.72, 136.11, 132.02, 131.94, 131.61, 131.49, 131.41, 131.36, 129.58, 129.25, 127.90, 127.76, 126.75, 126.65, 126.07, 124.00, 115.75, 115.64, 115.54, 115.42, 20.88 (Ar-CH3), 20.15 (-CH3), -1.69 (Pd-CH3).

[0068] Elemental analysis: calc. for C 37 H 29 ClF2N2Pd: C, 65.21; H, 4.29; N, 4.11. Found: C, 65.23; H, 4.36; N, 4.21.

[0069] Example 4

[0070] Preparation of novel 2,4,8-triarylnaphthylpyridine imine palladium catalyst

[0071] S1, 2,4,8-Triarylnaphthylpyridine Imine Ligand: Preparation Dissolve a solution of A4 (1.0 mmol, 1.0 equivalent), 2-acetylpyridine (1.0 mmol, 1.0 equivalent), and p-toluenesulfonic acid (20 mg) in toluene (20 mL) and stir at 90 °C for 24 hours. During the stirring process, samples are taken every 6 hours and observed on a thin-layer chromatography plate until a main spot appears on the thin-layer chromatography plate. Evaporate the solvent and concentrate it to 5 mL under vacuum. Dilute the remaining solution with methanol (20 mL) to form a solid. After filtration, wash it with 10 mL of ethanol and dry it under vacuum to obtain a solid powder (L4) with a yield of 84%.

[0072] Mass Spectrometry Analysis: ACPI-MS (m / z): calcd for C 44 H 45 N2 + : 601.3578, Found, 601.3563, [M+H] +

[0073] S2、Preparation of a Novel 2,4,8-Triarylnaphthylpyridine Imine Palladium Catalyst

[0074] Dissolve 0.4 mmol of the pyridine imine ligand prepared in S1 and (COD)PdMeCl (106 mg, 0.4 mmol) in 20 mL of dichloromethane and stir at room temperature for 12 h; during the stirring process, the color of the solution deepens. After the reaction, most of the dichloromethane is evaporated under reduced pressure, the solution is concentrated to 2 mL, the product is precipitated with 20 ml of ether, and washed with 3×5 ml of ether to obtain a pure compound as a solid for standby with a yield of 85%. The nuclear magnetic resonance analysis and elemental analysis of the pyridine imine palladium complex prepared in this example are as follows:

[0075] The nuclear magnetic resonance hydrogen spectrum is as Figure 4 shown;

[0076] Nuclear Magnetic Resonance Analysis: 11H NMR (400 MHz, CDCl3) δ 9.15, 8.97 (d, d, J = 5.1 Hz, 1H, Ar-H), 8.60, 8.28 (d, d, J = 7.7 Hz, 1H, Ar-H), 7.99 (d, J = 8.5 Hz, 1H, Ar-H), 7.75 (dd, J = 8.6, 2.0 Hz, 3H, Ar-H), 7.49–7.30 (m, 9H, Ar-H), 7.22 (dd, J = 6.9, 1.6 Hz, 2H, Ar-H), 7.07 (d, J = 7.8 Hz, 1H, Ar-H), 6.67–6.65 (m, 1H, Ar-H), 6.38 (d, J = 7.7 Hz, 1H, Ar-H), 1.96, 1.86 (s, s, 3H, Ar-CH3), 1.79, 1.71 (s, s, 3H, -CH3), 1.38 (s, 9H, -CH3), 1.16 (s, 9H, -CH3), 0.22, 0.21 (s, s, 3H, Pd-CH3). 13 13C NMR (101 MHz, CDCl3) δ 172.03 (C=N), 152.79, 150.52, 150.11, 148.50, 141.29, 140.11, 139.70, 139.12, 137.38, 137.29, 136.16, 135.69, 132.27, 131.22, 131.12, 129.95, 129.43, 129.32, 129.22, 127.86, 127.34, 126.79, 126.45, 125.36, 125.23, 124.71, 123.51, 34.64 (-C(CH3)3), 34.44 (-C(CH3)3), 31.41 (-C(CH3)3), 31.16 (-C(CH3)3), 20.73 (-CH3), 19.87 (Ar-CH3), -1.88 (Pd-CH3).

[0077] Elemental analysis: calc. for C 45 H 47 C l N2Pd: C, 71.33; H, 6.25; N, 3.70. Found: C, 71.26; H, 6.41; N, 3.81.

[0078] Experimental Example 1

[0079] Examine the effect of the catalysts prepared in Examples 1-4 on ethylene polymerization

[0080] Polymerization was carried out using a 350 mL high-pressure resistant glass reactor. The high-pressure resistant glass reactor was dried at 90 °C for 3 h. Under an air atmosphere, 40 mL of dichloromethane and the cocatalyst sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (2 equivalents) were added thereto. It was connected to a high-pressure resistant stainless steel gas pipeline. The gas pipeline was evacuated using a vacuum pump, and then nitrogen was introduced for gas displacement. After repeating the operation three times, the vacuum pump was closed. The temperature was raised to the required temperature (30 - 50 °C) using an oil bath heater, and then ethylene was introduced. The rotation speed of the magnetic stirrer was set at 300 r / min. Under an ethylene atmosphere, 2 mL of dichloromethane dissolving a palladium catalyst (10.0 μmol) was injected into the polymerization glass reactor using a syringe. The pressure reducing valve was adjusted to 4 atm. After 3 hours of polymerization, the pressure was released. After most of the polymerization solvent was removed by vacuum evaporation, it was placed on an Edwards vacuum pump at room temperature and pumped for 1 hour to obtain a polymer product.

[0081] The detailed carbon spectrum analysis diagram of the hyperbranched polyethylene generated by the catalyst prepared in Example 1 in No. 2 under catalytic reaction at 50 °C is as Figure 6 shown;

[0082] Table 1 below shows the experimental conditions for ethylene polymerization using the preferred catalysts provided by the present invention; polymerization result data such as the polymer molecular weight (Mn), the polymer molecular weight distribution (PDI), and the degree of branching (brs).

[0083] Table 1 Effects of the catalysts prepared in Examples 1 - 4 on the catalytic polymerization of ethylene

[0084]

[0085]

[0086] In the table: The activity is 10 4 g / (mol Pd·h), Mn is the number average molecular weight, Mw / Mn is the molecular weight distribution, and brs is the degree of branching (the number of methyl groups corresponding to every 1000 methylenes).

[0087] Table 1 shows that all palladium catalysts showed medium activity (10 4 g mol -1 h -1 ) during the ethylene polymerization process, and high-branched (90 - 96 / 1000C) polyethylene with a high molecular weight (16.8 - 60.8 kg / mol) could be generated. This type of hyperbranched polyethylene showed liquid flow characteristics at room temperature and had the potential to be used as a base oil for lubricants.

[0088] Experimental Example 2

[0089] Investigate the effects of the catalysts prepared in Examples 1 - 4 on the copolymerization of ethylene and methyl acrylate

[0090] A 350 mL high pressure glass kettle was used for polymerization. The high pressure glass kettle was dried at 90°C for 3 hours. 18 mL of dichloromethane, a cocatalyst sodium tetra(3,5-di(trifluoromethyl)phenyl)borate (2 equivalents) and a required amount of methyl acrylate (MA) were added thereto in an air atmosphere. The mixture was connected to a high pressure stainless steel gas pipeline. The vacuum pump was turned on to evacuate the gas pipeline. Nitrogen was then introduced for gas replacement. The operation was repeated three times and the vacuum pump was turned off. The temperature was raised to the required temperature using an oil bath and ethylene was introduced. The speed of the magnetic stirrer was set to 300 r / min. In an ethylene atmosphere, 2 mL of dichloromethane dissolved in a palladium catalyst (10.0 μmol) was injected into the polymerization glass kettle with a syringe. The pressure reducing valve was adjusted to 2 atm. After the polymerization time was 6 hours, the pressure was released. After the polymerization solvent was evaporated under reduced pressure to remove most of the solvent, the polymer product was obtained by pumping on an Edwards vacuum pump at room temperature for 1 hour.

[0091] The detailed carbon spectrum analysis of the hyperbranched polar functionalized polyethylene catalyzed by the catalyst prepared in Example 1 in No. 2 is shown in FIG. Figure 7 As shown;

[0092] Table 2 below shows the experimental conditions for copolymerization of ethylene and methyl acrylate using the preferred catalyst provided by the present invention; polymerization result data such as polymer molecular weight (Mn), polymer molecular weight distribution (PDI), degree of branching (brs), etc.

[0093] Table 2 Effect of the catalysts prepared in Examples 1-4 on the copolymerization of ethylene and methyl acrylate

[0094]

[0095]

[0096] In the table: Activity is 10 3 g / (mol Pd·h), X is the insertion ratio of the polar monomer into the polymer molecular chain, Mn is the number average molecular weight, Mw / Mn is the molecular weight distribution, and brs is the degree of branching (the number of methyl groups per 1000 methylene groups).

[0097] Table 2 shows that these catalysts all exhibit moderate activity (level 10 3 g mol -1 h -1 ) and generate copolymers with moderate molecular weight (3.0-14.0kg / mol). The most notable feature is that under mild copolymerization conditions, these copolymers have a high polar monomer insertion rate (9.21-21.00mol%), and this copolymer has good low-temperature fluidity and can be used in polar additives and special lubricants.

[0098] The above has introduced in detail a kind of catalyst, catalyst composition and preparation method of olefin polymer provided by the present invention. Specific examples are used in this article to elaborate on the principle and implementation manner of the present invention, but the present invention is not limited to the specific implementation manners described herein. Those skilled in the art understand that other changes and deformations can be made without departing from the scope of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A 2,4,8-triarylnaphthylpyridine imine palladium (II) catalyst, characterized in that, The catalyst contains a pyridine imine ligand of 2,4,8-triaryl naphthyl, and the structure of the catalyst is shown in Formula 1 below: ， Formula 1; Wherein, R is selected from H, methyl, F, tert-butyl.

2. A method for preparing a catalyst as described in claim 1, characterized in that, It includes the following steps: S1. Prepare a pyridine imine ligand containing 2,4,8-triaryl naphthyl: Heat and stir aniline solid containing triaryl naphthyl shown in Formula 2, 2-acetylpyridine and p-toluenesulfonic acid in a toluene solution at 90 °C until a main spot appears on the thin layer chromatography plate, evaporate the solvent and concentrate it to 5 ml under vacuum, dilute the remaining solution with methanol for recrystallization to form a solid, wash it with ethanol after filtration, and obtain a solid powder of a pyridine imine palladium (II) ligand containing 2,4,8-triaryl naphthyl shown in Formula 3 after vacuum drying; ， ， Formula 2; Formula 3; S2. Prepare a 2,4,8-triaryl naphthyl pyridine imine palladium (II) catalyst: Under the atmosphere of a protective gas, using dichloromethane as a solvent, mix the pyridine imine ligand containing 2,4,8-triaryl naphthyl prepared in Step S1 with (COD)PdMeCl, stir and react at room temperature, filter the suspension, remove the solvent from the mother liquor under vacuum conditions, wash it with ether, and dry it under vacuum to obtain a solid complex, namely a 2,4,8-triaryl naphthyl pyridine imine palladium (II) catalyst.

3. The preparation method according to claim 2, wherein The stirring reaction time in Step S1 is 24 h.

4. The preparation method according to claim 2, wherein, In Step S2, the molar ratio of the pyridine imine ligand containing 2,4,8-triaryl naphthyl to (COD)PdMeCl is 1:

1.

5. The preparation method according to claim 2, characterized in that, The stirring time in Step S2 is 12 h, and the protective gas is nitrogen.

6. Application of a 2,4,8-triaryl naphthyl pyridine imine palladium (II) catalyst as described in Claim 1 or a 2,4,8-triaryl naphthyl pyridine imine palladium (II) catalyst prepared by the preparation method described in any one of Claims 2-5 in the copolymerization reaction of ethylene and acrylate compounds.

7. The application according to claim 6, characterized in that, The application is carried out in a composite catalytic system composed of a 2,4,8-triaryl naphthyl pyridine imine palladium catalyst and a cocatalyst sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and the molar ratio of the 2,4,8-triaryl naphthyl pyridine imine palladium catalyst to the cocatalyst sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is 1:

2.

8. The application according to claim 6, characterized in that, The temperature for the catalytic ethylene polymerization reaction is 30-70 °C and the time is 180-360 minutes.

9. The application according to claim 6, wherein The acrylate compound is selected from any one of methyl acrylate, ethyl acrylate, and n-butyl acrylate.

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