Trifluoromethoxy-modified pyridine diimine metal complex with high catalytic activity, and preparation method and application thereof

Abstract

The application discloses a trifluoromethoxy-modified pyridine diimine metal complex with high catalytic activity and a preparation method and application thereof. The complex can realize precise regulation of the molecular weight and molecular weight distribution of a polymerization product by modifying and changing substituents on an imine aryl group and polymerization conditions, and high-molecular-weight highly linear polyethylene material (the molecular weight is up to 7.24*10 5 g·mol ‑1 ) is obtained. The application further provides a polymerization condition using an industrial commonly used solvent, namely, n-hexane, as a polymerization solvent, which also has super high catalytic activity and can greatly reduce the amount of a cocatalyst (for example, at 30 DEG C, when toluene is used as the solvent, the activity of Co1 / MAO is 4.90*10 6 g·mol ‑1 (Co)·h ‑1 ; and when n-hexane is used as the solvent, the Co1 / MAO can reach the optimal activity 11.2*10 6 g·mol ‑1 (Co)·h ‑1 ) at Al / Co=650. Meanwhile, the preparation method of the complex is simple, the cost is low, the performance is stable, and the complex has great industrial application potential.

Description

TECHNICAL FIELD

[0001] The present application relates to a trifluoromethoxy-modified pyridine diimine metal complex with high catalytic activity and a preparation method and application thereof, and belongs to the technical field of polyolefin catalysts. BACKGROUND

[0002] Polymer materials have the advantages of low cost, light weight, easy processing, etc., and are widely used in daily life, scientific research and other fields. Its importance and universality has far exceeded that of conventional materials such as metals, cement and ceramics. Its production and industrial application has become one of the pillars of the national economy. Among them, polyethylene material has the characteristics of good chemical resistance, low price, simple preparation, low density and good mechanical properties, etc. It is the largest product in the world of polymer materials. In 1995, Brookhart and Gibbson reported a class of iron and cobalt complexes based on 2,6-diacetylpyridine skeleton, which can efficiently catalyze ethylene polymerization to obtain highly linear polyethylene.

[0003]

[0004] The research group of the present application has carried out research work in the field of late transition metal olefin catalysts for 20 years. By modifying the ligand skeleton, the electronic effect and steric hindrance effect are adjusted to improve the catalytic activity and thermal stability, and the structure and performance of polyethylene products are precisely controlled. The international peers have paid close attention to it and highly recognized it. For example, in the following formula 2, the benzhydryl group is introduced into the imine aryl group, which effectively improves the thermal stability of the catalyst; the chlorine is introduced into the para position of the imine aryl group, which improves the catalytic activity of the catalyst.

[0005]

[0006] However, the catalytic performance, preparation method, etc. of the above-mentioned catalysts still need to be further improved. SUMMARY

[0007] The purpose of the present application is to provide a trifluoromethoxy-containing asymmetric pyridine diimine metal complex. By modifying the substituents on the imine aryl group and changing the ethylene polymerization conditions, the molecular weight and molecular weight distribution of the polymerization product can be precisely controlled, and high molecular weight highly linear polyethylene material (molecular weight up to 7.24×10 5 g·mol -1 ) can be obtained.

[0008] The present application first provides a ligand compound represented by formula II,

[0009]

[0010] In the formula, R1 R 2 Whether the groups are the same or different, each is independently selected from H, F, Cl, Br, I, nitro, and optionally substituted with one or more R groups. a The following groups are substituted: C 1-6 Alkyl or C 1-6 Alkoxy;

[0011] R 3 R 4 Whether the groups are the same or different, each is independently selected from H, F, Cl, Br, I, nitro, and optionally substituted with one or more R groups. b The following groups are substituted: C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 cycloalkyl, C 3-10 Cycloalkoxy, aryl, aryloxy, arylC 1-6 Alkylene;

[0012] R a R b Whether the samples are the same or different, they are each independently selected from H, F, Cl, Br, I, and C. 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 cycloalkyl, C 3-10 Cycloalkoxy, aryl, and aryloxy.

[0013] The ligand compound can specifically be any one of ligands L1-L5:

[0014] In ligand L1, R 1 =Me, all other groups are H; in ligand L2, R 1 =Et, all other groups are H; R in ligand L3 1 = i Pr, all other groups are H, and R in ligand L4 1 =R 2 =Me, all other groups are H; R in ligand L5 1 =Et,R 2 =Me, and all other groups are H.

[0015] The ligand compound can be prepared by a method comprising the following steps:

[0016] 1) The 2,6-diacetylpyridine of Formula III is condensed with the aniline of Formula IV to obtain the compound of Formula V (this step is performed according to the method described in Eur. J. Inorg. Chem., 2003, 1620–1631);

[0017] 2) The compound shown in Formula V is condensed with aniline shown in Formula VI to obtain the ligand compound shown in Formula II;

[0018] The condensation reaction was carried out under the catalysis of p-toluenesulfonic acid, with toluene as the solvent.

[0019] The condensation reaction is preferably carried out under reflux conditions for 2 to 10 hours.

[0020] The molar ratio of the compound shown in Formula V to the aniline shown in Formula VI is 1:1 to 2.

[0021]

[0022] Among them, R 1 R 2 R 3 R 4 The definition is the same as that of the ligand compounds shown in II;

[0023] After the reaction in step 2) is complete, the ligand compound shown in formula ) can be further purified. The purification method includes the following steps.

[0024] a) Remove the solvent from the solution obtained in step 2), and dissolve the resulting solid in dichloromethane;

[0025] b) Using alumina as the support, a mixed solution of petroleum ether and ethyl acetate (volume ratio of petroleum ether and ethyl acetate of 100:3) was used as the eluent. Column chromatography was performed using alumina, and the eluted fraction was detected by thin-layer chromatography (the developing solvent was a mixed solution of petroleum ether and ethyl acetate of 3:2, and the second fraction was collected).

[0026] c) Remove the solvent and recrystallize using dichloromethane and methanol to obtain the purified ligand compound shown in Formula II.

[0027] Based on the ligand compounds described above, this invention provides an asymmetric pyridine diimide metal complex of Formula I containing a trifluoromethoxy group.

[0028]

[0029] In the formula, M is selected from Fe and Co;

[0030] R 1 R 2 Whether the groups are the same or different, each is independently selected from H, F, Cl, Br, I, nitro, and optionally substituted with one or more R groups. a The following groups are substituted: C 1-6 Alkyl or C 1-6 Alkoxy;

[0031] R 3 R4 Whether the groups are the same or different, each is independently selected from H, F, Cl, Br, I, nitro, and optionally substituted with one or more R groups. b The following groups are substituted: C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 cycloalkyl, C 3-10 Cycloalkoxy, aryl, aryloxy, arylC 1-6 Alkylene;

[0032] X may be the same or different, and each is independently selected from F, Cl, Br and I;

[0033] R a R b Whether the samples are the same or different, they are each independently selected from H, F, Cl, Br, I, and C. 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 cycloalkyl, C 3-10 Cycloalkoxy, aryl, aryloxy.

[0034] Specifically, in formula I, R 1 R 2 Whether the two are the same or different, they are each independently selected from H and C. 1-3 alkyl;

[0035] R 3 R 4 Whether the samples are the same or different, they are each independently selected from H, F, Cl, Br, I, and C. 1-3 Alkyl or C 1-3 alkylene aryl;

[0036] X may be the same or different, and each is independently selected from Cl and Br.

[0037] Preferably, the asymmetric pyridine diimine metal complex is either complex Fe1-Fe5 or complex Co1-Co5.

[0038] In the complex Fe1, R 1 =Me, M=Fe, X=Cl, other groups are H; complex Fe2: where R 1 =Et, M=Fe, X=Cl, other groups are H; complex Fe3: where R 1 = i Pr, M = Fe, X = Cl, other groups are H; complex Fe4: where R 1 =R 2 =Me, M=Fe, X=Cl, other groups are H; complex Fe5: where R 1 =Et,R 2 =Me, M=Fe, X=Cl, and other groups are H;

[0039] Co1 complex: where R 1 =Me, M=Co, X=Cl, other groups are H; Complex Co2: where R 1 =Et, M=Co, X=Cl, other groups are H; Complex Co3: where R 1 = i Pr, M = Co, X = Cl, other groups are H; complex Co4: where R 1 =R 2 =Me, M=Co, X=Cl, other groups are H; Complex Co5: where R 1 =Et,R 2 =Me, M=Co, X=Cl, and other groups are H.

[0040] The present invention also provides a method for preparing the asymmetric pyridine diimine metal complex, comprising the following steps:

[0041] The ligand compound shown in Formula II is complexed with metal halide MX2 to obtain the asymmetric pyridinediimide metal complex as described in claim 4 or 5.

[0042] Where M is selected from Fe and Co, and X is selected from F, Cl, Br and I;

[0043] The complexation reaction is carried out under an inert gas atmosphere;

[0044] The molar ratio of the metal halide MX2 to the compound shown in Formula II is 1:1 to 2.

[0045] Based on the aforementioned asymmetric pyridinediimide metal complex, the present invention also provides a catalyst composition comprising a main catalyst and an optional co-catalyst, wherein the main catalyst is selected from the asymmetric pyridinediimide metal complex containing trifluoromethoxy as shown in Formula I.

[0046] The co-catalyst is selected from one or both of methylaluminoxane or triisobutylaluminum-modified methylaluminoxane;

[0047] The molar ratio of metal Al in the co-catalyst to the central metal Fe or Co of the asymmetric pyridine diimine metal complex containing trifluoromethoxy as shown in Formula I is 500–4000:1.

[0048] Preferably, when the co-catalyst is methylaluminoxane (MAO), the molar ratio of metal Al in methylaluminoxane (MAO) to the central metal Fe or Co of the complex shown in Formula I is 1000 to 3000:1, and more preferably the molar ratio is 2000:1;

[0049] Preferably, when the co-catalyst is triisobutylaluminum-modified methylaluminoxane (MMAO), the molar ratio of metal Al in triisobutylaluminum-modified methylaluminoxane (MMAO) to the central metal Fe or Co of the complex shown in Formula I is 1500 to 4000:1, and more preferably 3000:1.

[0050] The application of the trifluoromethoxy-containing asymmetric pyridine diimide metal complex of Formula I and the catalyst composition in the catalytic polymerization of olefins is also within the scope of protection of this invention; preferably, it is used in the polymerization of ethylene.

[0051] Furthermore, the present invention also provides an olefin polymerization reaction, including the step of using the catalyst composition to catalyze the polymerization reaction of ethylene;

[0052] Preferably, the polymerization reaction is carried out at a temperature of 20–100°C for a time of 5–60 min.

[0053] The polymerization reaction is carried out under a pressure of 0.5–10 atm;

[0054] The solvent for the polymerization reaction is selected from one or more of toluene, o-xylene, n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, dichloromethane, ethanol, and tetrahydrofuran. In particular, when the commonly used industrial solvents provided by this invention are used as polymerization solvents, the resulting catalytic activity is high and the amount of co-catalyst required is greatly reduced.

[0055] The polymerization reaction was carried out in an ethylene atmosphere.

[0056] The complexes provided by this invention can achieve precise control over the molecular weight and molecular weight distribution of the polymerization product by modifying the substituents on the imine aryl group and changing the ethylene polymerization conditions, thereby obtaining high molecular weight, highly linear polyethylene materials (with a molecular weight as high as 7.24 × 10⁻⁶). 5 g·mol -1 This invention also provides polymerization conditions using n-hexane, a commonly used industrial solvent, as the polymerization solvent. These conditions also exhibit extremely high catalytic activity and can significantly reduce the amount of co-catalyst required (for example, at 30°C, when toluene is used as the solvent, the Co1 / MAO activity is 4.90 × 10⁻⁶ at Al / Co = 1750). 6 g·mol -1 (Co)·h -1 In n-hexane, the Co1 / MAO ratio reaches its optimal activity (11.2 × 10⁻⁶) when Al / Co = 650. 6 g·mol -1 (Co)·h -1 Meanwhile, the preparation method of this type of complex is simple, low-cost, and stable, and it has great potential for industrial application. Attached Figure Description

[0057] Figure 1 The image shows the crystal structure of the Co2 complex prepared in Example 7.

[0058] Figure 2 The crystal structure diagram of the Co5 complex prepared in Example 10 is shown.

[0059] Figure 3 The crystal structure diagram of the complex Fe1 prepared in Example 11 is shown.

[0060] Figure 4 The crystal structure diagram of the Fe2 complex prepared in Example 12 is shown.

[0061] Figure 5 The temperature-controlled carbon NMR spectrum of the polymer prepared in Example 16a) is shown.

[0062] Figure 6 The heated carbon NMR spectrum of the polymer prepared in Example 16h is shown.

[0063] Figure 7 The temperature-controlled carbon NMR spectrum of the polymer prepared in Example 21a) is shown.

[0064] Figure 8 This study compares the catalytic performance of the Co4 / MAO system with similar systems previously reported.

[0065] Figure 9 This study compares the catalytic performance of the Fe3 / MAO system with similar systems previously reported. Detailed Implementation

[0066] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0067] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0068] The methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) used as reference standards were both purchased from Anhui Botai Electronic Materials Co., Ltd.

[0069] Example 1: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-dimethyl-aniline)ethyl)pyridine (L1)

[0070]

[0071] In a 100 mL round-bottom flask, 0.53 g (2 mmol) of 2-acetyl-6-(1-(2,6-dimethylaniline)ethylpyridine, 1.51 g (3 mmol) of 2,6-bis(diphenylmethyl)-4-trifluoromethoxyaniline, 0.61 g of p-toluenesulfonic acid, and 30 mL of toluene were added. The mixture was heated to reflux and reacted for 6 h. The solvent was removed using a rotary evaporator. The remaining solid was supported on alumina and eluent was obtained by column chromatography using alumina with a mixture of petroleum ether and ethyl acetate (volume ratio of 100:3). The eluent was analyzed by thin-layer chromatography (using a mixture of petroleum ether and ethyl acetate (volume ratio of 3:1), and the third fraction was collected). After removing the solvent, the solid was recrystallized from dichloromethane and methanol, filtered, and dried to obtain a yellow solid. Yield: 20%.

[0072] The structural evidence is as follows:

[0073] 1 H NMR (400MHz, CDCl3, TMS): δ8.42(d,J=7.6Hz,1H,Py-H),8.04(d,J=7.6Hz,1H,Py-H),7.84(t,J=7.8Hz,1H,Py-H),7.28-7.14(m,12H,Ar-H),7.08( d,J=7.6Hz,2H,Ar-H),7.03-6.93(m,9H,Ar-H),6.76(s,2H,Ar-H),5.30(s,2H,-CHPh2),2.11(s,3H,-CH3),2.06(s,6H,-CH3),1.10(s,3H,-CH3).

[0074] 13 C NMR (100MHz, CDCl3, TMS): δ170.56,167.22,155.03,154.61,148.69,146.95,142.62,141.67,136.72,134.15,129.71, 129.30,128.50,128.25,127.91,126.48,126.45,125.40,123.06,122.32,122.21,120.98,52.08,17.97,17.02,16.40.

[0075] 19 F NMR (470MHz, CDCl3, TMS): δ-58.15.

[0076] FT-IR (cm) -1):3065(w),3026(w),2965(w),2920(w),1635(m,v C＝N) ,1596(w,v C＝N ),1572(w),1494(w),1444(m),1366(w),1326(w),1300(w),1250(s),1217(m),1187(w),1166 (m),1123(w),1079(w),1033(w),1005(w),969(w),905(w),865(w),820(w),767(m),699(s).

[0077] Anal.calcd for C 50 H 42 F3N3O (757.90): C, 79.24; H, 5.59; N, 5.54. Found: C, 79.61; H, 5.96; N, 5.23%.

[0078] Example 2: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diethyl-aniline)ethyl)pyridine (L2)

[0079]

[0080] The method is basically the same as in Example 1, except that, while maintaining the same molar amount of reactants, the pyridine compound participating in the reaction is 2-acetyl-6-(1-(2,6-diethyl-aniline)ethylpyridine, and the product is a yellow solid. Yield: 22%.

[0081] The structural evidence is as follows:

[0082] 1 H NMR (400MHz, CDCl3, TMS): δ8.41 (d, J=7.2Hz, 1H, Py-H), 8.04 (d, J=8.0Hz, 1H, Py-H) ),7.84(t,J=7.8Hz,1H,Py-H),7.28-7.16(m,12H,Ar-H),7.13(d,J=7.6Hz,2H,Ar-H ),7.05-6.99(m,9H,Ar-H),6.76(s,2H,Ar-H),5.30(s,2H,-CHPh2),2.48-2.31(m,4 H,-CH2CH3),2.12(s,3H,-CH3),1.16(t,J=7.4Hz,6H,-CH2CH3),1.10(s,3H,-CH3).

[0083] 13 C NMR (100MHz, CDCl3, TMS): δ170.59,166.98,155.08,154.64,147.76,146.98,142.64,141.70,136.75,134.16,131.17,129 .73,129.31,128.50,128.26,126.48,126.46,125.96,123.36,122.28,122.18,120.98,52.09,24.59,17.04,16.76,13.76.

[0084] 19 F NMR (470MHz, CDCl3, TMS): δ-58.15.

[0085] FT-IR (cm) -1 ):3062(w),3024(w),2965(w),2932(w),1634(m,v C＝N) ,1596(w,v C＝N ),1574(w),1494(w),1446(m),1367(w),1325(w),1300(w),1250(s),1220(m),1189(w),1168(m),1123(w) ,1103(w),1077(w),1032(w),1010(w),966(w),903(w),866(w),823(w),803(w),769(m),747(w),700(s).

[0086] Anal.calcd for C 52 H 46 F3N3O·H2O (803.97): C, 77.69; H, 6.02; N, 5.23. Found: C, 77.90; H, 6.03; N, 5.22%.

[0087] Example 3: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diisopropyl-aniline)ethyl)pyridine (L3)

[0088]

[0089] The method is basically the same as in Example 1, except that, while maintaining the same molar amounts of reactants, the pyridine compound involved in the reaction is 2-acetyl-6-(1-(2,6-isopropyl-aniline)ethylpyridine, and the product is a yellow solid. Yield: 25%.

[0090] The structural confirmation evidence is as follows:

[0091] 1 H NMR (400 MHz, CDCl3, TMS): δ 8.40 (d, J = 7.6 Hz, 1H, Py-H), 8.04 (d, J = 7.2 Hz, 1H, Py-H), 7.85 (t, J = 7.8 Hz, 1H, Py-H), 7.28 - 7.23 (m, 4H, Ar-H), 7.22 - 7.16 (m, 10H, Ar-H), 7.14 - 7.09 (m, 1H, Ar-H), 7.03 - 6.96 (m, 9H, Ar-H), 6.76 (s, 2H, Ar-H), 5.30 (s, 2H, -CHPh2), 2.81 - 2.74 (m, 2H, -CH(CH3)2), 2.13 (s, 3H, -CH3), 1.18 (d, J = 6.8 Hz, 12H, -CH(CH3)2), 1.12 (s, 3H, -CH3).

[0092] 13 C NMR (100 MHz, CDCl3, TMS): δ 170.62, 167.05, 155.06, 154.64, 146.98, 146.42, 142.62, 141.69, 136.75, 135.79, 134.15, 129.72, 129.30, 128.49, 128.25, 126.47, 123.62, 123.02, 122.26, 120.98, 52.08, 28.30, 23.25, 22.93, 17.12, 17.04.

[0093] 19 F NMR (470 MHz, CDCl3, TMS): δ -58.14.

[0094] FT-IR (cm -1 ): 3062 (w), 3026 (w), 2959 (w), 2928 (w), 1631 (m, v C＝N) , 1598 (w, v C＝N ), 1574 (w), 1496 (w), 1441 (m), 1369 (w), 1326 (w), 1309 (w), 1255 (s), 1222 (m), 1187 (w), 1167 (s), 1126 (w), 1104 (w), 1077 (w), 1032 (w), 1006 (w), 967 (w), 863 (w), 824 (w), 798 (w), 769 (m), 744 (w), 700 (s).

[0095] Anal.calcd for C 54 H 50 F3N3O (814.01): C, 79.68; H, 6.19; N, 5.16. Found: C, 79.64; H, 6.20; N, 5.18%.

[0096] Example 4: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,4,6-trimethyl-aniline)ethyl)pyridine (L4)

[0097]

[0098] The method is basically the same as in Example 1, except that, while maintaining the same molar amounts of reactants, the pyridine compound involved in the reaction is 2-acetyl-6-(1-(2,4,6-trimethylaniline)ethylpyridine, and the product is a yellow solid. Yield: 19%.

[0099] The structural evidence is as follows:

[0100] 1 H NMR (400MHz, CDCl3, TMS): δ8.41 (d, J=7.2Hz, 1H, Py-H), 8.04 (d, J=7.6Hz, 1H, Py-H), 7.83 (t, J=7.8Hz, 1H, Py-H), 7.28-7.14 (m, 11H, Ar-H), 7.03-6.98 (m,9H,Ar-H),6.90(s,2H,Ar-H),6.75(s,2H,Ar-H),5.30(s,2H,-CHPh2),2 .30(s,3H,-CH3),2.10(s,3H,-CH3),2.02(s,6H,-CH3),1.10(s,3H,-CH3).

[0101] 13 C NMR (100MHz, CDCl3, TMS): δ170.53,167.37,155.15,154.55,146.94,146.16,144.54,142.60,141.66,136.65,134.13,132.22, 129.68,129.27,128.54,128.47,128.21,126.44,126.41,125.21,122.21,122.16,120.94,52.05,20.70,17.86,17.00,16.30.

[0102] 19F NMR (470MHz, CDCl3, TMS): δ-58.15.

[0103] FT-IR (cm) -1 ):3062(w),3026(w),2965(w),2916(w),1643(m,v C＝N) ,1600(w,v C＝N ),1575(w),1494(w),1447(m),1365(w),1326(w),1297(w),1253(s),1214(m),1190(w),1163(m) ,1123(w),1099(w),1078(w),1011(w),969(w),858(w),816(w),796(w),767(w),737(w),699(s).

[0104] Anal.calcd for C 51 H 44 F3N3O·2H2O (807.96): C, 75.82; H, 5.99; N, 5.20. Found: C, 75.51; H, 5.95; N, 5.02%.

[0105] Example 5: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diethyl-4-methyl-aniline)ethyl)pyridine (L5)

[0106]

[0107] The method is basically the same as in Example 1, except that, while maintaining the same molar amount of reactants, the pyridine compound participating in the reaction is 2-acetyl-6-(1-(2,6-diethyl-4-methyl-aniline)ethylpyridine, and the product is a yellow solid. Yield: 22%.

[0108] The structural evidence is as follows:

[0109] 1H NMR(400MHz,CDCl3,TMS):δ8.40(d,J=7.6Hz,1H,Py-H),8.03(d,J=7.2Hz,1H,Py-H),7.83(t,J=7.8Hz,1H,Py-H),7.28-7.14(m,12H,Ar-H),7.03-6.98(m,8H,Ar-H),6.94(s,2H,Ar-H),6.75(s,2H,Ar-H),5.30(s,2H,-CHPh2),2.44-2.28(m,7H,-CH2CH3,-CH3),2.11(s,3H,-CH3),1.14(t,J=7.6Hz,6H,-CH2CH3),1.10(s,3H,-CH3).

[0110] 13 C NMR(100MHz,CDCl3,TMS):δ170.60,167.17,155.22,154.59,147.00,145.24,144.57,142.65,141.71,136.70,134.16,132.48,131.07,129.73,129.31,128.50,128.25,126.71,126.48,126.45,122.20,120.97,52.09,24.58,21.01,17.04,16.70,13.87.

[0111] 19 F NMR(470MHz,CDCl3,TMS):δ-58.14.

[0112] FT-IR(cm -1 ):3062(w),3026(w),2969(w),2934(w),1641(m,v C＝N) ,1602(w,v C＝N ),1568(w),1494(m),1442(m),1361(m),1324(w),1295(w),1253(m),1223(w),1189(w),1149(m),1120(w),1080(w),1030(w),1012(w),972(w),917(w),861(w),821(w),800(w),768(w),739(m),697(s).

[0113] Anal.calcd for C 53 H 48F3N3O·H2O (818.00): C, 77.82; H, 6.16; N, 5.14. Found: C, 78.04; H, 6.09; N, 5.15%.

[0114] Example 6: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-dimethyl-aniline)ethyl)pyridinecobalt chloride (Co1)

[0115]

[0116] In a 25 mL Shrek flask, 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-dimethyl-aniline)ethyl)pyridine (0.12 g, 0.16 mmol), cobalt chloride hexahydrate (0.038 g, 0.16 mmol), dichloromethane (3 mL), and ethanol (4 mL) were added. The solution was stirred at room temperature under N2 atmosphere for 12 h. The solvent was removed under reduced pressure, and a solid precipitated upon the addition of diethyl ether. The precipitate was filtered, washed with diethyl ether, and dried to obtain a brown solid. Yield: 90%.

[0117] The structural evidence is as follows:

[0118] 19 F NMR (470MHz, CDCl3, TMS): δ-59.49.

[0119] FT-IR (cm) -1 ):3062(w),3020(w),2965(w),2916(w),1624(m,v C＝N) ,1586(w,v C＝N ),1494(w),1444(w),1371(w),1319(w),1262(s),1214(m),1203(w),1148(m),108 5(w),1030(w),1012(w),867(w),835(w),811(w),766(w),731(w),704(s),657(w).

[0120] Anal.calcd for C 50 H 42 Cl2CoF3N3O·H2O (905.75): C, 66.30; H, 4.90; N, 4.64. Found: C, 66.29; H, 4.76; N, 4.75%.

[0121] Example 7: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diethyl-aniline)ethyl)pyridinecobalt chloride (Co2)

[0122]

[0123] The method is basically the same as in Example 6, except that, while maintaining the same molar amounts of reactants, the pyridine compound participating in the reaction is 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diethyl-aniline)ethyl)pyridine, and the product is a brown solid. Yield: 78%. The molecular structure of Co2 is as follows: Figure 1 As shown.

[0124] The structural evidence is as follows:

[0125] 19 F NMR (470MHz, CDCl3, TMS): δ-59.33.

[0126] FT-IR (cm) -1 ):3061(w),3032(w),2973(w),2913(w),1624(m,v C＝N) ,1583(w,v C＝N ),1496(w),1446(m),1375(w),1317(w),1253(s),1218(m),1165(m),1079(w),1024(w ),986(w),922(w),901(w),873(w),842(w),810(m),770(w),744(w),702(s),658(w).

[0127] Anal.calcd for C 52 H 46 Cl2CoF3N3O·H2O (933.80): C, 66.88; H, 5.18; N, 4.50. Found: C, 67.33; H, 4.99; N, 4.21%.

[0128] Example 8: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diisopropyl-aniline)ethyl)pyridinecobalt chloride (Co3)

[0129]

[0130] The method is basically the same as in Example 6, except that, while maintaining the same molar amount of reactants, the pyridine compound participating in the reaction is 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diisopropyl-aniline)ethyl)pyridine, and the product is a brown solid. Yield: 82%.

[0131] The structural evidence is as follows:

[0132] 19 F NMR (470MHz, CDCl3, TMS): δ-59.29.

[0133] FT-IR (cm) -1 ):3064(w),3024(w),2963(w),1624(w,v C＝N) ,1586(w,v C＝N ),1493(w),1446(w),1368(w),1319(w),1252(s),1218(m),1166(m),1102(w),1077(w),1022(w),9 81(w),924(w),906(w),875(w),837(w),812(w),793(w),762(w),746(w),703(s),681(w),657(w).

[0134] Anal.calcd for C 54 H 50 Cl2CoF3N3O (943.84): C, 68.72; H, 5.34; N, 4.45. Found: C, 68.51; H, 5.29; N, 4.16%.

[0135] Example 9: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,4,6-trimethyl-aniline)ethyl)pyridinecobalt chloride (Co4)

[0136]

[0137] The method is basically the same as in Example 6, except that, while maintaining the same molar amount of reactants, the pyridine compound participating in the reaction is 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,4,6-trimethyl-aniline)ethyl)pyridine, and the product is a brown solid. Yield: 85%.

[0138] The structural evidence is as follows:

[0139] 19F NMR (470MHz, CDCl3, TMS): δ-59.49.

[0140] FT-IR (cm) -1 ):3064(w),3024(w),2968(w),2915(w),1626(w,v C＝N) ,1585(w,v C＝N ),1494(w),1442(w),1373(w),1321(w),1249(s),1212(m),1179(w),1077(w) ,1031(w),986(w),924(w),854(w),810(m),768(w),742(w),704(s),658(w).

[0141] Anal.calcd for C 51 H 44 Cl2CoF3N3O·H2O (919.78): C, 66.60; H, 5.04; N, 4.57. Found: C, 67.00; H, 4.85; N, 4.21%.

[0142] Example 10: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diethyl-4-methyl-aniline)ethyl)pyridinecobalt chloride (Co5)

[0143]

[0144] The method is basically the same as in Example 6, except that, while maintaining the same molar amounts of reactants, the pyridine compound involved in the reaction is 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diethyl-4-methyl-aniline)ethyl)pyridine, and the product is a brown solid. Yield: 85%. The molecular structure of Co5 is as follows: Figure 2 As shown.

[0145] The structural evidence is as follows:

[0146] 19 F NMR (470MHz, CDCl3, TMS): δ-59.34.FT-IR (cm -1 ):3062(w),2969(w),2906(w),1624(w,v C＝N) ,1585(w,v C＝N),1493(w),1448(w),1373(w),1321(w),1253(s),1212(w),1177(w),1113(w) ,1075(w),1032(w),920(w),863(w),813(w),766(w),740(w),702(s),659(w).

[0147] Anal.calcd for C 53 H 48 Cl2CoF3N3O·H2O (947.83): C, 67.16; H, 5.32; N, 4.43. Found: C, 67.25; H, 5.23; N, 4.10%.

[0148] Example 11: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-dimethyl-aniline)ethyl)pyridine ferric chloride (Fe1)

[0149]

[0150] In a 25 mL Shrek flask, 0.15 g (0.2 mmol) of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-dimethyl-aniline)ethyl)pyridine, 0.04 g (0.2 mmol) of ferrous chloride tetrahydrate, and 6 mL of tetrahydrofuran were added. The solution was stirred at room temperature under N2 atmosphere for 12 h. The solvent was removed under reduced pressure, and a solid precipitated upon the addition of diethyl ether. The precipitate was filtered, washed with diethyl ether, and dried to obtain a blue solid. Yield: 79%. The molecular structure of Fe1 is as follows: Figure 3 As shown.

[0151] The structural evidence is as follows:

[0152] 19 F NMR (470MHz, CDCl3, TMS): δ-57.38.

[0153] FT-IR (cm) -1 ):3062(w),3026(w),2954(w),2916(w),1621(m,v C＝N) ,1586(w,v C＝N ),1495(w),1445(w),1373(w),1253(s),1215(w),1166(w),1097(w),108 0(w),1029(w),981(w),922(w),871(w),809(w),768(w),700(s),657(w).

[0154] Example 12: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diethyl-aniline)ethyl)pyridine ferric chloride (Fe2)

[0155]

[0156] The method is basically the same as in Example 11, except that, while maintaining the same molar amounts of reactants, the pyridine compound involved in the reaction is 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diethyl-aniline)ethyl)pyridine, and the product is a blue solid. Yield: 87%. The molecular structure of Fe2 is as follows: Figure 4 As shown.

[0157] The structural evidence is as follows:

[0158] 19 F NMR (470MHz, CDCl3, TMS): δ-57.27.

[0159] FT-IR (cm) -1 ):3065(w),3032(w),2972(w),2920(w),1605(m,v C＝N) ,1581(w,v C＝N ),1496(w),1445(m),1376(w),1319(w),1253(s),1221(m),1166(m),1108(w),107 8(w),1032(w),924(w),903(w),875(w),809(m),770(w),742(w),702(s),657(w).

[0160] Example 13: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diisopropyl-aniline)ethyl)pyridine ferric chloride (Fe3)

[0161]

[0162] The method is basically the same as in Example 11, except that, while maintaining the same molar amount of reactants, the pyridine compound involved in the reaction is 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diisopropyl-aniline)ethyl)pyridine, and the product is a blue solid. Yield: 82%.

[0163] The structural evidence is as follows:

[0164] 19 F NMR (470MHz, CDCl3, TMS): δ-57.27.

[0165] FT-IR (cm) -1 ):3060(w),3024(w),2962(w),2923(w),1631(m,v C＝N) ,1583(w,v C＝N ),1494(w),1444(m),1372(w),1321(w),1252(s),1213(m),1162(m),1102(w) ,1083(w),1031(w),924(w),869(w),801(m),770(w),750(w),701(s),658(w).

[0166] Example 14: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,4,6-trimethyl-aniline)ethyl)pyridine ferric chloride (Fe4)

[0167]

[0168] The method is basically the same as in Example 11, except that, while maintaining the same molar amount of reactants, the pyridine compound participating in the reaction is 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,4,6-trimethyl-aniline)ethyl)pyridine, and the product is a blue solid. Yield: 84%.

[0169] The structural evidence is as follows:

[0170] 19 F NMR (470MHz, CDCl3, TMS): δ-57.29.

[0171] FT-IR (cm) -1 ):3062(w),3027(w),2961(w),2921(w),1616(m,v C＝N) ,1584(w,v C＝N ),1495(w),1475(w),1441(m),1373(m),1319(w),1249(s),1214(m),1198(w),1174(w) ,1078(w),1030(w),1009(w),924(w),858(w),810(m),764(w),733(w),703(s),658(w).

[0172] Example 15: Preparation of 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diethyl-4-methyl-aniline)ethyl)pyridine ferric chloride (Fe5)

[0173]

[0174] The method is basically the same as in Example 11, except that, while maintaining the same molar amounts of reactants, the pyridine compound involved in the reaction is 2-(1-(2,6-bis(diphenylmethyl))-4-trifluoromethoxy-aniline)ethyl-6-(1-(2,6-diethyl-4-methyl-aniline)ethyl)pyridine, and the product is a blue solid. Yield: 78%.

[0175] The structural evidence is as follows:

[0176] 19 F NMR (470MHz, CDCl3, TMS): δ-57.18.

[0177] FT-IR (cm) -1 ):3062(w),3027(w),2965(w),2935(w),1602(m,v C＝N) ,1582(w,v C＝N ),1495(m),1444(m),1373(m),1324(w),1254(s),1213(m),1200(w),1166(w),1112 (w),1078(w),1032(w),1015(w),859(w),817(w),768(w),732(w),701(s),660(w).

[0178] Example 16: Ethylene polymerization catalyzed by the Co1 / MAO system:

[0179] a) Under an ethylene atmosphere, 25 ml of toluene, 50 ml of a toluene solution containing 2 μmol of catalyst Co1, 2.4 ml of a 1.46 mol / L toluene solution of co-catalyst MAO, and 25 ml of toluene were sequentially added to a 250 ml high-pressure reactor. At this point, the Al / Co ratio was 1750:1. The stirring speed was maintained at 400 rpm. When the system temperature reached 30°C, the ethylene pressure inside the reactor was increased to 10 atm. During the reaction, the system temperature and the ethylene pressure remained constant at 10 atm. After reacting for 30 min, stirring was stopped, and the reaction solution was neutralized with a 10% hydrochloric acid ethanol solution to obtain a polymer precipitate. After washing several times with ethanol, the precipitate was dried under vacuum to constant weight, yielding 4.90 g of polymer. The polymerization activity was 4.90 × 10⁻⁶.6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =4.27×10 5 g·mol -1 PDI = 3.45 (polymer weight-average molecular weight M) w The molecular weight distribution (PDI) was obtained by high-temperature GPC testing, and the polymer T... m =135.4℃ (polymer melting temperature T) m (Originally obtained from DSC testing).

[0180] Take 30 mg of the obtained polymer, dissolve it in 1 ml of deuterated 1,1,2,2-tetrachloroethane, and test at 100 °C. 13 C NMR data. The obtained signal peak at 30 ppm indicates a methylene shift peak, proving that the obtained polymer is highly linear polyethylene (see details). Figure 5 ).

[0181] b) is basically the same as method a) in this embodiment, except that 1.4 ml of co-catalyst MAO (1.46 mol / L toluene solution) is used to make Al / Co = 1000:1. Polymerization activity: 2.72 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.94×10 5 g·mol -1 PDI = 2.62, polymer T m =135.5℃.

[0182] c) is basically the same as method a) in this embodiment, except that 3.4 ml of co-catalyst MAO (1.46 mol / L toluene solution) is used to make Al / Co = 2500:1. Polymerization activity: 3.86 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =1.99×10 5 g·mol -1 PDI = 2.45, polymer T m =135.9℃.

[0183] d) Basically the same as method a) in this embodiment, except that the polymerization temperature is 20℃. Polymerization activity: 4.84×10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w=6.40×10 5 g·mol -1 PDI = 3.31, polymer T m =134.8℃.

[0184] e) Basically the same as method a) in this embodiment, except that the polymerization temperature is 70℃. Polymerization activity: 3.12×10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =0.74×10 5 g·mol -1 PDI = 3.25, polymer T m =132.8℃.

[0185] f) is basically the same as method a) in this embodiment, except that the polymerization time is 60 min. Polymerization activity: 4.22 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =6.29×10 5 g·mol -1 PDI = 3.64, polymer T m =135.3℃.

[0186] g) is basically the same as method a) in this embodiment, except that the ethylene pressure is 1 atm. Polymerization activity: 1.57 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.12×10 5 g·mol -1 PDI = 3.01, polymer T m =134.7℃.

[0187] h) is basically the same as method a) in this embodiment, except that: n-hexane is used as the solvent; 0.89 ml of co-catalyst MAO (1.46 mol / L toluene solution) is added to make Al / Co = 650:1. Polymerization activity: 11.2 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =3.22×10 5 g·mol -1 PDI = 3.76, polymer T m =134.8℃.

[0188] Take 30 mg of the obtained polymer, dissolve it in 1 ml of deuterated 1,1,2,2-tetrachloroethane, and test at 100 °C. 13 C NMR data. The obtained signal peak at 30 ppm indicates a methylene shift peak, proving that the obtained polymer is highly linear polyethylene (see details). Figure 6 ).

[0189] Example 17: Ethylene polymerization catalyzed by a Co2 / MAO system:

[0190] a) Basically the same as Example 16a), except that the main catalyst is Co2. Polymerization activity: 5.37 × 10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =3.19×10 5 g·mol -1 PDI = 2.55, polymer T m =135.6℃.

[0191] b) Basically the same as Example 16h), except that the main catalyst is Co2. Polymerization activity: 8.17 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =3.80×10 5 g·mol -1 PDI = 3.66, polymer T m =135.2℃.

[0192] Example 18: Ethylene polymerization catalyzed by a Co3 / MAO system:

[0193] a) Same as Example 16a), except that the main catalyst is Co3. Polymerization activity: 2.40 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =4.40×10 5 g·mol -1 PDI = 1.77, polymer T m =135.6℃.

[0194] b) Basically the same as Example 16h), except that the main catalyst is Co3. Polymerization activity: 8.80 × 10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w=5.05×10 5 g·mol -1 PDI = 3.34, polymer T m =134.4℃.

[0195] Example 19: Ethylene polymerization catalyzed by a Co4 / MAO system:

[0196] a) Basically the same as Example 16a), except that the main catalyst is Co4. Polymerization activity: 7.40 × 10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =4.02×10 5 g·mol -1 PDI = 2.34, polymer T m =135.0℃.

[0197] b) Basically the same as Example 16h), except that the main catalyst is Co4. Polymerization activity: 4.90 × 10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =4.79×10 5 g·mol -1 PDI = 3.33, polymer T m =135.1℃.

[0198] Example 20: Ethylene polymerization catalyzed by a Co5 / MAO system:

[0199] a) Basically the same as Example 16a), except that the main catalyst is Co5. Polymerization activity: 9.87 × 10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =4.93×10 5 g·mol -1 PDI = 2.92, polymer T m =135.3℃.

[0200] b) Basically the same as Example 16h), except that the main catalyst is Co5. Polymerization activity: 10.8 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.92×10 5 g·mol -1PDI = 5.64, polymer T m =134.5℃.

[0201] Example 21: Ethylene polymerization catalyzed by the Co1 / MMAO system:

[0202] a) Under an ethylene atmosphere, 25 ml of toluene, 50 ml of a toluene solution containing 2 μmol of catalyst Co1, 2.6 ml of a 1.93 mol / L toluene solution of co-catalyst MMAO, and 25 ml of toluene were sequentially added to a 250 ml high-pressure reactor. At this point, the Al / Co ratio was 2500:1. The stirring speed was maintained at 400 rpm. When the system temperature reached 30°C, the ethylene pressure inside the reactor was increased to 10 atm. During the reaction, the system temperature and the ethylene pressure remained constant at 10 atm. After reacting for 30 min, stirring was stopped, and the reaction solution was neutralized with a 10% hydrochloric acid ethanol solution to obtain a polymer precipitate. After washing several times with ethanol, the precipitate was dried under vacuum to constant weight, yielding 7.02 g of polymer. The polymerization activity was 7.02 × 10⁻⁶. 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.24×10 5 g·mol -1 PDI = 2.81 (polymer weight-average molecular weight M) w The molecular weight distribution (PDI) was obtained by high-temperature GPC testing, and the polymer T... m =135.1℃ (polymer melting temperature T) m (Originally obtained from DSC testing).

[0203] Take 30 mg of the obtained polymer, dissolve it in 1 ml of deuterated 1,1,2,2-tetrachloroethane, and test at 100 °C. 13 C NMR data. The obtained signal peak at 30 ppm indicates a methylene shift peak, proving that the obtained polymer is highly linear polyethylene (see details). Figure 7 ).

[0204] b) is basically the same as method a) in this embodiment, except that 1.6 ml of the co-catalyst MMAO (1.93 mol / L toluene solution) makes Al / Co = 1500:1. Polymerization activity: 5.46 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.82×10 5 g·mol -1 PDI = 2.20, polymer T m =136.0℃.

[0205] c) is basically the same as method a) in this embodiment, except that 3.6 ml of the co-catalyst MMAO (1.93 mol / L toluene solution) makes Al / Co = 3500:1. Polymerization activity: 4.24 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.06×10 5 g·mol -1 PDI = 2.36, polymer T m =135.6℃.

[0206] d) Basically the same as method a) in this embodiment, except that the polymerization temperature is 20℃. Polymerization activity: 3.97×10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.75×10 5 g·mol -1 PDI = 2.58, polymer T m =135.5℃.

[0207] e) Basically the same as method a) in this embodiment, except that the polymerization temperature is 60℃. Polymerization activity: 2.85×10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =0.73×10 5 g·mol -1 PDI = 3.14, polymer T m =133.0℃.

[0208] f) is basically the same as method a) in this embodiment, except that the polymerization time is 60 min. Polymerization activity: 4.42 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.70×10 5 g·mol -1 PDI = 2.85, polymer T m =135.4℃.

[0209] g) is basically the same as method a) in this embodiment, except that the ethylene pressure is 1 atm. Polymerization activity: 1.97 × 10⁻⁶ 6 g·mol -1 (Co)·h-1 Polymer weight-average molecular weight M w =2.04×10 5 g·mol -1 PDI = 3.56, polymer T m =134.9℃.

[0210] h) is basically the same as method a) in this embodiment, except that: the polymerization temperature is 40℃, n-hexane is used as the solvent, and 1.6 ml of MMAO (1.93 mol / L toluene solution) is used to make Al / Co = 1500:1. Polymerization activity: 5.22 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =1.28×10 5 g·mol -1 PDI = 2.74, polymer T m =134.3℃.

[0211] Example 22: Ethylene polymerization catalyzed by a Co2 / MMAO system:

[0212] a) Basically the same as Example 21a), except that the main catalyst is Co2. Polymerization activity: 4.67 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =3.48×10 5 g·mol -1 PDI = 1.91, polymer T m =135.1℃.

[0213] b) Basically the same as Example 21h), except that the main catalyst is Co2. Polymerization activity: 8.72 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =1.96×10 5 g·mol -1 PDI = 2.94, polymer T m =134.3℃.

[0214] Example 23: Ethylene polymerization catalyzed by a Co3 / MMAO system:

[0215] a) Same as Example 21a), except that the main catalyst is Co3. Polymerization activity: 6.45 × 10⁻⁶ 6 g·mol -1(Co)·h -1 Polymer weight-average molecular weight M w =3.84×10 5 g·mol -1 PDI = 2.36, polymer T m =135.5℃.

[0216] b) Basically the same as Example 21h), except that the main catalyst is Co3. Polymerization activity: 10.2 × 10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.41×10 5 g·mol -1 PDI = 2.48, polymer T m =135.4℃.

[0217] Example 24: Ethylene polymerization catalyzed by the Co4 / MMAO system:

[0218] a) Basically the same as Example 21a), except that the main catalyst is Co4. Polymerization activity: 6.42 × 10 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.34×10 5 g·mol -1 PDI = 2.18, polymer T m =134.9℃.

[0219] b) Basically the same as Example 21h), except that the main catalyst is Co4. Polymerization activity: 7.01 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =2.12×10 5 g·mol -1 PDI = 2.61, polymer T m =134.9℃.

[0220] Example 25: Ethylene polymerization catalyzed by the Co5 / MMAO system:

[0221] a) Basically the same as Example 21a), except that the main catalyst is Co5. Polymerization activity: 4.56 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w=3.72×10 5 g·mol -1 PDI = 2.31, polymer T m =135.4℃.

[0222] b) Basically the same as Example 21h), except that the main catalyst is Co5. Polymerization activity: 3.90 × 10⁻⁶ 6 g·mol -1 (Co)·h -1 Polymer weight-average molecular weight M w =1.03×10 5 g·mol -1 PDI = 3.32, polymer T m =133.0℃.

[0223] Example 26: Ethylene polymerization catalyzed by the Fe1 / MAO system:

[0224] a) Under an ethylene atmosphere, 25 ml of toluene, 50 ml of a toluene solution of Fe1 (2 μmol) catalyst, 2.4 ml of a 1.46 mol / L toluene solution of MAO co-catalyst, and 25 ml of toluene were sequentially added to a 250 ml high-pressure reactor. At this point, the Al / Fe ratio was 1750:1. The stirring speed was maintained at 400 rpm. When the system temperature reached 60°C, the ethylene pressure inside the reactor was increased to 10 atm. During the reaction, the system temperature and the ethylene pressure remained constant at 10 atm. After reacting for 30 min, stirring was stopped, and the reaction solution was neutralized with a 10% hydrochloric acid ethanol solution to obtain a polymer precipitate. After washing several times with ethanol, the precipitate was dried under vacuum to constant weight, yielding 9.66 g of polymer. The polymerization activity was 9.66 × 10⁻⁶. 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =4.33×10 5 g·mol -1 PDI = 4.39 (polymer weight-average molecular weight M) w The molecular weight distribution (PDI) was obtained by high-temperature GPC testing, and the polymer T... m =134.4℃ (polymer melting temperature T) m (Originally obtained from DSC testing).

[0225] b) is basically the same as method a) in this embodiment, except that the polymerization temperature is 50℃, the solvent used is n-hexane, and 3.8 ml of MAO (1.46 mol / L toluene solution) is used as the co-catalyst to make Al / Fe = 2750:1. Polymerization activity: 16.0 × 10⁻⁶ 6 g·mol -1(Fe)·h -1 Polymer weight-average molecular weight M w =1.85×10 5 g·mol -1 PDI = 18.9, polymer T m =132.0℃.

[0226] Example 27: Ethylene polymerization catalyzed by the Fe2 / MAO system:

[0227] a) Basically the same as Example 26a), except that the main catalyst is Fe2+. Polymerization activity: 7.44 × 10⁻⁶ 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =3.11×10 5 g·mol -1 PDI = 3.77, polymer T m =134.5℃.

[0228] b) Basically the same as Example 26b), except that the main catalyst is Fe2. Polymerization activity: 14.9 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =0.91×10 5 g·mol -1 PDI = 18.2, polymer T m =129.5℃.

[0229] Example 28: Ethylene polymerization catalyzed by the Fe3 / MAO system:

[0230] a) Same as Example 26a), except that the main catalyst is Fe3+. Polymerization activity: 3.61 × 10⁻⁶ 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =7.24×10 5 g·mol -1 PDI = 3.38, polymer T m =134.6℃.

[0231] b) Basically the same as Example 26b), except that the main catalyst is Fe3+. Polymerization activity: 8.83 × 10⁻⁶ 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w=3.94×10 5 g·mol -1 PDI = 23.2, polymer T m =133.5℃.

[0232] Example 29: Ethylene polymerization catalyzed by the Fe4 / MAO system:

[0233] a) Basically the same as Example 26a), except that the main catalyst is Fe4. Polymerization activity: 6.31 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =2.21×10 5 g·mol -1 PDI = 5.38, polymer T m =133.7℃.

[0234] b) Basically the same as Example 26b), except that the main catalyst is Fe4. Polymerization activity: 16.2 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =2.03×10 5 g·mol -1 PDI = 26.2, polymer T m =129.2℃.

[0235] Example 30: Ethylene polymerization catalyzed by the Fe5 / MAO system:

[0236] a) Basically the same as Example 26a), except that the main catalyst is Fe5. Polymerization activity: 7.16 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =1.91×10 5 g·mol -1 PDI = 8.28, polymer T m =133.6℃.

[0237] b) Basically the same as Example 26b), except that the main catalyst is Fe5. Polymerization activity: 18.4 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =3.63×10 5 g·mol -1PDI = 20.5, polymer T m =131.5℃.

[0238] Example 31: Ethylene polymerization catalyzed by the Fe1 / MMAO system:

[0239] a) Under an ethylene atmosphere, 25 ml of toluene, 50 ml of a toluene solution of catalyst Fe1 (2 μmol), 3.6 ml of co-catalyst MMAO (1.93 mol / L toluene solution), and 25 ml of toluene were sequentially added to a 250 ml high-pressure reactor. At this point, the Al / Fe ratio was 3500:1. The stirring speed was maintained at 400 rpm. When the system temperature reached 60°C, the ethylene pressure in the reactor was increased to 10 atm. During the reaction, the system temperature and the ethylene pressure remained constant at 10 atm. After reacting for 30 min, stirring was stopped, and the reaction solution was neutralized with a 10% hydrochloric acid ethanol solution to obtain a polymer precipitate. After washing several times with ethanol, the precipitate was dried under vacuum to constant weight, yielding 15.8 g of polymer. The polymerization activity was 15.8 × 10⁻⁶. 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w = 7.60 kg·mol -1 PDI = 1.60 (polymer weight-average molecular weight M) w The molecular weight distribution (PDI) was obtained by high-temperature GPC testing, and the polymer T... m =128.4℃ (polymer melting temperature T) m (Originally obtained from DSC testing).

[0240] b) Basically the same as method a) in this embodiment, except that n-hexane is used as the solvent. Polymerization activity: 6.30 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =1.05×10 5 g·mol -1 PDI = 34.7, polymer T m =129.8℃.

[0241] Example 32: Ethylene polymerization catalyzed by the Fe2 / MMAO system:

[0242] a) Basically the same as Example 31a), except that the main catalyst is Fe2. Polymerization activity: 6.79 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w= 6.83 kg·mol -1 PDI = 2.99, polymer T m =127.2℃.

[0243] b) Basically the same as Example 31b), except that the main catalyst is Fe2. Polymerization activity: 1.79 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =1.43×10 5 g·mol -1 PDI = 86.4, polymer T m =126.3℃.

[0244] Example 33: Ethylene polymerization catalyzed by the Fe3 / MMAO system:

[0245] a) Same as Example 31a), except that the main catalyst is Fe3+. Polymerization activity: 2.90 × 10⁻⁶ 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w = 7.94 kg·mol -1 PDI = 2.39, polymer T m =128.5℃.

[0246] b) Basically the same as Example 31b), except that the main catalyst is Fe3+. Polymerization activity: 0.86 × 10⁻⁶ 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =0.26×10 5 g·mol -1 PDI = 14.9, polymer T m =126.0℃.

[0247] Example 34: Ethylene polymerization catalyzed by the Fe4 / MMAO system:

[0248] a) Basically the same as Example 31a), except that the main catalyst is Fe4. Polymerization activity: 6.76 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w = 6.96 kg·mol -1 PDI = 2.42, polymer T m =128.2℃.

[0249] b) Basically the same as Example 31b), except that the main catalyst is Fe4. Polymerization activity: 1.33 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =0.54×10 5 g·mol -1 PDI = 46.9, polymer T m =125.2℃.

[0250] Example 35: Ethylene polymerization catalyzed by the Fe5 / MMAO system:

[0251] a) Basically the same as Example 31a), except that the main catalyst is Fe5. Polymerization activity: 7.28 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w = 9.21 kg·mol -1 PDI = 2.97, polymer T m =128.2℃.

[0252] b) Basically the same as Example 31b), except that the main catalyst is Fe5. Polymerization activity: 1.99 × 10 6 g·mol -1 (Fe)·h -1 Polymer weight-average molecular weight M w =2.28×10 5 g·mol -1 PDI = 57.0, polymer T m =132.1℃.

[0253] Comparative Example 1: Comparison of catalytic effects between the Co4 / MAO system and similar previously reported systems

[0254] To investigate the effect of the introduction of trifluoromethoxy groups on the catalytic activity of cobalt complexes and the molecular weight of polymers, Figure 8 The catalytic effect of a similarly structured catalyst ((para-R=Cl,NO2)) under the same conditions (MAO as the co-catalyst, reaction temperature of 30℃, ethylene pressure of 10 atm, and toluene as the polymerization solvent; the figure shows catalytic activity and molecular weight from left to right). As can be seen from the figure, the introduction of trifluoromethoxy groups has a positive effect on catalytic activity, and the molecular weight of the resulting polymer is increased.

[0255] Comparative Example 2: Comparison of catalytic effects between the Fe3 / MAO system and similar previously reported systems

[0256] To investigate the effect of the introduction of trifluoromethoxy groups on the catalytic activity of iron complexes and the molecular weight of polymers, Figure 9 The catalytic effect of a similarly structured catalyst (para-R=Me, NO2) under the same conditions (MAO as the co-catalyst, reaction temperature of 60℃, ethylene pressure of 10 atm, and toluene as the polymerization solvent; the figure shows catalytic activity, molecular weight, and molecular weight distribution from left to right). As can be seen from the figure, although the introduction of trifluoromethoxy groups has a negative impact on catalytic activity, it increases the molecular weight of the resulting polymer and significantly reduces the molecular weight distribution.

Claims

1. The ligand compound shown in Formula II, Formula II In the formula, R 1 R 2 Same or different, C 1-6 alkyl; R 3 R 4 Whether the two are the same or different, they are each independently selected from H and C. 1-6 alkyl.

2. The ligand compound according to claim 1, characterized in that: The ligand compound is any one of ligands L1-L5: In ligand L1, R 1 = Me, all other groups are H; in ligand L2, R 1 = Et, all other groups are H; R in ligand L3 1 = i Pr, all other groups are H, and R in ligand L4 1 = R 2 = Me, all other groups are H; R in ligand L5 1 = Et,R 2 = Me, all other groups are H.

3. A method for preparing the ligand compound according to claim 1 or 2, comprising the following steps: 1) The condensation reaction of 2,6-diacetylpyridine (Formula III) with aniline (Formula IV) yields the compound (Formula V); 2) The compound shown in Formula V is subjected to a condensation reaction with the aniline shown in Formula VI to obtain the ligand compound shown in Formula II of claim 1 or 2; The condensation reaction was carried out under the catalysis of p-toluenesulfonic acid, with toluene as the solvent. The molar ratio of the compound shown in Formula V to the aniline shown in Formula VI is 1:1~2; Formula VI in, R 1 R 2 R 3 R 4 The definition is the same as that of the ligand compound represented by Formula II as described in claim 1 or 2.

4. The asymmetric pyridine diimine metal complex containing trifluoromethoxy group shown in Formula I, Formula I In the formula, M is selected from Fe and Co; R 1 R 2 Same or different, C 1-6 alkyl; R 3 R 4 Whether the two are the same or different, they are each independently selected from H and C. 1-6 alkyl; X may be the same or different, and each is independently selected from Cl and Br.

5. The asymmetric pyridine diimine metal complex according to claim 4, characterized in that: The asymmetric pyridine diimine metal complex is either complex Fe1-Fe5 or complex Co1-Co5. In the complex Fe1, R 1 = Me, M = Fe, X = Cl, other groups are H; complex Fe2: where R 1 = Et, M = Fe, X = Cl, other groups are H; complex Fe3: where R 1 = i Pr, M = Fe, X = Cl, other groups are H; complex Fe4: where R 1 = R 2 = Me, M = Fe, X = Cl, other groups are H; complex Fe5: where R 1 = Et,R 2 = Me, M = Fe, X = Cl, and other groups are H; Co1 complex: where R 1 = Me, M = Co, X = Cl, other groups are H; Complex Co2: where R 1 = Et, M = Co, X = Cl, other groups are H; Complex Co3: where R 1 = i Pr, M = Co, X = Cl, other groups are H; complex Co4: where R 1 = R 2 = Me, M = Co, X = Cl, other groups are H; Complex Co5: where R 1 = Et,R 2 = Me, M = Co, X = Cl, and other groups are H.

6. A method for preparing the asymmetric pyridine diimine metal complex according to claim 4 or 5, comprising the following steps: The ligand compound of formula II according to claim 1 or 2 is complexed with metal halide MX2 to obtain the asymmetric pyridinediimine metal complex according to claim 4 or 5. in, M is selected from Fe and Co, and X is selected from Cl and Br; The complexation reaction is carried out under an inert gas atmosphere; The molar ratio of the metal halide MX2 to the compound shown in Formula II is 1:1~2.

7. A catalyst composition comprising a main catalyst and an optional co-catalyst, wherein, The main catalyst is selected from the asymmetric pyridine diimide metal complex containing trifluoromethoxy as shown in Formula I of claim 4 or 5. The co-catalyst is selected from one or both of methylaluminoxane or triisobutylaluminum-modified methylaluminoxane; The molar ratio of metal Al in the co-catalyst to the central metal Fe or Co of the asymmetric pyridine diimine metal complex containing trifluoromethoxy as shown in Formula I is 500~4000:

1.

8. The use of the trifluoromethoxy-containing asymmetric pyridine diimide metal complex of formula I as described in claim 4 or 5, and the catalyst composition of claim 7, in the catalytic polymerization of olefins.

9. A method for preparing polyethylene, comprising the step of catalyzing the polymerization reaction of ethylene using the catalyst composition of claim 7.

10. The preparation method according to claim 9, characterized in that: The polymerization reaction is carried out at a temperature of 20~100℃ for a time of 5~60 min; The polymerization reaction is carried out under a pressure of 0.5~10 atm; The solvent for the polymerization reaction is selected from one or more of toluene, o-xylene, n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, dichloromethane, ethanol, and tetrahydrofuran; The polymerization reaction was carried out in an ethylene atmosphere.

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