Fluoroamine-imine nickel complex, preparation method and application thereof

Abstract

The present invention relates to a fluoroamine imine nickel complex, a preparation method and an application thereof. The structural formula of the complex is shown in formula (I). The above nickel complex provided by the present invention is used as a catalyst to catalyze the homopolymerization of ethylene or the copolymerization of ethylene and polar olefins to produce polyolefins with adjustable molecular weight and degree of branching. The present invention designs and synthesizes a series of fluoroamine imine nickel catalysts. Multiple fluorine atoms can not only have hydrogen bond interactions with β -H of the polymer chain, but also easily form intramolecular hydrogen bonds with amino hydrogen (N H -C) to stabilize the metal catalyst. It can efficiently catalyze the homopolymerization of ethylene or the copolymerization of ethylene and polar monomers within a wide temperature range to obtain polyolefin materials with high molecular weight and medium degree of branching. At the same time, under the regulation of fluorinated anilines with different steric hindrances, this type of catalyst can effectively increase the axial steric hindrance of the metal center to prepare polyolefin materials with high molecular weight and elastomeric properties.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and particularly relates to a fluoroamine imine nickel complex, a preparation method thereof, and an application thereof. Background Art

[0002] Polyolefins are one of the indispensable materials in contemporary life. Developing new catalysts is the key to synthesizing high-performance polyolefin materials, and the design of ligands is crucial in the development of catalysts. Transition metal catalysts synthesized based on various ligands have played a key role in the field of olefin polymerization. Among numerous ligands, the Brookhart-type bisimine is one of the most common structures. Compared with bisimine late transition metal catalysts, aminoimine catalysts for olefin polymerization can obtain polyolefins with a narrow molecular weight distribution (Chem. Commun., 2012, 48, 3312). And they can catalyze the preparation of polyolefin materials with thermoplastic elastomer properties (Inorg. Chem. 2023, 62, 5105), but such catalysts are prone to deactivation under high-temperature conditions (Angew. Chem., Int. Ed. 2017, 56, 11604.).

[0003] The present invention designs and synthesizes a series of fluoroamine imine nickel catalysts. Multiple fluorine atoms can not only have hydrogen bond interactions with the β-H of the polymer chain, but also easily form intramolecular hydrogen bonds with amino hydrogens (NH-C), thus stabilizing the metal catalyst. It can efficiently catalyze the homopolymerization of ethylene or the copolymerization of ethylene with polar monomers within a relatively wide temperature range to obtain polyolefin materials with high molecular weight and medium branching degree. At the same time, under the regulation of fluoroanilines with different steric hindrances, this type of catalyst can effectively increase the axial steric hindrance of the metal center and prepare polyolefin materials with high molecular weight and elastomer properties. Summary of the Invention

[0004] Aiming at the problems existing in the prior art, the present invention provides a synthesis method and an application of a fluoroamine imine nickel complex. The fluoroamine imine nickel complex is used as a catalyst for the homopolymerization of ethylene or the copolymerization of ethylene with polar monomers, and has high catalytic activity, and can obtain polyolefin materials with high molecular weight and elastomer properties.

[0005] To solve the above technical problems, the present invention adopts the following technical solutions:

[0006] The present invention provides an asymmetric fluoroamine imine nickel complex having the structure of formula (I):

[0007]

[0008] R 1 : refers to F, CF3 or OCF3;

[0009] R2 : refers to H, F, CH3 or CHPh2;

[0010] R 3 : refers to H, F or CHPh2;

[0011] —: refers to a covalent bond or a coordination bond.

[0012] The synthesis method of the asymmetric fluoroamine imine nickel complex is as follows: a fluoroamine imine compound reacts with (DME)NiBr2 in an organic solvent to obtain the fluoroamine imine nickel complex shown in formula (I); wherein, DME is ethylene glycol dimethyl ether, and the structural formula of the fluoroamine imine compound is as shown in formula (II):

[0013]

[0014] R in formula (II) 1 is F, CF3 or OCF3; R 2 is H, F, CH3 or CHPh2; R 3 is H, F or CHPh2.

[0015] The structural formulas of some fluoroamine imine compounds adopted in the present invention are as follows:

[0016]

[0017] The structural formulas of some fluoroamine imine nickel complexes of the present invention are as follows:

[0018]

[0019] In the process of preparing the nickel complex described above, the organic solvent is an organic solvent well-known to those skilled in the art. Preferably, the organic solvent is a halogenated alkane, and more preferably, the organic solvent is one or more of chloroform, dichloromethane and 1,2-dichloroethane. The molar ratio of the ligand to the nickel compound is 1:(0.1 - 6). In specific embodiments, the molar ratio of the ligand to the nickel compound is preferably 1:(1 - 3). The reaction is carried out at a temperature of 0°C - 50°C, and the reaction time is 12 - 50 h; in specific embodiments, the reaction time is preferably 12 - 24 h.

[0020] The preparation method of the fluoroamine imine compound shown in formula II of the present invention is as follows: the amino ketone compound shown in formula (III) undergoes a condensation reaction with the amine compound shown in formula (IV) under the catalysis of an acid to generate the fluoroamine imine compound shown in formula (II), and the reaction route is as shown below:

[0021]

[0022] wherein, R 1is F, CF3 or OCF3; R 2 is H, F, CH3 or CHPh2; R 3 is H, F or CHPh2.

[0023] Furthermore, the molar ratio of the amino ketone compound shown in formula (III) to the amine compound shown in formula (IV) is 1:(1 - 2), the condensation reaction temperature is 0°C to 100°C, and the reaction time is 12 - 48 hours.

[0024] The present invention also provides the application of the fluorinated amino imine nickel complex as a catalyst in the catalytic ethylene polymerization reaction: under the catalysis of the fluorinated amino imine nickel complex, ethylene undergoes a polymerization reaction to obtain a polymer with elastomeric properties. The temperature of the polymerization reaction is -78°C to 200°C, and the optimized polymerization reaction temperature is room temperature. The reaction solvent is one or more of toluene, dichloromethane, and n - hexane. The cocatalyst is one or more of methylaluminoxane (MAO), modified methylaluminoxane (MMAO), sesquiethylaluminum chloride (EASC), AlEt2Cl, Al i Bu. The polymerization reaction pressure is 0.01 - 10.0 Mpa, and the optimized polymerization reaction pressure is 8 atm. The molar ratio of Al / Ni = 300.

[0025] The present invention also provides the application of the fluorinated amino imine nickel complex as a catalyst in the catalytic copolymerization reaction of ethylene and polar monomers. Under the catalysis of the fluorinated amino imine nickel complex, ethylene is copolymerized with various polar monomers to obtain a copolymer with elastomeric properties. The temperature of the copolymerization reaction is room temperature, the pressure of the copolymerization reaction is 2 atm, the cocatalyst is one or more of MAO, MMAO, EASC, AlEt2Cl, Al i Bu. The polar monomers are methyl 10 - enoate, 11 - enol, 10 - enoic acid, 1 - butenoic acid, and methyl acrylate. The molar ratio of Al / Ni = 300.

[0026] The above - mentioned processes of olefin copolymerization or homopolymerization are well - known to those skilled in the art and will not be elaborated here. The difference is that the catalyst used in the above - mentioned olefin polymerization is the nickel complex provided by the present invention.

[0027] Advantages of the present invention: A series of nickel catalysts containing fluoroamine imine are designed and synthesized in the present invention. Multiple fluorine atoms can not only form hydrogen bond interactions with the β-H of the polymer chain, but also easily form intramolecular hydrogen bonds with the amino hydrogen (NH-C), thus stabilizing the metal catalyst. It can efficiently catalyze the homopolymerization of ethylene or the copolymerization of ethylene and polar monomers within a relatively wide temperature range to obtain polyolefin materials with relatively high molecular weight and medium degree of branching. At the same time, under the regulation of fluorinated anilines with different steric hindrances, this type of catalyst can effectively increase the axial steric hindrance of the metal center and prepare polyolefin materials with high molecular weight and elastomeric properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 1H- 1 H- 1 H NOESY 2D NMR spectrum of fluoroamine imine compound II1.

[0029] Figure 2 1H- 1 H- 1 Partial 1H-1H NOESY 2D NMR spectrum of fluoroamine imine compound II1.

[0030] Figure 3 1H- 1 H- 1 H NOESY 2D NMR spectrum of fluoroamine imine compound II2.

[0031] Figure 4 1H- 1 H- 1 H NOESY 2D NMR spectrum of fluoroamine imine compound II3.

[0032] Figure 5 1H- 1 H- 13 1H-13C HSQC 2D NMR spectrum of fluoroamine imine compound II4.

[0033] Figure 6 1H- 1 H- 1 H NOESY 2D NMR spectrum of fluoroamine imine compound II5.

[0034] Figure 7 1H- 1 H- 1 H NOESY 2D NMR spectrum of fluoroamine imine compound II6.

[0035] Figure 8 Single crystal structure of nickel compound I1.

[0036] Figure 9 Single crystal structure of nickel compound I2.

[0037] Figure 10 It is the single crystal structure of nickel compound I3. Detailed implementation manners

[0038] The following combines specific examples to further illustrate the present invention. It should be understood that the following embodiments help to further understand the present invention, but do not limit the scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the content of the above invention.

[0039] The data given in the present invention include the synthesis of ligands, the synthesis of metal complexes, polymerization operations, polymerization conditions, and polymerization products. All operations including reactions, preparations, and storage are carried out under a dry inert atmosphere using standard Schlenk operations. The molecular weight and molecular weight distribution of the polymer are determined by GPC. Using trichlorobenzene as the solvent, Agilent PLgel Olexis as the chromatographic column, and measuring on an Agilent PL-220 instrument. Using polystyrene as the standard substance, and correcting polyethylene through universal calibration using the Mark-Houwink parameter: K = 1.75×10 -2 cm 3 / g, R = 0.67 (polystyrene), K = 5.90×10 -2 cm 3 / g, R = 0.69 (polyethylene).

[0040] Test method for tensile strength and elongation at break: Melt press the polymer into a film (50 mm × 50 mm × 0.5 mm) at 0 - 200 °C, and then cut it into dumbbell-shaped specimens (gage length 13 mm, width 2 mm). Use a microcomputer-controlled electronic universal testing machine (UTM-2502) to conduct an elongation at break experiment at room temperature at a speed of 0 - 200 mm / min.

[0041] Test method for elastic recovery rate: Melt press the polymer into a film (50 mm × 50 mm × 0.5 mm) at 0 - 200 °C, and then cut it into dumbbell-shaped specimens (gage length 13 mm, width 2 mm). Use a microcomputer-controlled electronic universal testing machine (UTM-2502) to conduct a stress / strain experiment at room temperature at a speed of 0 - 200 mm / min, with a tensile strain of 0 - 1000%, and cycle 0 - 30 times.

[0042] The calculation formula for the elastic recovery rate is as follows:

[0043]

[0044] Wherein, L0 is the original straight length of the test sample without external force; L1 is the length of the test sample after elongation under external force; L2 is the straight length of the test sample after removing the external force for a certain time.

[0045] Example 1

[0046] The synthesis method of the fluoroamine imine compound II1 in this example is as follows:

[0047] In a 100 mL round-bottom flask, compound III (1.05 g, 4 mmol), o-fluoroaniline (0.67 g, 6 mmol), p-toluenesulfonic acid (0.69 g, 4 mmol), and 60 mL of toluene were added respectively. After heating at 80 °C for 48 h, it was cooled to room temperature, filtered and concentrated to obtain a crude product. Column chromatography separation (petroleum ether / ethyl acetate = 20 / 1) gave 1.00 g (71%) of the yellow oily fluoroamine imine compound II1. The experimental data of this compound: 1 H NMR (600 MHz, CDCl3) δ 7.12 (d, J = 7.6 Hz, 2H), 7.06 - 7.03 (m, 1H), 7.01 - 6.98 (m, 1H), 6.94 (t, J = 7.7 Hz, 1H), 6.83 (t, J = 8.0 Hz, 1H), 6.63 (dd, J = 12.5, 6.6 Hz, 1H), 4.65 (s, 1H, NH), 2.75 (hept, J = 6.9 Hz, 2H, CH(CH3)2), 1.73 (s, 3H, N=CCH3), 1.68 (s, 6H, C(CH3)2), 1.19 (d, J = 6.8 Hz, 6H, CH(CH3)2), 1.15 (d, J = 6.9 Hz, 6H, CH(CH3)2). 13 C NMR (151 MHz, CDCl3): δ 175.6, 151.9 (d, 1 J CF =238.3 Hz), 145.9, 135.9, 134.6 (d, 2 J CF =10.7 Hz), 124.0 (d, 3 J CF =3.3 Hz), 123.3, 122.9, 116.8 (d, 3 J CF =7.0 Hz), 114.7 (d, 2 J CF =18.9 Hz), 113.9, 59.5, 28.0, 26.6, 23.05, 23.00, 15.6. 19 F{ 11H NMR (564 MHz, CDCl3): δ -135.37 ppm. HRMS (ESI-TOF) m / z: [M+H] + calcd for C 23 H 32 FN2 + , 355.2544, found, 355.2545.

[0048] Example 2

[0049] The synthesis method of the fluoroamine imine compound II2 in this example is as follows:

[0050] In a 100 mL round-bottom flask, compound III (1.05 g, 4 mmol), 2-trifluoromethylaniline (0.97 g, 6 mmol), p-toluenesulfonic acid (0.69 g, 4 mmol), and 60 mL of toluene were added respectively. After heating at 60 °C for 24 h, it was cooled to room temperature, filtered and concentrated to obtain the crude product. Column chromatography separation (petroleum ether / ethyl acetate = 20 / 1) gave 0.79 g (49%) of the yellow oily fluoroamine imine compound II2. The experimental data of this compound: 1 1H NMR (600 MHz, CDCl3): δ 7.47 (d, J = 7.6 Hz, 1H), 7.30 (t, J = 7.8 Hz, 1H), 7.12 (d, J = 7.6 Hz, 2H), 7.07 - 7.04 (m, 1H), 6.88 (d, J = 8.3 Hz, 1H), 6.72 (t, J = 7.5 Hz, 1H), 5.16 (s, 1H, NH), 2.75 (hept, J = 6.9 Hz, 2H, CH(CH3)2), 1.71 (s, 3H, N = CCH3), 1.70 (s, 6H, C(CH3)2), 1.20 (d, J = 6.8 Hz, 6H, CH(CH3)2), 1.15 (d, J = 6.9 Hz, 6H, CH(CH3)2). 13 13C NMR (151 MHz, CDCl3): δ 175.3, 145.8, 143.8, 135.9, 132.3, 127.0 (q, 3 J CF = 5.5 Hz), 125.2 (q, 1 J CF = 272.8 Hz), 123.4, 123.0, 116.0, 114.2 (q, 2 J CF = 29.0 Hz), 113.6, 59.9, 28.0, 26.4, 23.04, 22.97, 15.5. 19 19F{ 11H NMR (564 MHz, CDCl3): δ -62.46 ppm. HRMS (ESI-TOF) m / z: [M+H] + calcd for C 24 H 32 F3N2 + 405.2512, found, 405.2516.

[0051] Example 3

[0052] The synthesis method of the fluorinated amino imine compound II3 in this example is as follows:

[0053] In a 100 mL round-bottom flask, compound III (1.05 g, 4 mmol), 2-trifluoromethoxyaniline (1.06 g, 6 mmol), p-toluenesulfonic acid (0.69 g, 4 mmol), and 60 mL of toluene were added respectively. After heating at 60 °C for 24 h, it was cooled to room temperature, filtered and concentrated to obtain the crude product. Column chromatography separation (petroleum ether / ethyl acetate = 20 / 1) gave 1.34 g (80%) of the yellow oily fluorinated amino imine compound II3. The experimental data of this compound: 1 1H NMR (600 MHz, CDCl3) δ 7.16 (d, J = 8.0 Hz, 1H), 7.12 (d, J = 7.6 Hz, 2H), 7.10 - 7.07 (m, 1H), 7.06 - 7.04 (m, 1H), 6.86 (dd, J = 8.2, 1.0 Hz, 1H), 6.68 - 6.65 (m, 1H), 4.96 (s, 1H, NH), 2.75 (hept, J = 6.8 Hz, 2H, CH(CH3)2), 1.71 (s, 3H, N=CCH3), 1.68 (s, 6H, C(CH3)2), 1.19 (d, J = 6.8 Hz, 6H, CH(CH3)2), 1.15 (d, J = 6.9 Hz, 6H, CH(CH3)2). 13 13C NMR (151 MHz, CDCl3): δ 175.4, 145.8, 138.7, 136.5, 135.9, 127.1, 123.4, 122.9, 122.6 (q, 1 J CF =258.2 Hz), 121.4, 116.5, 113.6, 59.4, 28.0, 26.3, 23.04, 22.97, 15.5. 19 19F{ 1 1H}NMR (564 MHz, CDCl3): δ -57.74 ppm. HRMS (ESI-TOF) m / z: [M+H] + calcd for C 24H 32 F3N2O + ,421.2461,found,421.2477.

[0054] Example 4

[0055] The synthesis method of the fluoroamine imine compound II4 in this example is as follows:

[0056] In a 100 mL round-bottom flask, compound III (1.05 g, 4 mmol), 2,4,6-trifluoroaniline (0.88 g, 6 mmol), p-toluenesulfonic acid (0.69 g, 4 mmol), and 60 mL of toluene were added respectively. After heating at 60 °C for 24 h, it was cooled to room temperature, filtered and concentrated to obtain the crude product. Column chromatography separation (petroleum ether / ethyl acetate = 20 / 1) gave 1.17 g (75%) of the yellow oily fluoroamine imine compound II4. The experimental data of this compound: 1 H NMR(600MHz,CDCl3)δ7.13(d,J=7.6Hz,2H),7.08-7.06(m,1H),6.67(t,J=8.4Hz,2H),5.69(s,1H,NH),2.71(hept,J=6.8Hz,2H,CH(CH3)2),1.82(s,3H,N=CCH3),1.48(s,6H,C(CH3)2),1.15(d,J=6.9Hz,12H,CH(CH3)2). 13 C NMR(151MHz,CDCl3):δ174.1,156.7(ddd,J CF =244.1,14.7,9.4Hz),156.3(dt,J CF =243.6,15.2Hz),145.3,136.2,123.5,123.0,120.4(td,J CF =16.8,4.5Hz),100.3-99.9(m),60.9,27.9,26.2,23.2,22.9,16.0. 19 F{ 1 H}NMR(564MHz,CDCl3):δ-118.27,-118.50ppm.HRMS(ESI-TOF)m / z:[M+H] + calcd for C 23 H 30 F3N2 + ,391.2356,found,391.2370.

[0057] Example 5

[0058] The synthesis method of the fluoroamine imine compound II5 in this example is as follows:

[0059] In a 100 mL round-bottom flask, add compound III (1.05 g, 4 mmol), 2-fluoro-6-methylaniline (0.75 g, 6 mmol), p-toluenesulfonic acid (0.69 g, 4 mmol), and 60 mL of toluene. Heat to 60 °C. After 24 h, cool to room temperature, filter and concentrate to obtain the crude product. Column chromatography separation (petroleum ether / ethyl acetate = 20 / 1) gives 0.66 g (45%) of the yellow oily fluoroamine imine compound II5. The experimental data of this compound are as follows: 1 H NMR (600 MHz, CDCl3) δ 7.14 (d, J = 7.6 Hz, 2H), 7.07 (t, J = 7.6 Hz, 1H), 6.91 (dd, J = 11.7, 7.9 Hz, 2H), 6.78 - 6.72 (m, 1H), 5.72 (s, 1H, NH), 2.76 (hept, J = 6.9 Hz, 2H, CH(CH3)2), 2.30 (s, 3H), 1.83 (s, 3H), 1.54 (s, 6H), 1.16 - 1.15 (m, 12H, CH(CH3)2). 13 C NMR (151 MHz, CDCl3) δ 175.71, 155.19 (d, 1 J CF = 239.5 Hz), 145.48, 136.46, 133.12 (d, 2 J CF = 11.7 Hz), 131.66 (d, 3 J CF = 4.3 Hz), 126.02 (d, 4 J CF = 2.6 Hz), 123.62, 123.21, 120.38 (d, 3 J CF = 8.5 Hz), 114.16 (d, 2 J CF = 22.5 Hz), 60.92, 27.93, 26.58, 26.54, 23.64, 23.15, 18.87 (d, 4 J CF = 3.1 Hz), 16.32. 19 F{ 1 H}NMR (564 MHz, CDCl3): δ -120.43 ppm. HRMS (ESI-TOF) m / z: [M + H] + calcd for C 24 H 34 FN2+ ,369.2701,found,369.2711.

[0060] Example 6

[0061] The synthesis method of the fluoroamine imine compound II6 in this example is as follows:

[0062] In a 100 mL round-bottom flask, compound III (1.05 g, 4 mmol), 2-fluoro-6-methylaniline (2.66 g, 6 mmol), p-toluenesulfonic acid (0.69 g, 4 mmol), and 60 mL of toluene were added respectively. After heating at 60 °C for 24 h, it was cooled to room temperature, filtered and concentrated to obtain a crude product. Column chromatography separation (petroleum ether / ethyl acetate = 20 / 1) gave 1.21 g (44%) of the yellow solid fluoroamine imine compound II6. The experimental data of this compound: 1 H NMR(600MHz,CDCl3)δ7.22(t,J=7.4Hz,4H),7.19–7.11(m,8H),7.11(s,1H),7.09(s,1H),7.05(dd,J=8.5,6.7Hz,1H),7.00(dd,J=7.2,1.8Hz,4H),6.92(dd,J=7.6,1.9Hz,4H),6.69(dd,J=13.0,2.1Hz,1H),6.36(d,J=2.1Hz,1H),5.84(s,1H),5.32(s,1H),5.23(s,1H,NH),2.70(hept,J=6.9Hz,2H,CH(CH3)2),1.79(s,3H),1.44(s,6H),1.07(d,J=6.9Hz,6H),0.97(d,J=6.8Hz,6H). 13 C NMR(151MHz,CDCl3)δ176.14,155.66(d, 1 J CF =241.0Hz),145.29,143.92,142.51,137.61(d, 3 J CF =3.8Hz),136.48,136.20(d, 3 J CF =7.2Hz),130.88(d, 2 J CF =12.2Hz),129.43,129.22,128.26,128.17,127.28,126.36,126.17,123.38,122.98,115.10(d, 2 J CF= 23.0 Hz), 61.34, 55.87, 51.67 (d, 4 J CF = 2.5 Hz), 27.66, 26.74, 26.70, 23.39, 23.33, 16.46. 19 F{ 1 H} NMR (564 MHz, CDCl3): δ -119.25 ppm. HRMS (ESI-TOF) m / z: [M + H] + calcd for C 49 H 52 FN2 + , 687.4109 found, 687.4122.

[0063] Figure 1-7 It is the two-dimensional NMR spectrum of the fluoroamine imine compounds II1-II6. It can be seen from the figure that during the preparation of the fluoroamine imine compounds above, there is an obvious spatial correlation between C(CH3)2 and the amino NH and the hydrogen on the fluorinated aniline (Ar-H). This indicates that during the formation of the ligand, the methyl group migrates to the side of the fluorinated aniline to form the thermodynamically more stable compounds II1-II6.

[0064] Example 7

[0065] The synthesis method of the fluoroamine imine nickel compound I1 in this example is as follows:

[0066] Under argon protection, in a 50 mL reaction flask, add fluoroamine imine compound II1 (0.36 g, 1.01 mmol), (DME)NiBr2 (0.31 g, 1.00 mmol), 20 mL of anhydrous dichloromethane, react at room temperature for 50 h, filter and concentrate. Recrystallize in dichloromethane and n-hexane solution, 0.53 g (92%). Experimental data of this compound: ESI-MS (m / z): [M - Br] + calcd for C 23 H 31 BrFN2Ni + , 491.1003, found, 491.1083.. Elemental analysis: C 23 H 31 Br2FN2Ni: C, 48.21; H, 5.45; N, 4.89; Found: C, 48.12; H, 5.43; N, 4.98.

[0067] Example 8

[0068] The synthesis method of the fluoroamine imine nickel compound I2 in this example is as follows:

[0069] Under argon protection, in a 50 mL reaction flask, fluorinated amino imine compound II1 (0.41 g, 1.01 mmol), (DME)NiBr2 (0.31 g, 1.00 mmol), and 20 mL of anhydrous dichloromethane were added. The reaction was carried out at room temperature for 50 h, filtered and concentrated. Recrystallization was carried out in a dichloromethane and n - hexane solution to obtain 0.20 g (32%). Experimental data of this compound: ESI - MS (m / z): [M - Br] + calcd for C 24 H 31 BrF3N2Ni + ,541.0971,found,541.0987. Elemental analysis: C 24 H 31 Br2F3N2Ni: C, 46.27; H, 5.02; N, 4.50; Found: C, 46.39; H, 5.05; N, 4.41.

[0070] Example 9

[0071] The synthesis method of the fluorinated amino imine nickel compound I3 in this example is as follows:

[0072] Under argon protection, in a 50 mL reaction flask, fluorinated amino imine compound II4 (0.42 g, 1.01 mmol), (DME)NiBr2 (0.31 g, 1.00 mmol), and 20 mL of anhydrous dichloromethane were added. The reaction was carried out at room temperature for 50 h, filtered and concentrated. Recrystallization was carried out in a dichloromethane and n - hexane solution to obtain 0.54 g (85%). Experimental data of this compound: ESI - MS (m / z): [M - Br] + calcd for C 24 H 31 BrF3N2NiO + ,557.0920,found,557.0942. Elemental analysis: C 24 H 31 Br2F3N2NiO: C, 45.11; H, 4.89; N, 4.38; Found: C, 45.22; H, 4.85; N, 4.30.

[0073] Example 10

[0074] The synthesis method of the fluorinated amino imine nickel compound I4 in this example is as follows:

[0075] Under argon protection, in a 50 mL reaction flask, fluoroamine imine compound II4 (0.39 g, 1.01 mmol), (DME)NiBr2 (0.31 g, 1.00 mmol), and 20 mL of anhydrous dichloromethane were added, and the reaction was carried out at room temperature for 50 h. After filtration, it was concentrated. Recrystallization was carried out in a dichloromethane and n-hexane solution to obtain 0.54 g (88%). Experimental data of this compound: ESI-MS (m / z): [M - Br] + calcd for C 23 H 29 BrF3N2Ni + ,527.0814,found,527.0781. Elemental analysis: C 23 H 29 Br2F3N2Ni: C, 45.36; H, 4.80; N, 4.60; Found: C, 45.02; H, 4.82; N, 4.76.

[0076] Example 11

[0077] The synthesis method of the fluoroamine imine nickel compound I5 in this example is as follows:

[0078] Under argon protection, in a 50 mL reaction flask, fluoroamine imine compound II5 (0.37 g, 1.01 mmol), (DME)NiBr2 (0.31 g, 1.00 mmol), and 20 mL of anhydrous dichloromethane were added, and the reaction was carried out at room temperature for 48 h. After filtration, it was concentrated. Recrystallization was carried out in a dichloromethane and n-hexane solution to obtain 0.50 g (85%). Experimental data of this compound: ESI-MS (m / z): [M - Br] + calcd for C 24 H 33 BrFN2Ni + ,505.1159,found,505.1162. Elemental analysis: C 24 H 33 Br2FN2Ni: C, 49.10; H, 5.67; N, 4.77; Found: C, 49.23; H, 5.71; N, 4.65.

[0079] Example 12

[0080] The synthesis method of the fluoroamine imine nickel compound I6 in this example is as follows:

[0081] Under argon protection, in a 50 mL reaction flask, fluoroamine imine compound II6 (0.69 g, 1.01 mmol), (DME)NiBr2 (0.31 g, 1.00 mmol), and 20 mL of anhydrous dichloromethane were added, and the reaction was carried out at room temperature for 48 h. After filtration, it was concentrated. Recrystallization was carried out in a dichloromethane and n-hexane solution to obtain 0.74 g (82%). Experimental data of this compound: ESI-MS (m / z): [M - Br] + calcd for C 49 H 51 BrFN2Ni + , 823.2568, found, 823.2581. Elemental analysis: C 49 H 51 Br2FN2Ni: C, 65.00; H, 5.68; N, 3.09; Found: C, 65.15; H, 5.62; N, 2.98.

[0082] Examples 13 to 21 show that fluoroamine imine nickel complexes exhibit special catalytic characteristics in ethylene homopolymerization and ethylene copolymerization with polar monomers: they can efficiently catalyze ethylene homopolymerization or ethylene copolymerization with polar monomers within a relatively wide temperature range to obtain polyolefin materials with high molecular weight and medium degree of branching. At the same time, under the regulation of fluoroanilines with different steric hindrances, such catalysts can effectively increase the axial steric hindrance of the metal center and prepare polyolefin materials with high molecular weight and elastomeric properties.

[0083] Example 13

[0084] Under anhydrous and anaerobic conditions, dry toluene (48 mL) and Et2AlCl (0.6 mL, 1 M toluene solution) were successively added to a 350 mL thick-walled reaction flask. Ethylene was introduced until saturated, and then 2 mL of a dichloromethane solution of fluoroamine imine nickel catalyst I1 (2 μmol) (Al / Ni = 300) was added. The reaction was carried out at 8 atm and different temperatures for 30 min, and the reaction was terminated with ethanol containing 5% hydrochloric acid. The polymer was precipitated, filtered, washed, and then dried in vacuo at 50 °C to constant weight to obtain the polymerization product, which was then analyzed.

[0085] Table 1

[0086] Example Temperature / °C Yield / g <![CDATA[Activity (10 6 g·mol -1 ·h -1 )]]> Degree of branching <![CDATA[M n (×10 5 )]]> PDI 13a 25 2.59 25.9 96 4.51 2.09 13b 50 1.64 16.4 105 3.29 2.20 13c 80 0.81 8.10 108 2.01 2.25

[0087] Example 14

[0088] Under anhydrous and anaerobic conditions, successively add dry toluene (48 mL), Et2AlCl (0.6 mL, 1 M toluene solution) to a 350 mL thick-walled reaction flask, introduce ethylene until saturated, then add 2 mL of a dichloromethane solution containing fluoroamine imine nickel catalyst I2 (2 μmol) (Al / Ni = 300), 8 atm, adjust to different temperatures and react for 30 min, and terminate the reaction with ethanol containing 5% hydrochloric acid. After the polymer is precipitated, filtered, and washed, it is dried under vacuum at 50 °C to constant weight to obtain the polymerization product, and analysis is carried out.

[0089] Table 2

[0090] Example Temperature / °C Yield / g <![CDATA[Activity (10 6 g·mol -1 ·h -1 )]]> Degree of branching <![CDATA[M n (×10 5 )]]> PDI 14a 25 0.58 5.80 96 4.65 2.58 14b 50 0.81 8.10 100 4.18 2.26 14c 80 0.55 5.50 102 3.53 2.86

[0091] Example 15

[0092] Under anhydrous and anaerobic conditions, successively add dry toluene (48 mL), Et2AlCl (0.6 mL, 1 M toluene solution) to a 350 mL thick-walled reaction flask, introduce ethylene until saturated, then add 2 mL of a dichloromethane solution containing fluoroamine imine nickel catalyst I3 (2 μmol) (Al / Ni = 300), 8 atm, adjust to different temperatures and react for 30 min, and terminate the reaction with ethanol containing 5% hydrochloric acid. After the polymer is precipitated, filtered, and washed, it is dried under vacuum at 50 °C to constant weight to obtain the polymerization product, and analysis is carried out.

[0093] Table 3

[0094] Example Temperature / °C Yield / g <![CDATA[Activity (10 6 g·mol -1 ·h -1 )]]> Degree of branching <![CDATA[M n (×10 5 )]]> PDI 15a 25 2.20 22.0 84 3.12 3.12 15b 50 1.66 16.6 97 2.84 2.84 15c 80 1.05 10.5 106 1.85 1.85

[0095] Example 16

[0096] Under anhydrous and anaerobic conditions, successively add dry toluene (48 mL), Et2AlCl (0.6 mL, 1 M toluene solution) to a 350 mL thick-walled reaction flask, introduce ethylene until saturated, then add 2 mL of a dichloromethane solution containing fluoroamine imine nickel catalyst I4 (2 μmol) (Al / Ni = 300), 8 atm, adjust to different temperatures and react for 30 min, and terminate the reaction with ethanol containing 5% hydrochloric acid. After the polymer is precipitated, filtered, and washed, it is dried under vacuum at 50 °C to constant weight to obtain the polymerization product, and analysis is carried out.

[0097] Table 4

[0098] Example Temperature / °C Yield / g <![CDATA[Activity (10 6 g·mol -1 ·h -1 )]]> Degree of branching <![CDATA[M n (×10 5 )]]> PDI 16a 25 1.08 10.8 103 7.22 1.95 16b 50 0.99 9.90 107 3.75 2.10 16c 80 0.65 6.50 111 2.57 2.12

[0099] Example 17

[0100] Under anhydrous and anaerobic conditions, dry toluene (48 mL), Et2AlCl (0.6 mL, 1 M toluene solution) were successively added to a 350 mL thick-walled reaction flask. Ethylene was introduced until saturation, and then 2 mL of a dichloromethane solution containing fluoroamine imine nickel catalyst I5 (2 μmol) (Al / Ni = 300) was added. At 8 atm, the reaction was carried out at different temperatures for 30 min, and the reaction was terminated with ethanol containing 5% hydrochloric acid. The polymer was precipitated, filtered, washed, and then dried in vacuo at 50 °C to constant weight to obtain the polymerization product, which was analyzed. The breaking stress value of the polymerization product at 25 °C was 5.0 Mpa, the breaking strain value was 1924%, and the elastic recovery rate was 83%.

[0101] Table 5

[0102] Example Temperature / °C Yield / g <![CDATA[Activity (10 6 g·mol -1 ·h -1 )]]> Degree of branching <![CDATA[M n (×10 5 )]]> PDI 17a 25 1.23 12.3 96 2.50 2.30 17b 50 1.34 13.4 103 2.04 2.32 17c 80 0.58 5.80 108 1.15 2.57

[0103] Example 18

[0104] Under anhydrous and anaerobic conditions, dry toluene (48 mL), Et2AlCl (0.6 mL, 1 M toluene solution) were successively added to a 350 mL thick-walled reaction flask. Ethylene was introduced until saturation, and then 2 mL of a dichloromethane solution containing fluoroamine imine nickel catalyst I6 (2 μmol) (Al / Ni = 300) was added. At 8 atm, the reaction was carried out at different temperatures for 30 min, and the reaction was terminated with ethanol containing 5% hydrochloric acid. The polymer was precipitated, filtered, washed, and then dried in vacuo at 50 °C to constant weight to obtain the polymerization product, which was analyzed. The breaking stress value of the polymerization product at 50 °C was 21 Mpa, the breaking strain value was 1010%, and the elastic recovery rate was 87%.

[0105] Table 6

[0106] Example Temperature / °C Yield / g <![CDATA[Activity (10 6 g·mol -1 ·h -1 )]]> Degree of branching <![CDATA[M n (×10 5 )]]> PDI 18a 25 0.74 7.40 71 3.59 1.91 18b 50 1.61 16.1 72 3.62 2.01 18c 80 1.38 13.8 78 2.72 2.11 18d 100 0.84 8.4 80 1.06 2.77

[0107] Example 19

[0108] Under anhydrous and anaerobic conditions, dry toluene, Et2AlCl (6 mL, 1 M toluene solution) were successively added to a 350 mL thick-walled reaction flask. Ethylene was introduced until saturation, and then 1 mL of a dichloromethane solution containing fluoroamine imine nickel catalyst I6 (20 μmol) (Al / Ni = 300), methyl 10-enoate (0.25 M) were added. The reaction volume was kept at 20 mL. At 2 atm, the reaction was carried out at room temperature for 30 min. The reaction was terminated with ethanol containing 5% hydrochloric acid. The polymer was precipitated, filtered, washed, and then dried in vacuo at 50 °C to constant weight to obtain 1.62 g of the polymerization product. The catalytic activity was 1.62×10 5 g PE·mol -1 ·h -1 . The molecular weight M of the obtained polymer n = 1.53×10 4g / mol, the molecular weight distribution is 2.45, and the insertion rate is 0.81%.

[0109] Example 20

[0110] Under anhydrous and anaerobic conditions, dry toluene and Et2AlCl (6 mL, 1 M toluene solution) were successively added to a 350 mL thick-walled reaction flask. Ethylene was introduced until saturation, and then 1 mL of a dichloromethane solution containing the fluoroamine imine nickel catalyst I6 (20 μmol) (Al / Ni = 300), 11-enol (0.25 M) were added. The reaction volume was maintained at 20 mL, 2 atm, and the reaction was carried out at room temperature for 30 min. The reaction was terminated with ethanol containing 5% hydrochloric acid. The polymer was precipitated, filtered, washed, and then dried in vacuo at 50 °C to constant weight to obtain 0.31 g of the polymerization product. The catalytic activity was 3.10×10 4 g PE·mol -1 ·h -1 The molecular weight M of the obtained polymer n = 3.24×10 4 g / mol, the molecular weight distribution is 2.32, and the insertion rate is 0.04%.

[0111] Example 21

[0112] Under anhydrous and anaerobic conditions, dry toluene and Et2AlCl (6 mL, 1 M toluene solution) were successively added to a 350 mL thick-walled reaction flask. Ethylene was introduced until saturation, and then 1 mL of a dichloromethane solution containing the fluoroamine imine nickel catalyst I6 (20 μmol) (Al / Ni = 300), 10-enoic acid (0.25 M) were added. The reaction volume was maintained at 20 mL, 2 atm, and the reaction was carried out at room temperature for 30 min. The reaction was terminated with ethanol containing 5% hydrochloric acid. The polymer was precipitated, filtered, washed, and then dried in vacuo at 50 °C to constant weight to obtain 1.58 g of the polymerization product. The catalytic activity was 1.58×10 5 g PE·mol -1 ·h -1 The molecular weight M of the obtained polymer n = 6.40×10 4 g / mol, the molecular weight distribution is 2.54, the insertion rate is 1.18%, the breaking stress value is 7.31 Mpa, the breaking strain value is 1255%, and the elastic recovery rate is 76%.

[0113] Example 22

[0114] Under anhydrous and anaerobic conditions, dry toluene, Et2AlCl (6 mL, 1 M toluene solution) were successively added to a 350 mL thick-walled reaction flask. Ethylene was introduced until saturation, and then 1 mL of a dichloromethane solution containing fluoroamine imine nickel catalyst I6 (20 μmol) (Al / Ni = 300), 1-butenoic acid (0.25 M) were added. The reaction volume was maintained at 20 mL, 2 atm, and the reaction was carried out at room temperature for 30 min. The reaction was terminated with ethanol containing 5% hydrochloric acid. After the polymer was precipitated, filtered, and washed, it was dried in vacuo at 50 °C to a constant weight, and 0.54 g of the polymerization product was obtained. The catalytic activity was 5.40×10 4 g PE·mol -1 ·h -1 . The molecular weight M of the obtained polymer n = 4.69×10 4 g / mol, the molecular weight distribution was 2.03, and the insertion rate was 0.54%.

[0115] Example 23

[0116] Under anhydrous and anaerobic conditions, dry toluene, Et2AlCl (6 mL, 1 M toluene solution) were successively added to a 350 mL thick-walled reaction flask. Ethylene was introduced until saturation, and then 1 mL of a dichloromethane solution containing fluoroamine imine nickel catalyst I6 (20 μmol) (Al / Ni = 300), methyl acrylate (0.25 M) were added. The reaction volume was maintained at 20 mL, 2 atm, and the reaction was carried out at room temperature for 30 min. The reaction was terminated with ethanol containing 5% hydrochloric acid. After the polymer was precipitated, filtered, and washed, it was dried in vacuo at 50 °C to a constant weight, and 1.79 g of the polymerization product was obtained. The catalytic activity was 1.79×10 5 g PE·mol -1 ·h -1 . The molecular weight M of the obtained polymer n = 1.72×10 4 g / mol, the molecular weight distribution was 2.46, and the insertion rate was 0.12%.

[0117] The experimental results show that: the nickel complex provided by this application has high catalytic activity for olefin polymerization, and can obtain polyolefin materials with high molecular weight and elastomeric properties.

[0118] In summary, the fluoroamine imine nickel complex provided by the present invention can efficiently catalyze ethylene homopolymerization or ethylene copolymerization with polar monomers in a wide temperature range to obtain polyolefin materials with high molecular weight and medium degree of branching. At the same time, under the regulation of fluorinated anilines with different steric hindrances, this type of catalyst can effectively increase the axial steric hindrance of the metal center and prepare polyolefin materials with high molecular weight and elastomeric properties.

Claims

1. A fluoroamine imine nickel complex, the structural formula of which is shown in formula (I): ; R1 is F, CF3 or OCF3; R2 is H, F, CH3 or CHPh2; R3 is H, F or CHPh2.

2. The preparation method of the fluoroamine imine nickel complex according to claim 1, characterized in that: The fluorinated amino-imine compound reacts with (DME)NiBr2 in an organic solvent to obtain a fluorinated amino-imine nickel complex shown in formula (I); wherein, DME is ethylene glycol dimethyl ether, and the structural formula of the fluorinated amino-imine compound is shown in formula (II): ； R in formula (II) 1 is F, CF3 or OCF3; R 2 is H, F, CH3 or CHPh2; R 3 is H, F or CHPh2.

3. The preparation method of the fluoroamine imine nickel complex according to claim 2, characterized in that: The organic solvent is one or more of chloroform, dichloromethane, and 1,2-dichloroethane.

4. The preparation method of the fluoroamine imine nickel complex according to claim 2, characterized in that: The molar ratio of the fluorinated amino-imine compound to (DME)NiBr2 is 1:(0.1 - 6).

5. The preparation method of the fluoroamine imine nickel complex according to claim 2, characterized in that: The reaction temperature is 0°C - 50°C, and the reaction time is 12 - 50 h.

6. The preparation method of the fluoroamine imine compound according to claim 2, characterized in that, The preparation method of the fluorinated amino-imine compound is as follows: The amino-ketone compound shown in formula (III) undergoes a condensation reaction with the amine compound shown in formula (IV) under the catalysis of an acid to generate the fluorinated amino-imine compound shown in formula (II), and the reaction route is as follows: ； Wherein, R1 is F, CF3, or OCF3; R2 is H, F, CH3, or CHPh2; R3 is H, F, or CHPh2.

7. The preparation method of the fluoroamine imine nickel complex according to claim 6, characterized in that, The molar ratio of the amino-ketone compound shown in formula (III) to the amine compound shown in formula (IV) is 1:(1 - 2), the condensation reaction temperature is 0°C - 100°C, and the reaction time is 12 - 48 hours.

8. The application of the fluoroamine imine nickel complex according to claim 1 as a catalyst in the catalytic ethylene polymerization reaction, characterized in that: Under the catalytic action of the fluorinated amino-imine nickel complex, ethylene undergoes a polymerization reaction to obtain a polymer with elastomeric properties. The temperature of the polymerization reaction is -78°C - 200°C, the polymerization reaction pressure is 0.01 - 10.0 Mpa, the reaction solvent is one or more of toluene, dichloromethane, and n-hexane, the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane, sesquiethylaluminum chloride, and AlEt2Cl, and the molar ratio of Al / Ni = 300.

9. The application of the fluoroamine imine nickel complex according to claim 1 as a catalyst in the catalytic copolymerization reaction of ethylene and polar monomers, characterized in that: Under the catalytic action of the fluorinated amino-imine nickel complex, ethylene is copolymerized with a polar monomer to obtain a copolymer with elastomeric properties. The temperature of the copolymerization reaction is room temperature, and the pressure of the copolymerization reaction is 2 atm; the polar monomer is methyl 10-enoate, 11-enol, 10-enoic acid, 1-butenoic acid, methyl acrylate, the reaction solvent is one or more of toluene, dichloromethane, and n-hexane, the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane, sesquiethylaluminum chloride, and AlEt2Cl, and the molar ratio of Al / Ni = 300.

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