Decahydroquinoline-imine metal catalyst and its preparation method and application

Abstract

The present invention belongs to the technical field of polymer compounds, and in particular to a decahydroquinoline-imine metal catalyst and its preparation method and application. Under a nitrogen atmosphere, a metal salt is added to an anhydrous solvent, and then a methylmagnesium bromide solution is added for stirring reaction; a decahydroquinoline-imine ligand is added for light-avoiding reaction, and the reaction is continued after the light-avoiding reaction ends, the solvent is removed under reduced pressure, a good solvent is added for extraction, and filtering is performed to obtain a decahydroquinoline-imine metal catalyst. An olefin monomer, a decahydroquinoline-imine metal catalyst and a co-catalyst are added to a solvent for polymerization reaction to obtain a polymer. The present invention has excellent activity, a high product yield, and excellent high temperature resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer compounds, and specifically relates to a decahydroquinoline-imine metal catalyst and a preparation method and application thereof. Background Art

[0002] Polyolefin elastomer (POE) is a random copolymer of ethylene and α-olefin, in which the mass percentage of α-olefin is greater than 20wt.%. Due to the special two-phase microstructure, POE has both high elasticity of rubber and good thermoplastic processing properties. Polyolefin elastomers are synthesized by high-temperature solution polymerization technology, so it is very necessary to develop high-temperature resistant catalysts. In 1989, Dow Chemical Company first synthesized and reported the constrained geometry metallocene catalyst (Constrained Geometry Catalyst, CGC), and achieved industrialization in 1993 (Chem. Rev. 1998, 98, 2587-2598). In addition, they also reported a series of non-metallocene catalysts (Acc. Chem. Res. 2015, 48, 2004-2016). In recent years, due to the diversity of non-metallocene catalysts and excellent catalytic performance, non-metallocene catalysts have attracted widespread attention. Summary of the invention

[0003] The purpose of the present invention is to provide a decahydroquinoline-imine metal catalyst having excellent activity, high product yield and excellent high temperature resistance; the present invention also provides a preparation method and application of the decahydroquinoline-imine metal catalyst.

[0004] The decahydroquinoline-imine metal catalyst of the present invention has the following structural formula:

[0005]

[0006] Wherein, M is one of hafnium, titanium or zirconium, X is one of -Cl, methyl or benzyl, R 1 is -H, methyl, ethyl or isopropyl, R 2 is -H, methyl, ethyl or isopropyl, R 3 It is one of -H, methyl, tert-butyl or methoxy.

[0007] The structural formula of the decahydroquinoline-imine metal catalyst of the present invention is preferably one of the following structural formulas:

[0008]

[0009] The 2,6-dimethylphenyl or 2,6-diisopropylphenyl in the catalyst structure of the present invention can improve the polymerization activity of the catalyst and the insertion rate of the comonomer alpha-olefin.

[0010] The preparation method of the decahydroquinoline-imine metal catalyst of the present invention comprises the following steps:

[0011] (1) Under a nitrogen atmosphere, a metal salt is added to an anhydrous solvent, and then a methylmagnesium bromide solution is added to carry out a stirring reaction;

[0012] (2) adding a decahydroquinoline-imine ligand to carry out a light-protected reaction, and continuing the reaction after the light-protected reaction is completed, removing the solvent under reduced pressure, adding a good solvent for extraction, and filtering to obtain a decahydroquinoline-imine metal catalyst.

[0013] In step (1), the metal salt is one of HfCl4, TiCl4 or ZrCl4, and the solvent is one of toluene, xylene or n-hexane; the ratio of the metal salt to the solvent is 0.8-1.1:10, wherein the metal salt is measured in mmol and the solvent is measured in ml; and the molar ratio of the metal salt to the methylmagnesium bromide in the methylmagnesium bromide solution is 0.8-1.1:4.8.

[0014] The stirring reaction time in step (1) is 2-3 hours, and the stirring reaction temperature is -42 to -38°C.

[0015] The preparation method of the decahydroquinoline-imine ligand in step (2) is as follows: 2-formyl-decahydroquinoline, an aniline compound and p-toluenesulfonic acid are added to a solvent for reaction, concentrated under reduced pressure, filtered, and dried in vacuo to obtain the decahydroquinoline-imine ligand, wherein the aniline compound is 2,6-diisopropylaniline or 2,6-dimethylaniline, and the solvent is ethanol; the ratio of 2-formyl-decahydroquinoline, the aniline compound, p-toluenesulfonic acid and the solvent is 10:10-11:20-25:100, wherein 2-formyl-decahydroquinoline is measured in mmol, the aniline compound is measured in mmol, the p-toluenesulfonic acid is measured in mg, and the solvent is measured in ml; and the reaction temperature is 24-26°C.

[0016] The molar ratio of the decahydroquinoline-imine ligand in step (2) to the metal salt in step (1) is 1:0.8-1.1; and the good solvent is one of toluene, n-hexane or cyclohexane.

[0017] In step (2), the temperature of the light-proof reaction is -42 to -38°C, and the light-proof reaction time is 1 to 3 hours; the temperature of the continued reaction is room temperature, and the continued reaction time is 4 to 6 hours.

[0018] The present invention uses p-toluenesulfonic acid to catalyze 2-aldehyde-decahydroquinoline and aniline compounds to carry out amine-aldehyde condensation reaction to obtain a decahydroquinoline-imine ligand, and the decahydroquinoline-imine ligand and MMe4 (M = Ti, Zr or Hf) obtained by in-situ synthesis of a metal salt are reacted in one pot to obtain a decahydroquinoline-imine metal catalyst.

[0019] The application of the decahydroquinoline-imine metal catalyst of the present invention is to add olefin monomer, decahydroquinoline-imine metal catalyst and co-catalyst into solvent to carry out polymerization reaction to obtain polymer.

[0020] The polymerization reaction temperature is 80-180°C, and the polymerization reaction pressure is 0.5-3MPa.

[0021] The olefin monomer is one or more of ethylene, propylene, 1-octene, 1-hexene or 1-butene; the cocatalyst is one or more of triphenylcarbonium tetrakis(pentafluorophenyl)borate, tri(pentafluorophenyl)boron, alkylaluminum, alkylaluminum chloride or aluminoxane; the alkylaluminum is one of trimethylaluminum, triisobutylaluminum, triethylaluminum or tri-n-hexylaluminum; the alkylaluminum chloride is one of diethylaluminum monochloride, ethylaluminum dichloride or diethylaluminum sesquichloride; the aluminoxane is one of methylaluminoxane, ethylaluminoxane or isobutylaluminoxane; the solvent is one or more of toluene, n-hexane or n-pentane.

[0022] The beneficial effects of the present invention are as follows:

[0023] In the presence of a co-catalyst, the decahydroquinoline-imine metal catalyst prepared by the present invention exhibits excellent activity (activity up to 1×10 4 kg(POE)·mol -1 (M) ·h -1 In addition, the decahydroquinoline-imine metal catalyst prepared by the present invention also exhibits excellent high temperature resistance (greater than 160°C), is suitable for high temperature solution polymerization, and can prepare high performance polyolefin elastomer. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the NMR carbon spectrum of the polymer obtained in Example 12.

[0025] Figure 2 is the gel permeation chromatogram of the polymer prepared in Example 13.

[0026] Figure 3 This is the carbon NMR spectrum of the polymer obtained in Example 15.

[0027] Figure 4 This is the NMR carbon spectrum of the polymer obtained in Example 16.

[0028] Figure 5 is a gel permeation chromatogram of the polymer prepared in Example 19. DETAILED DESCRIPTION

[0029] The present invention is further described below with reference to the embodiments.

[0030] Example 1

[0031] Under nitrogen atmosphere, 10 mmol of 2-formyl-decahydroquinoline, 10 mmol of 2,6-dimethylaniline and 20 mg of p-toluenesulfonic acid were added to 100 mL of ethanol and stirred at 24 °C overnight. The resulting reaction solution was concentrated under reduced pressure and filtered. After vacuum drying for 6 h, the ligand 2-(2,6-Me2-C6H3-N=CH)-decahydroquinoline was obtained with a yield of 92%. 1 H NMR (CDCl3): δ 8.50 (s, 1 H), 7.27 (d, J = 7.5 Hz, 2 H), 7.08 (t, J = 7.5 Hz, 1 H), 2.95 (m, 1 H), 2.68 (m, 1 H), 2.25 (s, 6 H), 2.04 (m, 1 H), 1.83-1.31 (m, 10 H), 1.11-1.03 (m, 3 H)ppm. 13 C NMR (CDCl3): δ159.72, 149.55, 130.14, 128.34, 127.43, 61.30, 52.94, 36.30,31.85, 31.42, 28.92, 26.77, 25.82, 25.43, 18.60ppm. Anal. Calcd for C 18 H 26 N2:C, 79.95; H, 9.69; N, 10.36. Found: C, 79.90; H, 9.62; N, 10.22.

[0032]

[0033] Under nitrogen atmosphere, 0.8 mmol of hafnium tetrachloride was added to 10 mL of dry toluene, and 1.6 mL of methylmagnesium bromide solution (3 M) was slowly added at -40 °C (acetonitrile-liquid nitrogen bath) and stirred for 2 hours; then 1 mmol of ligand 2-(2,6-Me2-C6H3-N=CH)-decahydroquinoline was added, and the reaction was stirred for 2 hours at -40 °C in the dark, and the reaction was continued for 5 hours after returning to room temperature; after the reaction was completed, the solvent was removed under reduced pressure, and toluene was added for extraction and filtration to obtain catalyst C1 with a yield of 80%. 1 H NMR (400MHz, C6D6): δ8.45 (s, 1 H), 7.25 (d, J = 7.5 Hz, 2 H), 7.11 (t, J= 7.5 Hz, 1H), 2.88 (m, 1 H), 2.55 (m, 1 H), 2.32 (s, 3 H), 2.18 (s, 3 H), 2.04-2.00 (m, 1 H), 1.73-1.29 (m, 9 H), 1.14-1.02 (m, 3 H), 0.90 (s, 9 H) ppm. 13 C NMR (400MHz, C6D6): δ161.44, 150.23, 131.78, 128.66, 127.34, 62.50, 55.38, 51.77,36.88, 31.63, 31.40, 28.91, 26.71, 25.80, 25.43, 18.63, 18.32 ppm. Anal.Calcd for C 21 H 34 HfN2: C, 51.16; H, 6.95; N, 5.68. Found: C, 51.25; H, 6.87; N, 5.58.

[0034]

[0035] Example 2

[0036] Under nitrogen atmosphere, 10 mmol of 2-formyl-decahydroquinoline, 11 mmol of 2,6-diisopropylaniline and 25 mg of p-toluenesulfonic acid were added to 100 mL of ethanol and stirred at 26 °C overnight. The resulting reaction solution was concentrated under reduced pressure and filtered. After vacuum drying for 8 h, the ligand 2-(2,6- i Pr2-C6H3-N=CH)-decahydroquinoline, yield 90%. 1 H NMR (CDCl3): δ8.55 (s, 1 H),7.22 (d, J = 7.5 Hz, 2 H), 7.02 (t, J = 7.5 Hz, 1 H),3.21 (sept, J = 6.7 Hz,2H), 2.96-2.90 (m, 1 H), 2.69-2.65(m, 1 H), 2.02-1.94 (m, 1 H), 1.83-1.31 (m,10 H), 1.11-1.03 (m, 3 H) 1.14 (d, J = 6.7 Hz, 12 H)ppm. 13C NMR (CDCl3): δ161.34, 148.32, 130.78, 128.22, 127.09,61.45, 52.31, 36.67, 31.49, 31.24,30.86, 28.92, 26.77, 25.82, 25.23, 18.66ppm. Anal. Calcd for C 22 H 34 N2: C, 80.92; H, 10.50; N, 8.58. Found: C, 80.87; H, 10.45; N, 8.32.

[0037]

[0038] Under nitrogen atmosphere, 1.1 mmol of hafnium tetrachloride was added to 10 mL of dry toluene, and 1.6 mL of methylmagnesium bromide solution (3 M) was slowly added at -42 °C (acetonitrile-liquid nitrogen bath) and stirred for 3 hours; then the ligand 2-(2,6- i Pr2-C6H3-N=CH)-decahydroquinoline 1mmol, stir and react in the dark at -42℃ for 1 hour, then continue to react for 6 hours after returning to room temperature. After the reaction, remove the solvent under reduced pressure, extract with cyclohexane, filter and obtain catalyst C2 with a yield of 85%. 1 H NMR (400 MHz, C6D6): δ8.58 (s, 1 H), 7.30 (d, J = 7.5 Hz, 2 H), 7.10 (t, J = 7.5Hz, 1 H), 3.76 (sept, J = 6.7 Hz,1 H),3.22 (sept, J = 6.7 Hz, 1 H), 2.88-2.80 (m, 1 H), 2.64-2.60 (m, 1 H), 2.03-1.97 (m, 1 H), 1.85-1.39 (m, 9 H), 1.15-1.08 (m, 3 H), 1.18 (d, J = 6.7 Hz, 6 H),1.10 (d, J = 6.7 Hz, 6 H), 0.96 (s, 9 H) ppm. 13C NMR (400 MHz, C6D6): δ162.45, 149.87, 131.58, 129.00, 127.21,61.39, 52.21, 36.12, 31.87, 31.33, 31.09, 30.86, 28.96, 26.63, 25.92, 25.73,18.68, 18.22ppm. Anal. Calcd for C 25 H 42 HfN2: C, 54.68; H, 7.71; N, 7.71. Found: C, 54.45; H, 7.62; N, 7.56.

[0039]

[0040] Example 3

[0041] 2-(2,6- i The preparation method of Pr2-C6H3-N=CH)-decahydroquinoline is the same as that in Example 2.

[0042] Under nitrogen atmosphere, 1.0 mmol of zirconium tetrachloride was added to 10 mL of dry n-hexane, and 1.6 mL of methylmagnesium bromide solution (3 M) was slowly added at -38 °C (acetonitrile-liquid nitrogen bath) and stirred for 2.5 hours. Then, the ligand 2-(2,6- i Pr2-C6H3-N=CH)-decahydroquinoline 1mmol, stirred at -38℃ in the dark for 2 hours, and continued to react for 5 hours after returning to room temperature; after the reaction, the solvent was removed under reduced pressure, toluene was added for extraction, and the catalyst C3 was obtained by filtration with a yield of 88%. 1 H NMR (400 MHz, C6D6): δ8.64 (s, 1 H), 7.32 (d, J = 7.5 Hz, 2 H), 7.11 (t, J = 7.5Hz, 1 H), 3.72 (sept, J = 6.7 Hz, 1 H),3.20 (sept, J = 6.7 Hz, 1 H), 2.86-2.77 (m, 1 H), 2.64-2.58 (m, 1 H), 2.04-1.97 (m, 1 H), 1.82-1.33 (m, 9 H), 1.13-1.08 (m, 3 H), 1.18 (d, J = 6.7 Hz, 6 H), 1.11 (d, J= 6.7 Hz, 6 H),0.87 (s, 9 H) ppm. 13 C NMR (400 MHz, C6D6): δ161.49, 149.66, 131.31, 129.76,127.29, 61.55, 52.23, 36.77, 31.96, 31.58, 31.21, 30.78, 28.45, 26.27, 25.99,25.79, 18.24, 18.02ppm. Anal. Calcd for C 25 H 42 ZrN2: C, 65.02; H, 9.17; N, 6.07. Found: C, 65.22; H, 9.09; N, 5.96.

[0043]

[0044] Example 4

[0045] 2-(2,6- i The preparation method of Pr2-C6H3-N=CH)-decahydroquinoline is the same as that in Example 2.

[0046] Under nitrogen atmosphere, 1.1 mmol of titanium tetrachloride was added to 10 mL of dry xylene, and 1.6 mL of methylmagnesium bromide solution (3 M) was slowly added at -40 °C (acetonitrile-liquid nitrogen bath) and stirred for 2 hours. Then, the ligand 2-(2,6- i Pr2-C6H3-N=CH)-decahydroquinoline 1mmol, stirred at -40℃ in the dark for 3 hours, and continued to react for 4 hours after returning to room temperature; after the reaction, the solvent was removed under reduced pressure, extracted with n-hexane, and filtered to obtain catalyst C4 with a yield of 80%. 1 H NMR (400 MHz, C6D6): δ8.53 (s, 1 H), 7.19 (d, J = 7.5 Hz, 2 H), 7.02 (t, J = 7.5Hz, 1H), 3.89 (sept, J = 6.7 Hz, 1 H),3.08(sept, J = 6.7 Hz, 1 H), 2.79-2.70(m, 1 H), 2.64-2.59 (m, 1 H), 2.01-1.94 (m, 1 H), 1.80-1.43 (m, 9 H), 1.15-1.07 (m, 3 H), 1.19 (d,J = 6.7 Hz, 6 H), 1.10 (d, J = 6.7 Hz, 6 H), 0.56 (s, 9 H) ppm. 13 C NMR (400 MHz, C6D6): δ160.33, 149.78, 131.86, 129.87, 127.56,61.89, 52.10, 36.39, 31.95, 31.45, 31.11, 30.99, 28.44, 26.37, 25.85, 25.00,18.76, 18.18ppm.Anal. Calcd for C 25 H 42 TiN2: C, 71.75; H, 10.12; N, 6.69. Found: C, 71.56; H, 10.09; N, 6.58.

[0047]

[0048] Example 5

[0049] In a nitrogen atmosphere, the temperature in a glass reactor equipped with a magnet was raised to 80°C, 50 mL of toluene was added, 2 µmol of catalyst C1, 100 µmol of methylaluminoxane and 2.2 µmol of triphenylcarbonium tetrakis(pentafluorophenyl)borate were added to the glass reactor; during the polymerization process, ethylene gas was continuously introduced to ensure that the polymerization pressure was 0.5 MPa and the polymerization temperature was 80°C. After 2 minutes of reaction, 30 mL of ethanol was added to the glass reactor in a nitrogen atmosphere. After cooling, the reaction solution was poured into a large amount of ethanol for sedimentation, and the polymer was obtained by filtration and drying. Polymerization activity: 32000 kg·mol -1 (Hf) h -1 , polymer Mw = 206 kg·mol -1 , Mw / Mn= 2.0.

[0050] Example 6

[0051] The polymerization reaction temperature was changed from 80°C to 120°C, and the other steps were the same as in Example 5. Polymerization activity: 56000 kg·mol -1 (Hf) h -1 , polymer Mw = 160 kg·mol -1 , Mw / Mn=2.1.

[0052] Example 7

[0053] The polymerization reaction pressure was changed from 0.5 MPa to 1 MPa, the polymerization reaction temperature was changed from 80°C to 160°C, and the other steps were the same as in Example 5. Polymerization activity: 95000 kg·mol -1 (Hf) h -1 , polymer Mw = 152 kg·mol -1 , Mw / Mn=2.2.

[0054] Example 8

[0055] The polymerization reaction pressure was changed from 0.5 MPa to 1 MPa, the polymerization reaction temperature was changed from 80°C to 180°C, and the other steps were the same as in Example 5. Polymerization activity: 87000 kg·mol -1 (Hf) h -1 . Polymer Mw = 140 kg·mol -1 , Mw / Mn =2.0.

[0056] Example 9

[0057] Catalyst C1 was replaced by catalyst C2, and the other steps were the same as in Example 5. Polymerization activity: 68800 kg·mol -1 (Hf) h -1 , polymer Mw = 450 kg·mol -1 , Mw / Mn= 2.0.

[0058] Example 10

[0059] Catalyst C1 was replaced by catalyst C3, and the other steps were the same as in Example 5. Polymerization activity: 35500 kg·mol -1 (Zr)·h -1 , polymer Mw = 220 kg·mol -1 , Mw / Mn=2.1.

[0060] Embodiment 11

[0061] Catalyst C1 was replaced by catalyst C4, and the other steps were the same as in Example 5. Polymerization activity: 10500 kg·mol -1 (Ti) h -1 , polymer Mw = 120 kg·mol -1 , Mw / Mn=2.0.

[0062] Example 12

[0063] Catalyst C1 was replaced by catalyst C2, the polymerization temperature was replaced by 120°C from 80°C, 50 mL of toluene was replaced by 26.6 mL of toluene and 23.4 mL of 1-octene, and the other steps were the same as in Example 5. Polymerization activity: 98050 kg·mol -1(Hf) h -1 , polymer Mw = 560 kg·mol -1 , Mw / Mn=2.1, the content of 1-octene in the polymer is 43.0mol%. The NMR carbon spectrum of the polymer is shown in Figure 1 .

[0064] Example 13

[0065] The polymerization reaction pressure was changed from 0.5 MPa to 1 MPa, the polymerization reaction temperature was changed from 120°C to 140°C, and the other steps were the same as in Example 12. Polymerization activity: 155000 kg·mol -1 (Hf) h -1 , polymer Mw = 920 kg·mol -1 , Mw / Mn=2.2, the content of 1-octene in the polymer is 23.0mol%. The gel permeation chromatogram of the polymer is shown in Figure 2 .

[0066] Embodiment 14

[0067] The polymerization reaction pressure was changed from 0.5 MPa to 1 MPa, the polymerization reaction temperature was changed from 120°C to 160°C, and the other steps were the same as in Example 12. Polymerization activity: 148000 kg·mol -1 (Hf) h -1 , polymer Mw = 850 kg·mol -1 , Mw / Mn=2.0, the content of 1-octene in the polymer is 21.8 mol%.

[0068] Embodiment 15

[0069] 26.6 mL toluene and 23.4 mL 1-octene were replaced by 34.4 mL toluene and 15.6 mL 1-octene, and the other steps were the same as in Example 12. Polymerization activity: 90100 kg·mol -1 (Hf) h -1 , polymer Mw = 510 kg·mol -1 , Mw / Mn=2.0, the content of 1-octene in the polymer is 33.1mol%. The NMR carbon spectrum of the polymer is shown in Figure 3 .

[0070] Example 16

[0071] 26.6 mL toluene and 23.4 mL 1-octene were replaced by 42.2 mL toluene and 7.8 mL 1-octene, and the other steps were the same as in Example 12. Polymerization activity: 78000 kg·mol -1 (Hf) h -1 , polymer Mw = 440 kg·mol -1, Mw / Mn=2.2, the content of 1-octene in the polymer is 15.2mol%. The NMR carbon spectrum of the polymer is shown in Figure 4 .

[0072] Embodiment 17

[0073] The polymerization reaction pressure was changed from 0.5 MPa to 1 MPa, and the other steps were the same as in Example 12. Polymerization activity: 137000 kg·mol -1 (Hf) h -1 , polymer Mw = 670 kg·mol -1 , Mw / Mn=2.1, the content of 1-octene in the polymer is 30.8mol%.

[0074] Embodiment 18

[0075] The polymerization reaction pressure was changed from 0.5 MPa to 2 MPa, and the other steps were the same as in Example 12. Polymerization activity: 260000 kg·mol -1 (Hf) h -1 , polymer Mw = 720 kg·mol -1 , Mw / Mn=2.1, the content of 1-octene in the polymer is 20.8mol%.

[0076] Embodiment 19

[0077] The polymerization reaction pressure was changed from 0.5 MPa to 3 MPa, and the other steps were the same as in Example 12. Polymerization activity: 350,000 kg·mol -1 (Hf) h -1 , polymer Mw = 1250 kg·mol -1 , Mw / Mn=2.0, the content of 1-octene in the polymer is 10.1 mol%. The gel permeation chromatogram of the polymer is shown in Figure 5 .

[0078] Embodiment 20

[0079] Catalyst C2 was replaced by catalyst C1, and the other steps were the same as in Example 12. Polymerization activity: 67000 kg·mol -1 (Hf) h -1 , polymer Mw = 500 kg·mol -1 , Mw / Mn=2.1, the content of 1-octene in the polymer is 31.9mol%.

[0080] Embodiment 21

[0081] Catalyst C2 was replaced by catalyst C3, and the other steps were the same as in Example 12. Polymerization activity: 32400 kg·mol -1 (Zr)·h -1, polymer Mw = 480 kg·mol -1 , Mw / Mn=2.1, the content of 1-octene in the polymer is 29.3 mol%.

[0082] Embodiment 22

[0083] Catalyst C2 was replaced by catalyst C4, and the other steps were the same as in Example 12. Polymerization activity: 10200 kg·mol -1 (Ti) h -1 , polymer Mw = 440 kg·mol -1 , Mw / Mn=2.1, the content of 1-octene in the polymer is 13.2 mol%.

Claims

1. A decahydroquinoline-imine metal catalyst, characterized in that The structural formula is as follows: Wherein, M is one of hafnium, titanium or zirconium, X is methyl, R 1 is methyl or isopropyl, R 2 is methyl or isopropyl, R 3 is -H.

2. A method for preparing the decahydroquinoline-imine metal catalyst according to claim 1, characterized in that The steps include: (1) Under a nitrogen atmosphere, a metal salt is added to an anhydrous solvent, and then a methylmagnesium bromide solution is added to carry out a stirring reaction; (2) adding a decahydroquinoline-imine ligand to carry out a light-protected reaction, continuing the reaction after the light-protected reaction is completed, removing the solvent under reduced pressure, adding a good solvent for extraction, filtering, and obtaining a decahydroquinoline-imine metal catalyst; The preparation method of the decahydroquinoline-imine ligand in step (2) is to add 2-aldehyde-decahydroquinoline, an aniline compound and p-toluenesulfonic acid to a solvent for reaction, concentrate under reduced pressure, filter, and vacuum dry to obtain the decahydroquinoline-imine ligand, wherein the aniline compound is 2,6-diisopropylaniline or 2,6-dimethylaniline, and the solvent is ethanol.

3. The method for preparing the decahydroquinoline-imine metal catalyst according to claim 2, characterized in that In step (1), the metal salt is one of HfCl4, TiCl4 or ZrCl4, and the solvent is one of toluene, xylene or n-hexane; the ratio of the metal salt to the solvent is 0.8-1.1:10, wherein the metal salt is measured in mmol and the solvent is measured in ml; and the molar ratio of the metal salt to the methylmagnesium bromide in the methylmagnesium bromide solution is 0.8-1.1:4.

8.

4. The method for preparing the decahydroquinoline-imine metal catalyst according to claim 2, characterized in that The stirring reaction time in step (1) is 2-3 hours, and the stirring reaction temperature is -42 to -38°C.

5. The method for preparing the decahydroquinoline-imine metal catalyst according to claim 2, characterized in that The molar ratio of the decahydroquinoline-imine ligand in step (2) to the metal salt in step (1) is 1:0.8-1.1; and the good solvent is one of toluene, n-hexane or cyclohexane.

6. The method for preparing the decahydroquinoline-imine metal catalyst according to claim 2, characterized in that In step (2), the temperature of the light-proof reaction is -42 to -38°C, and the light-proof reaction time is 1 to 3 hours; the temperature of the continued reaction is room temperature, and the continued reaction time is 4 to 6 hours.

7. Use of the decahydroquinoline-imine metal catalyst according to claim 1, characterized in that The olefin monomer, the decahydroquinoline-imine metal catalyst and the co-catalyst are added into a solvent to carry out a polymerization reaction to obtain a polymer.

8. Use of the decahydroquinoline-imine metal catalyst according to claim 7, characterized in that The polymerization reaction temperature is 80-180°C, and the polymerization reaction pressure is 0.5-3MPa.

9. The use of the decahydroquinoline-imine metal catalyst according to claim 7, characterized in that The olefin monomer is one or more of ethylene, propylene, 1-octene, 1-hexene or 1-butene; the co-catalyst is one or more of triphenylcarbonium tetrakis(pentafluorophenyl)borate, tri(pentafluorophenyl)boron, alkylaluminum, alkylaluminum chloride or aluminoxane; and the solvent is one or more of toluene, n-hexane or n-pentane.

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