Preparation method of quinoline-amine coordination titanium-zirconium-hafnium metal catalyst and high-performance polyolefin synthesized by quinoline-amine coordination titanium-zirconium-hafnium metal catalyst

Abstract

A series of quinoline-amine coordinated titanium zirconium hafnium metal catalysts are reported in the invention, are used for olefin high-temperature solution polymerization, and successfully synthesize polyolefin materials such as high-density polyethylene, polyolefin elastomer POE and the like. The catalytic performance of the catalyst is obviously changed by changing the ligand structure of the catalyst and changing different metal centers. The quinoline-amine coordination titanium zirconium hafnium metal catalyst has the advantages of simple synthesis, high product yield and the like. It is worth noting that the quinoline-amine coordination titanium zirconium hafnium metal catalyst can be used in cooperation with various co-catalysts, shows extremely high polymerization activity (the highest polymerization activity can reach 35500 kg (PE) mol <-1 > (M) h <-1 >), has good high-temperature resistance and copolymerization performance, is suitable for olefin high-temperature solution polymerization, and can be used for preparing a high-performance polyolefin elastomer POE. Therefore, the report of the invention has original innovation, can provide thinking and guidance for efficient design and improvement of the catalyst, and can enhance the competitive power of the polyolefin high polymer material technology market in China.

Description

TECHNICAL FIELD

[0001] The present application relates to the preparation of olefin coordination polymerization metal catalysts and their application in the field of olefin polymerization. BACKGROUND

[0002] Olefins are the most widely used polymer materials, accounting for more than 50% of the global synthetic polymer production, especially polyethylene (PE) and isotactic polypropylene (i-PP), which have extremely wide applications in our daily life. In recent years, significant progress has been made in the field of catalysis, reaction engineering and polyolefin processing, greatly improving the manufacturing, performance and economy of polyolefin products. Compared with other materials, the production, processing, application and recycling of polyolefins have a cleaner life cycle, and are therefore considered to be ideal materials that can be applied in many fields, such as packaging and other disposable materials, agriculture, electrical appliances, electronics, construction, communication, automobiles, etc. After the first oil crisis in the late 1970s, energy efficiency became a successful marketing tool, and Union Carbide promoted LLDPE as a substitute for LDPE. In the 20 years after the first oil crisis, the production of LLDPE has increased dramatically, with an annual output of more than 1 million tons. Compared with paper and other packaging materials, LLDPE has a lower density, reducing weight and carbon dioxide emissions during transportation. In addition, thin and strong LLDPE packaging films can be easily manufactured by blow molding. The demand for high-end polyolefin materials in China is increasing, such as the random copolymerization of ethylene with long-chain alpha-olefins to obtain thermoplastic polyolefin elastomers (POE), and the preparation of ethylene-based block copolymers (OBC) by Dow Chemical through chain shuttling technology, which is a high-end polyolefin product with very high added value. China's polyolefin industry started relatively late, and was limited by foreign patents, so it is particularly important to develop new polyolefin catalysts or improve the polymerization process.

[0003] In 2000, Murray et al. of Union Carbide reported NN bidentate coordination pyridine-amine zirconium and hafnium metal catalysts suitable for high-temperature solution polymerization (Acc. Chem. Res. 2015, 48, 2004-2016), which can produce high-performance polyolefin elastomer materials. Jerzy research group and Philip P research group reported amine-based quinoline zirconium and hafnium complexes catalyzing olefin polymerization (Organometallics 2011, 30, 251-262; Organometallics 2012, 31, 6244-6251), which have high activity and high-temperature resistant catalytic performance for the copolymerization of ethylene and 1-octene, and are suitable for high-temperature solution polymerization process.

[0004] The present application reports a series of quinoline-amine coordination titanium zirconium hafnium metal catalysts with high yield synthesis, which are used for olefin high temperature solution polymerization, and successfully synthesized polyethylene, polyolefin elastomer POE and other polyolefin materials. By designing to change the structure of the catalyst ligand and changing different metal centers, the catalytic performance of the catalyst changes significantly. The quinoline-amine coordination titanium zirconium hafnium metal catalysts reported in the present application have the advantages of simple synthesis, high product yield, etc. It is worth noting that the quinoline-amine coordination titanium zirconium hafnium metal catalysts reported in the present application can be used with various cocatalysts, and all show extremely high polymerization activity (up to 35500 kg (PE) mol -1 (M)h -1 ), and have good high temperature resistance and copolymerization performance, and are suitable for olefin high temperature solution polymerization, and can be used to prepare high performance polyolefin elastomer POE. Therefore, the present application has original innovation, can provide ideas and guidance for the design and improvement of catalysts, and can enhance the competitiveness of China's polyolefin polymer material technology market. SUMMARY

[0005] The purpose of the present application is to provide a preparation method of a quinoline-amine coordination metal catalyst and its synthesis of polyolefin materials.

[0006] The present application provides a quinoline-amine coordination titanium zirconium hafnium metal catalyst represented by formula (I):

[0007]

[0008] wherein M is selected from titanium, zirconium, hafnium; R 1 selected from hydrogen, methyl, ethyl, isopropyl, phenyl, chlorine, fluorine; R 2 selected from hydrogen, methyl, ethyl, isopropyl, phenyl, chlorine, fluorine; R 3 selected from hydrogen, methyl, methoxy, tert-butyl, R 4 selected from hydrogen, C1-C6 straight chain alkyl, phenyl, benzyl, isopropylphenyl.

[0009] Preferably, the metal compound of the present application is selected from any one of the metal catalysts represented by formula (II):

[0010]

[0011] The present application provides a preparation method of the above-mentioned quinoline-amine coordination titanium zirconium hafnium metal catalyst, comprising the following steps:

[0012] The metal salt is dissolved in 10-80 mL of anhydrous solvent under a nitrogen atmosphere, 4.0-5.0 molar equivalents of methyl magnesium bromide are added, and the reaction is carried out at low temperature under nitrogen protection for 2-6 hours, then 1 molar equivalent of quinoline amine ligand is added and the reaction is carried out for 5-12 hours; after the reaction is completed, the solvent is removed under reduced pressure, and a good solvent is used for extraction to obtain the sulfide-amine coordinated titanium zirconium hafnium metal catalyst of claim 1.

[0013] In the above preparation method, the anhydrous solvent is selected from toluene, n-hexane, xylene and benzene; and the good solvent is selected from n-hexane, toluene, pentane, heptane and cyclohexane.

[0014] In the above preparation method, the metal salt is selected from one of TiCl4, ZrCl4 and HfCl4.

[0015] The application also provides the use of the above-mentioned quinoline-amine coordinated titanium zirconium hafnium metal catalyst in catalyzing olefin polymerization.

[0016] In the above use, the olefin monomer is one or more of ethylene, propylene, 1-butene, styrene, 1-hexene, norbornene and 1-octene.

[0017] The quinoline-amine coordinated titanium zirconium hafnium metal catalyst needs to be combined with a cocatalyst for catalysis, and the cocatalyst is one or more of trifluorophenyl boron, triphenyl carbonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl aniline tetrakis (pentafluorophenyl) borate, aluminoxane, alkyl aluminum and chlorinated alkyl aluminum. The aluminoxane is methyl aluminoxane, ethyl aluminoxane or isobutyl aluminoxane; the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum or tri-n-hexyl aluminum; and the chlorinated alkyl aluminum is monochlorodiethyl aluminum, sesqui-monochlorodiethyl aluminum or dichloroethyl aluminum.

[0018] In the above polymerization reaction, the polymerization temperature is 0-200℃, the polymerization pressure is 0.1-5 MPa, and the polymerization solvent is one or more of n-hexane, heptane, pentane and toluene.

[0019] The application provides the preparation of quinoline-amine coordinated titanium zirconium hafnium metal catalyst and the use of the catalyst in catalyzing olefin polymerization. The quinoline-amine coordinated titanium zirconium hafnium metal catalyst reported in the application has the advantages of simple synthesis, easy availability of raw materials, high product yield, high temperature resistance (120℃), high catalytic activity (the highest activity can reach 35500 kg (PE) mol -1 (M)h -1 ), and good copolymerization performance, and is especially suitable for high-temperature solution polymerization for preparing high-quality and high-performance polyolefin materials. The metal catalyst provided by the application has original innovation and can promote the development of high-end polyolefin chemical industry in China. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1NMR spectrum of the catalyst C1.

[0021] Figure 2 NMR spectrum of the catalyst C2.

[0022] Figure 3 NMR spectrum of the catalyst C3.

[0023] Figure 4 NMR spectrum of the catalyst C4.

[0024] Figure 5 NMR spectrum of the catalyst C5.

[0025] Figure 6 Infrared spectrum of the polyolefin with 1-octene insertion rate of 5.10%.

[0026] Figure 7 Infrared spectrum of the polyolefin with 1-octene insertion rate of 3.28%.

[0027] Figure 8 Crystal pattern of the catalyst C1.

[0028] Figure 9 Crystal pattern of the catalyst C3. DETAILED DESCRIPTION

[0029] The present application is further illustrated by the following examples without being limited thereto. The examples of the present application can make the skilled in the art more fully understand the present application.

[0030] The experimental methods used in the following examples are conventional methods unless otherwise specified.

[0031] The raw materials and reagents used in the following examples are commercially available unless otherwise specified.

[0032] As shown in formula (III), the quinoline-amine ligand 8-quinoline-CH=N-2,6- i Pr2-C6H3(C1-L), 8-quinoline-CH2-N-2,6- i Pr2-C6H3(C2-L), 1,2-dihydroquinoline-2-(2- i Pr-C6H4)-8-CH=N-2,6- i Pr2-C6H3(C3-L), 8-quinoline-CH=N-2,6-Me2-C6H3(C4-L), 8-quinoline-CH=N-2,4,6-Me3-C6H2(C5-L) were synthesized according to the literature method (Chin. J. Polym. Sci. 2013, 31, 769-777).

[0033]

[0034] The present invention is described below with reference to specific embodiments.

[0035] Example 1: Preparation of Catalyst C1

[0036] Weigh out 3.14 g (20.0 mmol) of 8-quinoline carbaldehyde, 3.54 g (20.0 mmol) of 2,6-diisopropylaniline, and 30 mg (0.174 mmol) of p-toluenesulfonic acid, and dissolve them in 50 mL of a mixed solvent of ethanol and dichloromethane. Stir at room temperature for 12 hours. After removing the solvent using a rotary evaporator, add an appropriate amount of methanol and recrystallize to give a yellow solid Cl-L (4.94 g, 78% yield). 1 HNMR (400MHz, CDCl3): δ9.70 (s, 1H), 8.96 (dd, J=4.2, 1.8Hz, 1H), 8.74 (dd, J=7.3, 1.5Hz, 1H), 8.21 (dd, J=8.3, 1.9Hz, 1H), 7.99 (dd, J=8.1, 1.6Hz, 1H), 7.74(t,J=7.7Hz,1H),7.46(dd,J=8.3,4.2Hz,1H),7.26–7.21(m,2H),7.17( dd,J=8.8,6.4Hz,1H),3.14(hept,J=6.9Hz,2H),1.27(d,J=7.0Hz,12H)ppm. 13 C NMR (100MHz, CDCl3): δ160.08,150.50,150.28,148.00,137.88,136.22,133.15,131 .09,128.42,127.47,126.65,124.14,123.07,121.53,28.13,23.66ppm.Anal.Calcd for C 22 H 24 N2:C,83.50;H,7.64;N,8.85.Found:C,83.27;H,7.53;N,8.98.

[0037] Hafnium tetrachloride (0.352 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. The mixture was then slowly added to a 1.6 mL / 4.8 mmol methyl magnesium bromide solution (3 M) at -40 °C (acetonitrile-liquid nitrogen bath), and stirred for 2 hours. Then, ligand C1-L (0.32 g, 1 mmol) was added, and the reaction was carried out at -40 °C in the dark for 2 hours, followed by a 5-hour reaction at room temperature. After the reaction was complete, the solvent was removed, and the product was extracted with toluene and filtered to obtain 0.39 g of product C1, with a yield of 71%. 1H NMR (400MHz, C6D6): δ8.93(dd,J=4.8,1.7Hz,1H),7.42(dd,J=8.2,1.7Hz,1H),7.34(dd,J=7.7,1.7Hz,1H),7.19(s,1 H),7.11(dd,J=8.2,1.5Hz,1H),7.03(dd,J=7.7,1.7Hz,1H),6.89(dd,J=8.1,7.0Hz,1H),6.74(dd,J=7.0,1.5Hz,1H) ,6.62(dd,J=8.2,4.8Hz,1H),4.36(q,J=7.4Hz,1H),4.20(hept,J=6.9Hz,1H),2.79(hept,J=6.7Hz,1H),2.07(d,J=7 .5Hz,3H),1.57(d,J=6.8Hz,3H),1.46(d,J=6.8Hz,3H),0.99(d,J=6.8Hz,3H),0.62(s,9H),0.32(d,J=6.7Hz,3H)ppm. 13 CNMR (101MHz, C6D6): δ150.56,148.13,147.78,147.17,143.91,143.65,140.42,129.76,129.35,128.57,127.49, 127.18,125.94,125.31,124.12,120.58,67.37,59.94,28.63,26.73,26.61,25.91,25.01,24.94ppm.Anal.Calcd for C 26 H 36 HfN2:C,56.26;H,6.54;N,5.05.Found:C,56.29;H,6.48;N,5.13.

[0038] Example 2: Preparation of catalyst C2

[0039] C1-L (3.16 g, 10.0 mmol) was weighed and dissolved in 50 mL of a mixed solvent of ethanol and dichloromethane. NaBH4 (3.78 g, 100.0 mmol) was slowly added in several batches, and the mixture was stirred at room temperature for 12 hours. The reaction was quenched by slowly adding 100 mL of distilled water. The reaction solution was extracted with dichloromethane, separated, and the organic phase was collected. The organic phase was dried over anhydrous magnesium sulfate, filtered, and then the filtrate was removed by rotary evaporation to obtain a yellow oily substance. Yellow crystals of C2-L (2.42 g, 76% yield) rapidly precipitated at room temperature. 1H NMR (400MHz, CDCl3): δ9.09 (dd, J=4.2, 1.8Hz, 1H), 8.29 (dd, J=8.3, 1.8Hz, 1H), 7 .88(dd,J=8.2,1.5Hz,1H),7.80(dd,J=7.0,1.5Hz,1H),7.61(dd,J=8.2,6.9Hz,1 H),7.54(dd,J=8.3,4.2Hz,1H),7.28(d,J=2.0Hz,2H),7.21(dd,J=8.8,6.1Hz,1H ), 4.84 (s, 1H), 4.70 (s, 2H), 3.70 (hept, J = 6.8Hz, 2H), 1.39 (d, J = 6.9Hz, 12H) ppm. 13 C NMR (100MHz, CDCl3): δ149.62,147.38,144.02,143.05,138.38,136.48,128.86,12 8.67,127.47,126.58,123.76,123.64,121.23,53.91,27.76,24.50ppm.Anal.Calcd for C 22 H 26 N2:C,82.97;H,8.23;N,8.80.Found:C,82.83;H,8.31;N,8.69.

[0040] Hafnium tetrachloride (0.352 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. The mixture was then slowly added to a 1.6 mL / 4.8 mmol methyl magnesium bromide solution (3 M) at -40 °C (acetonitrile-liquid nitrogen bath), and stirred for 2 hours. Then, ligand C2-L (0.32 g, 1 mmol) was added, and the reaction was carried out at -40 °C in the dark for 2 hours, followed by a 5-hour reaction at room temperature. After the reaction was complete, the solvent was removed, and the product was extracted with toluene and filtered to obtain product C2 (0.46 g, yield 84%). 1 H NMR(400MHz,C6D6):)δ8.76(dd,J=4.8,1.7Hz,1H),7.39(dd,J=8.3,1.7Hz,1H),7.12–7.07(m,4H),6.79(dd,J=8.1,6.9Hz,1H),6.71(dd,J=6.9 ,1.5Hz,1H),6.61(dd,J=8.3,4.8Hz,1H),4.78(s,2H),3.21(hept,J=6.8Hz,2H),1.23(d,J=6.9Hz,6H),0.76(d,J=6.7Hz,6H),0.71(s,9H)ppm. 13C NMR (100MHz, C6D6): δ150.49,148.34,145.92,145.84,139.32,137.30,129.65,129.12,12 7.56,127.04,125.53,124.38,121.03,57.78,47.59,28.59,25.45,25.28ppm.Anal.Calcd forC 25 H 34 HfN 2: C,55.50;H,6.33;N,5.18.Found:C,55.38;H,6.41;N,5.25.

[0041] Example 3: Preparation of catalyst C3

[0042] C1-L (3.16 g, 10.0 mmol) was weighed and dissolved in 30 mL of anhydrous diethyl ether. Isopropylphenyl lithium salt (1.89 g, 15.0 mmol) was added, and the mixture was stirred at room temperature for 6 hours. The reaction was quenched by slowly adding 50 mL of NH4Cl aqueous solution. The reaction solution was extracted with anhydrous diethyl ether, separated, and the organic phase was collected. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was removed by rotary evaporation to obtain a yellow oily substance. After separation by column chromatography and removal of the solvent, a yellow solid C3-L (3.14 g, 72% yield) was obtained. 1 H NMR (400MHz, CDCl3): δ9.61(s,1H),8.29(s,1H),7.73(dd,J=7.5,1.7Hz,1H),7.39(dd,J=7.6,1.8Hz, 1H),7.36–7.28(m,2H),7.23–7.15(m,4H),7.04(d,J=7.2Hz,1H),6.66(t,J=7.5Hz,1H),6.54(dd,J=10 .0,1.9Hz,1H),6.20(s,1H),5.75(dd,J=10.0,3.7Hz,1H),3.40(hept,J=6.7Hz,1H),2.98(hept,J=6.9 Hz,2H),1.38(d,J=6.9Hz,3H),1.31(d,J=6.8Hz,3H),1.20(d,J=6.9Hz,6H),1.11(d,J=6.9Hz,6H)ppm. 13C NMR (100MHz, CDCl3): δ165.00,148.77,145.94,144.34,142.21,138.27,134.12,129.39,128.37,127.77,126.53,125. 57,124.97,124.51,124.30,123.07,119.53,115.03,114.72,53.28,28.37,28.03,24.31,24.29,23.51ppm.Anal.Calcd for C 31 H 36 N2:C,85.27;H,8.31;N,6.42.Found:C,85.13;H,8.42;N,6.28.

[0043] Hafnium tetrachloride (0.352 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. The mixture was then slowly added to a 1.6 mL / 4.8 mmol methyl magnesium bromide solution (3 M) at -40 °C (acetonitrile-liquid nitrogen bath), and stirred for 2 hours. Then, ligand C3-L (0.44 g, 1 mmol) was added, and the reaction was carried out at -40 °C in the dark for 2 hours. The reaction was then continued at room temperature for 8 hours. After the reaction was complete, the solvent was removed, and the product was extracted with toluene and filtered to obtain product C3 (0.42 g), with a yield of 63%. 1 H NMR (400MHz, C6D6): δ8.23(s,1H),7.22(dd,J=7.9,1.4Hz,1H),7.15–7.06(m,3H),7.00(dd,J=7.4,1.4Hz,1H),6.99–6.95( m,2H),6.82(dd,J=7.0,1.6Hz,1H),6.81–6.77(m,1H),6.69(d,J=5.5Hz,1H),6.43(dd,J=7.9,7.0Hz,1H),6.22(d,J=9.5Hz, 1H),6.16(dd,J=9.5,5.5Hz,1H),3.39(hept,J=6.7Hz,1H),2.92(hept,J=6.9Hz,1H),2.67(hept,J=6.6Hz,1H),1.27(dd,J= 6.7, 4.3Hz, 6H), 1.21 (d, J = 6.8Hz, 3H), 1.06 (d, J = 6.8Hz, 3H), 0.86 (d, J = 6.7Hz, 3H), 0.80 (d, J = 6.6Hz, 3H), 0.58 (s, 9H) ppm. 13C NMR (100MHz, C6D6): δ167.32,151.53,149.22,143.63,142.72,142.00,140.29,135.19,132.75,127.56,127.48,126.56,126.42,125.94,12 5.51,124.71,124.24,123.23,119.89,116.79,62.02,52.18,29.92,28.95,28.63,26.48,26.23,25.50,24.20,23.68,20.95ppm.Anal.Calcd for C 34 H 44 HfN2:C,61.95;H,6.73;N,4.25.Found:C,61.89;H,6.81;N,4.18.

[0044] Example 4: Preparation of Catalyst C4

[0045] Weigh out 3.14 g (20.0 mmol) of 8-quinoline carbaldehyde, 2.42 g (20.0 mmol) of 2,6-dimethylaniline, and 30 mg (0.174 mmol) of p-toluenesulfonic acid, and dissolve them in 50 mL of a mixed solvent of ethanol and dichloromethane. Stir at room temperature for 12 hours. After removing the solvent using a rotary evaporator, add an appropriate amount of methanol and recrystallize to give a yellow solid C4-L (4.37 g, yield 84%). 1 HNMR (400MHz, CDCl3): δ9.66(s,1H),8.95(dd,J=4.2,1.8Hz,1H),8.73(dd,J=7.3,1.5Hz,1H),8.22(dd,J=8.4,1.9Hz,1H),8.00(dd, J=8.1,1.5Hz,1H),7.71(t,J=7.4Hz,1H),7.46(dd,J=8.3,4.2Hz,1H),7.11(d,J=7.5Hz,2H),6.98(t,J=7.1Hz,1H),2.24(s,6H)ppm. 13 CNMR (100MHz, CDCl3): δ161.18,152.12,150.49,147.21,136.42,133.17,131.14 ,128.42,128.12,127.46,127.34,126.65,123.70,121.54,18.56ppm.Anal.Calcd forC 18 H 16N2:C,83.04;H,6.19;N,10.76.Found:C,83.23;H,6.07;N,10.85.

[0046] Hafnium tetrachloride (0.352 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. The mixture was then slowly added to a 1.6 mL / 4.8 mmol methyl magnesium bromide solution (3 M) at -40 °C (acetonitrile-liquid nitrogen bath), and stirred for 2 hours. Then, ligand C4-L (0.26 g, 1 mmol) was added, and the reaction was carried out at -40 °C in the dark for 2 hours. The reaction was then continued at room temperature for 12 hours. After the reaction was complete, the solvent was removed, and the product was extracted with toluene and filtered to obtain product C4 0.38 g, with a yield of 76%. 1 H NMR (400MHz, C6D6): δ8.92(dd,J=4.8,1.8Hz,1H),7.40(dd,J=8.2,1.8Hz,1H),7.23(d,J=6.7Hz,1H),7.11(dd,J=8.2,1.5Hz,1H),6.98–6.89(m,3H ),6.74(dd,J=7.0,1.5Hz,1H),6.61(dd,J=8.3,4.8Hz,1H),4.38(q,J=7.4 Hz, 1H), 2.68 (s, 3H), 2.02 (d, J = 7.4Hz, 3H), 1.60 (s, 3H), 0.58 (s, 9H) ppm. 13 C NMR (100MHz, C6D6): δ150.48,149.75,144.15,144.11,140.06,137.62,136.53,129.72,129.34,12 8.91,128.57,128.45,127.37,127.27,125.15,65.53,59.69,26.83,20.70,19.70ppm.Anal.Calcd for C 22 H 28 HfN2:C,52.96;H,5.66;N,5.61.Found:C,52.91;H,5.72;N,5.68.

[0047] Example 5: Preparation of Catalyst C5

[0048] Weigh out 3.14 g (20.0 mmol) of 8-quinoline carbaldehyde, 2.75 g (20.0 mmol) of 2,4,6-dimethylaniline, and 30 mg (0.174 mmol) of p-toluenesulfonic acid, and dissolve them in 50 mL of a mixed solvent of ethanol and dichloromethane. Stir at room temperature for 12 hours. After removing the solvent using a rotary evaporator, add an appropriate amount of methanol and recrystallize to give a yellow solid C5-L (4.44 g, yield 81%). 1 HNMR (400MHz, CDCl3): δ9.64(s,1H),8.94(dd,J=4.1,1.8Hz,1H),8.70(dd,J=7.2,1.5Hz,1H),8.20(dd,J=8.3,1.8Hz,1H), 7.97(dd,J=8.1,1.5Hz,1H),7.70(t,J=7.7Hz,1H),7.45(dd,J=8.3,4.2Hz,1H),6.91(s,2H),2.31(s,3H),2.20(s,6H)ppm. 13 C NMR (100MHz, CDCl3): δ161.26,150.48,149.65,147.23,136.33,133.35,132.95,131 .01,128.81,128.43,127.43,127.29,126.66,121.51,20.92,18.51ppm.Anal.Calcd for C 19 H 18 N2:C,83.18;H,6.61;N,10.21.Found:C,83.06;H,6.73;N,10.36.

[0049] Hafnium tetrachloride (0.352 g, 1.1 mmol) was weighed and added to 10 mL of anhydrous toluene. The mixture was then slowly added to a 1.6 mL / 4.8 mmol methyl magnesium bromide solution (3 M) at -40 °C (acetonitrile-liquid nitrogen bath), and stirred for 2 hours. Then, ligand C5-L (0.27 g, 1 mmol) was added, and the reaction was carried out at -40 °C in the dark for 2 hours. The reaction was then continued at room temperature for 12 hours. After the reaction was complete, the solvent was removed, and the product was extracted with toluene and filtered to obtain product C5 0.38 g, with a yield of 73%. 1H NMR (400MHz, C6D6): δ8.94 (dd, J=4.8, 1.8Hz, 1H), 7.40 (dd, J=8.3, 1.8Hz, 1H), 7 .11(dd,J=8.2,1.6Hz,1H),7.05(s,1H),6.92(dd,J=8.2,7.0Hz,1H),6.79(dd,J =7.1,1.6Hz,1H),6.73(s,1H),6.61(dd,J=8.2,4.8Hz,1H),4.39(q,J=7.4Hz,1H ),2.67(s,3H),2.14(s,3H),2.04(d,J=7.4Hz,3H),1.58(s,3H),0.60(s,9H)ppm. 13 C NMR (100MHz, C6D6): δ150.48,146.29,144.24,144.21,140.44,137.33,136.21,134.08,130.56,129.7 4,129.65,128.44,127.37,127.25,120.56,65.29,59.43,26.90,20.91,20.61,19.64ppm.Anal.Calcd for C 23 H 30 HfN2:C,53.85;H,5.89;N,5.46.Found:C,53.92;H,5.83;N,5.38.

[0050] Example 6: C1-catalyzed ethylene polymerization

[0051] A 100 mL steel reactor equipped with a magnetic induction device was used for the polymerization reaction. 50 mL of toluene was injected using a syringe, and the reactor contents were heated to 40 °C. The reactor was then saturated with ethylene at 40 atm. In a glove box, 5 μmol of catalyst C1, 0.25 mmol of methylaluminoxane (MAO), and 6 μmol of triphenylmethyltetra(pentafluorophenyl)borate were added, dissolved in toluene, and transferred to a catalyst storage tube through a stainless steel pipe. Nitrogen gas (above 45 atm) was then pressurized into the reactor, and the reaction pressure was maintained at 40 atm by continuously introducing ethylene gas during polymerization. After the set reaction time of 2 minutes, 2 mL of ethanol was pressurized into the reactor under nitrogen (above 45 atm). The reactor was cooled and vented. The contents of the reactor were poured into a large amount of ethanol, causing polymer precipitation. The polymer was obtained by filtration, washed with a small amount of ethanol, and finally vacuum dried overnight before weighing. Polymerization activity: 17900 kg·mol⁻¹ -1 (Hf)·h -1 The polymer Mw = 34.6 kg·mol -1 Mw / Mn = 6.2.

[0052] Example 7: C1-catalyzed ethylene polymerization

[0053] The polymerization process and conditions were the same as in Example 7, with a polymerization temperature of 60°C and a polymerization pressure of 5 atm. Polymerization activity: 1920 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 0.62 kg·mol⁻¹ -1 Mw / Mn = 1.4.

[0054] Example 8: C1-catalyzed ethylene polymerization

[0055] The polymerization process and conditions were the same as in Example 7, with a polymerization temperature of 60°C and a polymerization pressure of 20 atm. Polymerization activity: 11300 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 53.8 kg·mol⁻¹ -1 Mw / Mn = 5.7.

[0056] Example 9: C1-catalyzed ethylene polymerization

[0057] The polymerization process and conditions were the same as in Example 7, with a polymerization temperature of 60°C. Polymerization activity: 21900 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 32.2 kg·mol⁻¹ -1 Mw / Mn = 2.6.

[0058] Example 10: C1-catalyzed ethylene polymerization

[0059] A 100 mL steel reactor equipped with a magnetic induction device was used for the polymerization reaction. 50 mL of toluene was injected using a syringe, and the reactor contents were heated to 60 °C. The reactor was then saturated with 40 atm ethylene. 5 μmol of catalyst C1 and 2.5 mmol of methylaluminoxane (MAO) were added to a glove box, dissolved in toluene, and transferred to a catalyst storage tube through a stainless steel pipe. Nitrogen gas (above 45 atm) was then pressurized into the reactor, and the reaction pressure was maintained at 40 atm by continuously introducing ethylene gas during polymerization. After the set reaction time of 2 minutes, 2 mL of ethanol was pressurized into the reactor under nitrogen (above 45 atm). The reactor was cooled and vented. The contents of the reactor were poured into a large amount of ethanol, causing polymer precipitation. The polymer was obtained by filtration, washed with a small amount of ethanol, and finally vacuum dried overnight before weighing. Polymerization activity: 35500 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 0.57 kg·mol -1 Mw / Mn = 2.5.

[0060] Example 11: C1-catalyzed ethylene polymerization

[0061] A 100 mL steel reactor equipped with a magnetic induction device was used for the polymerization reaction. 50 mL of toluene was injected using a syringe, and the reactor contents were heated to 60 °C. The reactor was then saturated with 40 atm ethylene. In a glove box, 5 μmol of catalyst C1, 0.25 mmol of methylaluminoxane (MAO), and 6 μmol of trifluorophenylborone were added, dissolved in toluene, and transferred to a catalyst storage tube through a stainless steel pipe. Nitrogen gas (above 45 atm) was then pressurized into the reactor. During polymerization, the reaction pressure was maintained at 40 atm by continuously introducing ethylene gas. Two minutes after the set reaction time was reached, 2 mL of ethanol was pressurized into the reactor under nitrogen (above 45 atm). After the reactor cooled and the atmosphere was vented, the contents were poured into a large amount of ethanol, causing polymer precipitation. The polymer was obtained by filtration, washed with a small amount of ethanol, and finally vacuum-dried overnight before weighing. Polymerization activity: 5900 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 19.7 kg·mol -1 Mw / Mn = 35.0.

[0062] Example 12: C1-catalyzed ethylene polymerization

[0063] The polymerization process and reaction conditions were the same as in Example 12, and the co-catalyst used was N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate. Polymerization activity: 13500 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 26.7 kg·mol -1 Mw / Mn = 2.1.

[0064] Example 13: C1-catalyzed ethylene polymerization

[0065] The polymerization process and conditions were the same as in Example 7, with a polymerization temperature of 80°C. Polymerization activity: 16900 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 18.6 kg·mol -1 Mw / Mn = 3.0.

[0066] Example 14: C1-catalyzed ethylene polymerization

[0067] The polymerization process and conditions were the same as in Example 7, with a polymerization temperature of 100°C. Polymerization activity: 9720 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 10.6 kg·mol -1 Mw / Mn = 3.2.

[0068] Example 15: C1-catalyzed ethylene polymerization

[0069] The polymerization process and conditions were the same as in Example 7, with a polymerization temperature of 120°C. Polymerization activity: 4080 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 2.0 kg·mol -1 Mw / Mn = 2.3.

[0070] Example 16: C2-catalyzed ethylene polymerization

[0071] The polymerization process and reaction conditions were the same as in Example 10, and the catalyst used was C2. Polymerization activity: 23900 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 102.5 kg·mol -1 Mw / Mn = 5.1.

[0072] Example 17: C3-catalyzed ethylene polymerization

[0073] The polymerization process and reaction conditions were the same as in Example 10, and the catalyst used was C3. Polymerization activity: 960 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 138.0 kg·mol -1 Mw / Mn = 3.3.

[0074] Example 18: C4-catalyzed ethylene polymerization

[0075] The polymerization process and reaction conditions were the same as in Example 10, and the catalyst used was C4. Polymerization activity: 20000 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 17.0 kg·mol -1 Mw / Mn = 2.1.

[0076] Example 19: C5 Catalytic Ethylene Polymerization

[0077] The polymerization process and reaction conditions were the same as in Example 10, and the catalyst used was C5. Polymerization activity: 23000 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 8.5 kg·mol -1 Mw / Mn = 2.5.

[0078] Example 20: C1-catalyzed copolymerization of ethylene / 1-octene

[0079] A 100 mL steel reactor equipped with a magnetic induction chamber was used for the polymerization reaction. A mixture of 26 mL toluene and 24 mL 1-octene (total 50 mL) was injected using a syringe. The reactor contents were heated to 60 °C, and the reactor was saturated with 5 atm ethylene. In a glove box, 5 μmol of catalyst C1, 0.25 mmol of methylaluminoxane (MAO), and 6 μmol of triphenylmethyltetra(pentafluorophenyl)borate were added, dissolved in toluene, and transferred to a catalyst storage tube through a stainless steel pipe. Nitrogen gas (above 5 atm) was then pressurized into the reactor. During polymerization, the reaction pressure of 5 atm was maintained by continuously introducing ethylene gas. After the set reaction time of 2 minutes, 2 mL of ethanol was pressurized into the reactor under nitrogen (above 5 atm). After the reactor cooled and the atmosphere was vented, the contents of the reactor were poured into a large amount of ethanol, causing polymer precipitation. The polymer was obtained by filtration, washed with a small amount of ethanol, and finally vacuum dried overnight and weighed. Polymerization activity: 900 kg·mol⁻¹ -1 (Hf)·h -1 The polymer Mw = 0.97 kg·mol -1 Mw / Mn = 2.0, and the copolymer contains 3.52 mol% 1-octene.

[0080] Example 21: C1-catalyzed copolymerization of ethylene / 1-octene

[0081] The polymerization process and conditions were the same as in Example 22, with the polymerization pressure at 20 atm. Polymerization activity: 10000 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 1.5 kg·mol -1 Mw / Mn = 1.7, and the copolymer contains 2.28 mol% 1-octene.

[0082] Example 22: C1-catalyzed copolymerization of ethylene / 1-octene

[0083] The polymerization process and conditions were the same as in Example 22, with the ethylene polymerization pressure at 40 atm. Polymerization activity: 10000 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 9.6 kg·mol -1 Mw / Mn = 2.8, and the copolymer contains 0.90 mol% 1-octene.

[0084] Example 23: C1-catalyzed copolymerization of ethylene / 1-octene

[0085] A 100 mL steel reactor equipped with a magnetic inductor was used for the polymerization reaction. A mixture of 34 mL toluene and 16 mL 1-octene (total 50 mL) was injected using a syringe. The reactor contents were heated to 60 °C, and the reactor was saturated with ethylene at 20 atm. In a glove box, 5 μmol of catalyst C1, 0.25 mmol of methylaluminoxane MAO, and 6 μmol of triphenylmethyltetra(pentafluorophenyl)borate were added, dissolved in toluene, and transferred to a catalyst storage tube through a stainless steel pipe. Nitrogen gas (above 20 atm) was then pressurized into the reactor. During polymerization, the reaction pressure was maintained at 20 atm by continuously introducing ethylene gas. After the set reaction time of 2 minutes, 2 mL of ethanol was pressurized into the reactor under nitrogen (above 20 atm). After the reactor cooled and the atmosphere was vented, the contents were poured into a large amount of ethanol, causing polymer precipitation. The polymer was obtained by filtration, washed with a small amount of ethanol, and finally vacuum dried overnight and weighed. Polymerization activity: 16300 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 3.9 kg·mol -1 Mw / Mn = 2.1, and the copolymer contains 1.27 mol% 1-octene.

[0086] Example 24: C1-catalyzed copolymerization of ethylene / 1-octene

[0087] The polymerization process and conditions were the same as in Example 25, using 42 mL of toluene and 8 mL of 1-octene. Polymerization activity: 23600 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 12.1 kg·mol -1 Mw / Mn = 3.4, and the copolymer contains 1.08 mol% 1-octene.

[0088] Example 25: C2-catalyzed copolymerization of ethylene / 1-octene

[0089] The polymerization process and reaction conditions were the same as in Example 25, and the catalyst used was C2. Polymerization activity: 21700 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 8.5 kg·mol -1 Mw / Mn = 2.5, and the copolymer contains 5.10 mol% 1-octene.

[0090] Example 26: C3-catalyzed copolymerization of ethylene / 1-octene

[0091] The polymerization process and reaction conditions were the same as in Example 25, and the catalyst used was C3. Polymerization activity: 120 kg·mol⁻¹ -1 (Hf)·h -1Polymer Mw = 147.9 kg·mol -1 Mw / Mn = 31.5, and the copolymer contains 1.07 mol% 1-octene.

[0092] Example 27: C4-catalyzed copolymerization of ethylene / 1-octene

[0093] The polymerization process and reaction conditions were the same as in Example 25, and the catalyst used was C4. Polymerization activity: 17200 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 16.9 kg·mol -1 Mw / Mn = 2.5, and the copolymer contains 3.28 mol% 1-octene.

[0094] Example 28: C5-catalyzed copolymerization of ethylene / 1-octene

[0095] The polymerization process and reaction conditions were the same as in Example 25, and the catalyst used was C5. Polymerization activity: 18400 kg·mol⁻¹ -1 (Hf)·h -1 Polymer Mw = 12.9 kg·mol -1 Mw / Mn = 2.8, and the content of 1-octene in the copolymer is 4.19 mol%.

Claims

1. A class of quinoline-amine coordinated titanium-zirconium-hafnium metal catalysts, the structure of which is shown in formula (I): in, M is selected from titanium, zirconium, and hafnium; R 1 Selected from hydrogen, methyl, ethyl, isopropyl, phenyl, chlorine, fluorine; R 2 Selected from hydrogen, methyl, ethyl, isopropyl, phenyl, chlorine, fluorine; R 3 Selected from hydrogen, methyl, methoxy, tert-butyl, R 4 Selected from hydrogen, C1-C6 straight-chain alkyl, phenyl, benzyl, isopropylphenyl.

2. The preparation method of the quinoline-amine coordinated titanium-zirconium-hafnium metal catalyst according to claim 1 comprises the following steps: under a nitrogen atmosphere, dissolving the metal salt in 10-80 mL of anhydrous solvent, adding 4.0-5.0 molar equivalents of methyl magnesium bromide, reacting at low temperature for 2-6 hours under nitrogen protection, then adding 1 molar equivalent of quinoline-amine ligand and reacting for 5-12 hours; after the reaction is completed, removing the solvent under reduced pressure, extracting with a good solvent to obtain the quinoline-amine coordinated titanium-zirconium-hafnium metal catalyst according to claim 1.

3. The preparation method according to claim 2, characterized in that: The anhydrous solvent is selected from toluene, n-hexane, xylene, and benzene; the good solvent is selected from n-hexane, toluene, pentane, heptane, and cyclohexane.

4. The preparation method according to claim 2, characterized in that: The metal salt is selected from one of TiCl4, ZrCl4, and HfCl4.

5. A method for olefin polymerization, characterized in that: The catalyst used is the quinoline-amine coordinated titanium zirconium hafnium metal catalyst as described in claim 1.

6. The method according to claim 5, characterized in that: The olefin monomer is one or more of ethylene, propylene, 1-butene, styrene, 1-hexene, norbornene, and 1-octene.

7. The method according to claim 5, characterized in that: The quinoline-amine coordinated titanium zirconium hafnium metal catalyst requires the use of a co-catalyst for catalysis. The co-catalyst is one or more of the following: tripentafluorophenylboron, triphenylcarbium tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, aluminoxane, alkylaluminum, and alkylaluminum chloride.

8. The method according to claim 7, characterized in that: The aluminum oxane is methylaluminoxane, ethylaluminoxane, or isobutylaluminoxane; the alkylaluminum is trimethylaluminum, triethylaluminum, triisobutylaluminum, or tri-n-hexylaluminum; and the alkylaluminum chloride is diethylaluminum chloride, sesqui-diethylaluminum chloride, or ethylaluminum dichloride.

9. The method according to claim 5, characterized in that: The polymerization temperature is 0-200℃, the polymerization pressure is 0.1-5MPa, and the solvent used for polymerization is one or more of n-hexane, n-heptane, n-pentane, and toluene.

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