A [nn] bidentate coordination metal catalyst based on quinoline skeleton and preparation method and application thereof

Abstract

The present application relates to a kind of [NN] bidentate coordination metal catalyst based on quinoline skeleton and its preparation method and application, the present application is directly carried out aldehyde amine condensation by quinoline-8-formaldehyde and aniline under the catalysis of p-TsOH, and quinoline-imino ligand is synthesized.The obtained ligand is used in one-pot reaction with in-situ synthesized MMe4 (M=Ti, Zr or Hf), and [NN] bidentate coordination metal catalyst based on quinoline skeleton is prepared.And the quinoline skeleton [NN] bidentate coordination metal catalyst is used for the synthesis of polyolefin.The present application has simple synthesis process, raw material is easy to obtain, product yield is high, has high temperature resistance simultaneously, is suitable for high temperature solution polymerization, and can prepare high-performance polyolefin elastomer.

Description

TECHNICAL FIELD

[0001] The present application relates to a coordination polymerization metal catalyst, in particular to a [NN] bidentate coordination metal catalyst based on quinoline skeleton and its preparation method and application in the field of polyolefins. BACKGROUND

[0002] Polyolefin elastomers (POEs) are a new type of material with properties between traditional thermoplastics and elastomers (such as rubber), which are copolymerized from ethylene and other α-olefins such as 1-octene, 1-butene or 1-hexene. Polyolefin elastomers (POEs) are widely used in the fields of automobiles, photovoltaic packaging, clothing, etc. due to their flexibility, elasticity, low density and easy processability.

[0003] The production of polyolefin elastomers adopts high-temperature solution method, because this process can improve the catalyst activity and reaction rate at a higher temperature, and at the same time, through the uniform distribution of monomers by the solvent, the molecular weight distribution and the comonomer content of the polymer can be precisely controlled, generating a low crystallinity, high-elasticity material. In addition, the solution method is suitable for processing high α-olefin content systems, has higher product uniformity and processing flexibility, and the solvent is easy to recycle, environmentally friendly and economical, which is an ideal choice for industrial production of POEs.

[0004] Constrained geometry catalysts (CGC) were successfully used in the commercial production of POEs in the 1990s due to their good high-temperature resistance (Chem. Rev. 1998, 98, 2587-2598). However, the synthesis of CGC catalysts is difficult, and the technical route is complex; non-metallocene catalysts have been rapidly developed due to their strong structural adjustability and simple synthesis process. In 1999, Fujita et al. reported [NO] bidentate salicylaldiminate titanium and zirconium metal catalysts (FI catalysts) (Chem. Rev. 2011, 111, 30, 2363-2449), but their high-temperature resistance is poor. In 2000, Union Carbide reported [NN] bidentate pyridine-amine zirconium and hafnium metal catalysts, which are suitable for high-temperature solution polymerization (Acc. Chem. Res. 2015, 48, 2004-2016). Kloin reported [NN] bidentate amine-quinoline zirconium and hafnium metal catalysts (Organometallics 2012, 31, 6244-6251), although the catalyst provides good high-temperature resistance and copolymerization performance, but it uses expensive Pd catalyst to catalyze the coupling reaction in the process of synthesizing the ligand, which makes it difficult to be industrialized.

[0005] Therefore, it has been a technical problem in the field to provide a catalyst suitable for the synthesis of polyolefin elastomers in industry. SUMMARY

[0006] The present application aims at the problems existing in the prior art, and provides a quinoline skeleton [NN] bidentate metal catalyst which is resistant to high temperature and suitable for industrial application.

[0007] Another object of the present application is to provide a preparation method of the quinoline skeleton [NN] bidentate metal catalyst which is low in cost and high in yield.

[0008] Another object of the present application is also to provide an application of the quinoline skeleton [NN] bidentate metal catalyst in the preparation of polyolefins.

[0009] The present application provides a quinoline skeleton [NN] bidentate coordination metal catalyst, and the structural formula is shown in formula (I):

[0010]

[0011] In the formula, M is selected from any one of titanium, zirconium or hafnium, and R1, R2 and R3 are selected from any one of fluorine, chlorine, bromine, iodine and alkyl.

[0012] Preferably, the quinoline ligand structure of the quinoline skeleton [NN] bidentate coordination metal catalyst is selected from any one of formula (II):

[0013]

[0014] The present application provides a preparation method of the above-mentioned quinoline skeleton [NN] bidentate metal catalyst, which comprises the following steps:

[0015] Under a nitrogen atmosphere, 0.6-1.5 g of quinoline-8-formaldehyde is dissolved in 10-30 mL of an ethanol solvent, the molar concentration of the ethanol solvent is 0.2-1.0 mol / L, 1.0-1.5 molar equivalents of aniline and 5-10 mg of p-toluenesulfonic acid are added, and reaction is carried out at room temperature for 3 hours; after the ethanol is removed under reduced pressure, anhydrous methanol is added for extraction and filtration to obtain a quinoline-imino ligand; 1.0-1.2 molar equivalents of a metal chloride MCl4 are dissolved in 10-50 mL of an anhydrous solvent, 4.0-6.0 molar equivalents of methylmagnesium bromide are added, stirring is carried out under nitrogen protection at-20 to-50 ℃ for 2 hours, then 1 molar equivalent of the quinoline-imino ligand is added, stirring is carried out at-20 to-50 ℃ for 2 hours, and stirring is carried out at room temperature for 4 hours; the solvent is removed under reduced pressure, extraction is carried out with a good solvent, and the filtrate is concentrated to obtain the quinoline skeleton [NN] bidentate coordination metal catalyst.

[0016] The anhydrous solvent is selected from any one of benzene, toluene and xylene; and the good solvent is selected from any one of n-hexane, cyclohexane, n-pentane and n-heptane.

[0017] The metal chloride MCl4 is selected from one of TiCl4, ZrCl4, HfCl4.

[0018] The application also provides the use of the above-mentioned quinoline skeleton [NN] bidentate coordination metal catalyst in the preparation of polyolefins.

[0019] In the above use, the olefin monomer in the polyolefin is one or several of ethylene, propylene, 1-butene, 1-hexene, 1-octene, styrene, norbornene.

[0020] In the above use, the quinoline skeleton [NN] bidentate coordination metal catalyst is used in combination with a cocatalyst to catalyze the polymerization of olefins, and the cocatalyst is one or several of triphenylboron, triphenylmethyl tetrakis(pentafluorophenyl)borate, alkyl aluminum, aluminoxane.

[0021] Preferably, the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum or tri-n-hexyl aluminum; and the aluminoxane is methyl aluminoxane, ethyl aluminoxane or isobutyl aluminoxane.

[0022] In the above use, the polymerization temperature is 0-200°C, the polymerization pressure is 0.1-5 MPa, and the polymerization solvent is one or several of toluene, xylene, n-hexane, cyclohexane.

[0023] The application has the following advantages and effects:

[0024] In the application, a series of new quinoline-amine ligands are directly synthesized through p-TsOH-catalyzed aldehyde-amine condensation between quinoline-8-formaldehyde and various anilines. The quinoline-amine metal catalysts are obtained through one-pot reaction of the obtained ligands and in-situ synthesized MMe4 (M = Ti, Zr or Hf), which has the advantages of simple synthesis, easy availability of raw materials, high product yield and high catalytic activity (1.62 x 10 7 g (POE) · mol -1 (Hf) · h -1 ), good copolymerization performance (alpha olefin insertion rate greater than 21.6 mol%) and excellent high-temperature resistance (greater than 140°C), and is suitable for the preparation of polyolefin materials through high-temperature solution polymerization.

[0025] The obtained quinoline skeleton [NN] bidentate coordination metal catalyst is used in the synthesis of polyolefin elastomers, and it is found that the molecular weight and alpha olefin insertion rate of the obtained polymer can be effectively improved by changing the substituents on the structure of the catalyst, which can promote the development of high-end polyolefin chemical industry in China and provide a new direction for the development of the polyolefin material field. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 NMR spectrum of the catalyst C1.

[0027] Figure 2 NMR spectrum of catalyst C2.

[0028] Figure 3 NMR spectrum of catalyst C3.

[0029] Figure 4 NMR spectrum of catalyst C4.

[0030] Figure 5 NMR spectrum of catalyst C5.

[0031] Figure 6 NMR spectrum of catalyst C6. DETAILED DESCRIPTION

[0032] The technical solutions of the present application are further explained in the following detailed description in conjunction with the specific embodiments. It should be pointed out that the detailed description is only a specific embodiment and explanation of the essence of the technical solutions of the present application, and should not be understood as a limitation of the protection scope of the present application.

[0033] The raw materials and reagents used in the following examples, unless otherwise specified, can be obtained commercially or prepared by known methods. The experimental methods used in the following examples, unless otherwise specified, are conventional methods known in the art. The concentrations in the following examples, unless otherwise specified, are molar concentrations.

[0034] The compounds synthesized in the following examples are characterized by infrared spectrometer and nuclear magnetic resonance instrument.

[0035] The molecular weight and molecular weight distribution of the polymers obtained in the following polymerization examples are tested at 150°C by high temperature gel permeation chromatography GPC-IR with 1,2,4-trichlorobenzene as solvent. The melting points of the polymers are determined according to the conventional DSC (Q2000) method, and the polymerization activity of the polymers is calculated according to the following formula: Polymerization activity = polymer mass / (molar amount of catalyst x polymerization time). The calculation method of 1-octene insertion rate is referred to the literature (Macromolecules 1999, 32, 3817, Macromolecules 2007, 40, 6879). The high temperature nuclear magnetic resonance of the polymers is tested at 125°C using deuterated o-dichlorobenzene as solvent by Bruker AC400.

[0036] Methylaluminoxane (MAO) used in the examples is purchased. In the following examples, the definition of Al / Hf is the molar ratio of metal Al in the cocatalyst MAO to Hf in the metal complex, not the molar ratio of aluminum element to metal Hf.

[0037] The synthesis of the complexes in the following examples was carried out according to the following reaction scheme:

[0038]

[0039] M = Ti, Zr, Hf.

[0040] Synthesis Example 1, Preparation of Catalyst Cat 1

[0041] Take 0.79 g of quinoline-8-carboxaldehyde (5 mmol), add 20 mL of anhydrous ethanol, slowly add 0.61 g of 2,6-dimethylaniline (5 mmol) at room temperature, catalyze the reaction with 5 mg of p-toluenesulfonic acid for 3 hours, remove the ethanol under reduced pressure using a rotary evaporator, where the rotary evaporation temperature is 60°C, the vacuum degree is 0.7 bar, and the rotation speed is 120 revolutions per minute, add 5 mL of anhydrous methanol and stir for 5 minutes, filter to obtain 8-(2,6-Me2-C6H3-N=CH)-quinoline ligand L1 1.12 g, yield 85%. NMR data 1 H NMR (400 MHz, Chloroform-d) δ 8.90 (dd, J = 3.9, 1.7 Hz, 1H), 8.83 (s, 1H), 8.25 (dt, J = 8.3, 1.7 Hz, 1H), 8.03-7.96 (m, 1H), 7.89-7.82 (m, 1H), 7.54 (ddd, J = 8.2, 6.0, 2.1 Hz, 2H), 7.20-7.12 (m, 1H), 6.96 (d, J = 7.0 Hz, 2H), 2.21 (s, 6H). 13 C NMR (100 MHz, Benzene-d6) δ 159.47, 150.93, 149.35, 148.86, 136.79, 134.09, 133.10, 130.51, 129.14, 127.47, 127.24, 126.90, 126.17, 121.63, 17.93.

[0042] Take 0.64 g of hafnium tetrachloride (2 mmol), add 20 mL of anhydrous toluene, slowly add 3 mL / 9 mmol of methyl magnesium bromide solution (3M) at -40°C (using aluminum block as refrigerant medium), stir for 2 hours. Add 0.52 g of 8-(2,6-Me2-C6H3-N=CH)-quinoline ligand L1 (2 mmol), react for 2 hours at -40°C in the dark, and continue to react for 4 hours after returning to room temperature. After the reaction is completed, remove the solvent under reduced pressure (30°C oil pump to extract the solvent, vacuum degree 1 bar), add 20 mL of toluene, stir for 5 minutes, filter to obtain a yellow filtrate, and concentrate the filtrate (30°C oil pump to extract the solvent, vacuum degree 1 bar) to obtain the product 0.76 g, yield 78%. NMR data 1H NMR (400 MHz, Chloroform-d) δ 8.26 (dd, J = 6.6, 1.7 Hz, 1H), 7.81 (dd, J = 7.9, 1.7 Hz, 1H), 7.76 (dd, J = 6.6, 1.7 Hz, 1H), 7.49 - 7.39 (m, 2H), 7.17 - 7.06 (m, 2H), 6.98 (d, J = 7.9 Hz, 2H), 4.81 (qd, J = 7.9, 0.6 Hz, 1H), 2.07 (s, 6H), 1.56 (d, J = 7.9 Hz, 3H). 13 C NMR (100 MHz, Benzene-d6) δ 151.35, 138.01, 136.36, 135.34, 134.98, 134.22, 130.55, 127.92, 126.77, 126.40, 125.91, 125.81, 125.17, 57.47, 20.26, 18.80, 18.77, 18.75, 18.06.

[0043] Cat 1 structure is as follows:

[0044]

[0045] Synthesis Example 2, preparation of catalyst Cat 2

[0046] Take 0.79 g of quinoline-8-formaldehyde (5 mmol), add 20 mL of anhydrous ethanol, slowly add 0.68 g of 2,4,6-trimethyl aniline (5 mmol) at room temperature, add 5 mg of p-toluenesulfonic acid to catalyze the reaction for 3 hours, remove the ethanol under reduced pressure, then add anhydrous methanol to extract and filter, to obtain 8-(2,4,6-Me3-C6H3-N=CH)-quinoline ligand L2 1.13 g, yield 82%. NMR data 1 H NMR (400 MHz, Chloroform-d) δ 8.90 (dd, J = 3.9, 1.7 Hz, 1H), 8.83 (s, 1H), 8.25 (dt, J = 8.3, 1.7 Hz, 1H), 8.03 - 7.96 (m, 1H), 7.89 - 7.82 (m, 1H), 7.54 (ddd, J = 8.2, 6.0, 2.1 Hz, 2H), 6.89 (d, J = 0.8 Hz, 2H), 2.27 (d, J = 1.0 Hz, 2H). 13C NMR (100 MHz, Benzene-d6) δ 159.23, 149.36, 149.35, 148.86, 136.79, 133.85, 133.10, 131.29, 130.51, 129.14, 128.71, 127.47, 127.24, 121.63, 20.77, 18.16.

[0047] Weigh 0.64 g hafnium tetrachloride (2 mmol), add 20 mL anhydrous toluene, slowly add 3 mL / 9 mmol methyl magnesium bromide solution (3M) at -40°C (use aluminum block as refrigerant), stir for 2 hours. Add 0.55 g 8-(2,4,6-Me3-C6H3-N=CH)-quinoline ligand L2 (2 mmol), react for 2 hours at -40°C in the dark, continue to react for 4 hours after recovering to room temperature. After the reaction is completed, remove the solvent, add toluene to extract, filter, and concentrate the filtrate to obtain the product 0.83 g, with a yield of 80%. NMR data 1 H NMR (400 MHz, Chloroform-d) δ 8.26 (dd, J = 6.6, 1.7 Hz, 1H), 7.81 (dd, J = 7.9, 1.7 Hz, 1H), 7.76 (dd, J = 7.8, 6.6 Hz, 1H), 7.49 - 7.39 (m, 2H), 7.14 (dd, J = 8.3, 1.8 Hz, 1H), 6.78 (s, 2H), 4.81 (qd, J = 7.9, 0.6 Hz, 1H), 2.26 (d, J = 0.9 Hz, 3H), 1.95 (s, 4H), 1.56 (d, J = 7.9 Hz, 3H). 13 C NMR (100 MHz, Benzene-d6) δ 148.09, 138.01, 136.27, 135.34, 135.05, 134.98, 134.22, 130.55, 128.58, 126.77, 126.40, 125.81, 125.17, 57.47, 20.68, 20.26, 18.80, 18.77, 18.75, 18.27.

[0048] The structure of Cat 2 is as follows:

[0049]

[0050] Synthesis Example 3, preparation of catalyst Cat 3

[0051] Take 0.79 g of quinoline-8-formaldehyde (5 mmol), add 20 mL of anhydrous ethanol, slowly add 0.82 g of 2,4-dichloroaniline (5 mmol) at room temperature, catalyze the reaction with 5 mg of p-toluenesulfonic acid for 3 hours, remove the ethanol under reduced pressure, then add anhydrous methanol for extraction, filter, and obtain 8-(2,6-Cl2-C6H3-N=CH)-quinoline ligand L3 1.31 g with a yield of 86%. NMR data 1 H NMR (400 MHz, Chloroform-d) δ 9.03 (s, 1H), 8.90 (dd, J = 3.9, 1.7 Hz, 1H), 8.25 (dt, J = 8.3, 1.7 Hz, 1H), 8.03-7.96 (m, 1H), 7.92-7.85 (m, 1H), 7.54 (ddd, J = 8.3, 6.0, 2.1 Hz, 2H), 7.45-7.39 (m, 2H), 7.30 (dd, J = 8.1, 6.8 Hz, 1H). 13 C NMR (100 MHz, Benzene-d6) δ 159.66, 149.35, 148.68, 147.01, 136.79, 133.59, 130.51, 130.17, 129.74, 129.14, 127.47, 127.32, 126.28, 121.63.

[0052] Take 0.64 g of hafnium tetrachloride (2 mmol), add 20 mL of anhydrous toluene, slowly add 3 mL / 9 mmol of methyl magnesium bromide solution (3M) at -40°C (using aluminum block as refrigerant), stir for 2 hours. Add 0.61 g of 8-(2,6-Cl2-C6H3-N=CH)-quinoline ligand L3 (2 mmol), react for 2 hours at -40°C in the dark, and continue to react for 4 hours after the temperature is restored to room temperature. After the reaction is completed, remove the solvent, add toluene for extraction, filter, and concentrate the filtrate to obtain 0.84 g of product with a yield of 78%. NMR data 1 H NMR (400 MHz, Chloroform-d) δ 8.26 (dd, J = 6.6, 1.7 Hz, 1H), 7.84-7.72 (m, 2H), 7.49-7.39 (m, 2H), 7.31 (d, J = 1.3 Hz, 1H), 7.29 (s, 1H), 7.24-7.10 (m, 2H), 4.78 (qd, J = 7.8, 0.6 Hz, 1H), 1.56 (d, J = 7.9 Hz, 3H). 13C NMR (100 MHz, Benzene-d6) δ 148.17, 138.01, 135.36, 134.98, 134.20, 132.22, 130.55, 128.34, 127.11, 126.77, 126.40, 125.81, 125.17, 57.44, 20.37, 18.81, 18.79, 18.77.

[0053] Cat 3 has the following structure:

[0054]

[0055] Synthesis Example 4, Preparation of Catalyst Cat 4

[0056] Quinoline-8-carboxaldehyde (0.79 g, 5 mmol) was weighed into 20 mL of anhydrous ethanol, and 2,6-diisopropylaniline (0.89 g, 5 mmol) was slowly added at room temperature. The reaction was catalyzed by the addition of 5 mg of p-toluenesulfonic acid, and was allowed to proceed for 3 hours. After removing the ethanol under reduced pressure, anhydrous methanol was added to extract and filter, and 8-(2,6-i-Pr2-C6H3-N=CH)-quinoline ligand L4 was obtained in a yield of 97% (1.31 g). NMR data 1 HNMR (400 MHz, Chloroform-d) δ 8.90 (dd, J = 3.9, 1.7 Hz, 1H), 8.84 (d, J = 0.6 Hz, 1H), 8.25 (dt, J = 8.3, 1.7 Hz, 1H), 8.03 - 7.96 (m, 1H), 7.92 - 7.86 (m, 1H), 7.54 (ddd, J = 8.3, 6.0, 2.1 Hz, 2H), 7.26 (dd, J = 8.3, 6.4 Hz, 1H), 7.19 (dd, J = 7.3, 0.8 Hz, 2H), 3.14 - 3.00 (m, 2H), 1.27 (d, J = 6.2 Hz, 12H). 13 C NMR (100 MHz, Benzene-d6) δ 159.25, 149.35, 148.86, 146.04, 137.78, 136.79, 133.31, 130.51, 129.14, 127.92, 127.47, 127.25, 124.65, 121.63, 29.43, 22.25.

[0057] Take 0.64 g of hafnium tetrachloride (2 mmol), add 20 mL of anhydrous toluene, slowly add 3 mL / 9 mmol of methyl magnesium bromide solution (3M) under the condition of -40°C (use aluminum block as refrigerant), stir for 2 hours. Add 8-(2,6-i-Pr2-C6H3-N=CH)-quinoline ligand L4 (0.63 g, 2 mmol), react for 2 hours under the condition of -40°C in the dark, continue to react for 4 hours after recovering to room temperature. After the reaction is completed, remove the solvent, add toluene for extraction, filter, and concentrate the filtrate to obtain the product 1.03 g, with a yield of 92%. NMR data 1 HNMR (400 MHz, Chloroform-d) δ 8.26 (dd, J = 6.6, 1.7 Hz, 1H), 7.81 (dd, J = 7.9, 1.7 Hz, 1H), 7.76 (dd, J = 7.8, 6.6 Hz, 1H), 7.49-7.39 (m, 2H), 7.32 (t, J = 8.3 Hz, 1H), 7.14 (dd, J = 8.2, 1.9 Hz, 1H), 7.10-7.03 (m, 2H), 4.83 (qd, J = 7.9, 0.6 Hz, 1H), 3.26-3.11 (m, 2H), 1.56 (d, J = 7.9 Hz, 3H), 1.22 (dd, J = 19.9, 6.9 Hz, 12H). 13 C NMR (100 MHz, Benzene-d6) δ 149.03, 145.21, 138.01, 135.34, 134.98, 134.22, 130.55, 127.21, 126.77, 126.40, 125.81, 125.17, 124.51, 57.63, 29.14, 24.28, 20.26, 18.80, 18.77, 18.75.

[0058] The structure of Cat 4 is as follows:

[0059]

[0060] Synthesis Example 5, preparation of catalyst Cat 5

[0061] Take 0.38 g of titanium tetrachloride (2 mmol), add 20 mL of anhydrous toluene, slowly add 3 mL / 9 mmol of methyl magnesium bromide solution (3M) under the condition of -40°C (use aluminum block as refrigerant), stir for 2 hours. Add 0.63 g of 8-(2,6-i-Pr2-C6H3-N=CH)-quinoline ligand L4 (2 mmol), react for 2 hours under the condition of -40°C in the dark, continue to react for 4 hours after recovering to room temperature. After the reaction is completed, remove the solvent, add toluene for extraction, filter, and obtain the product 0.70 g, with a yield of 82%. NMR data 1H NMR (400 MHz, Chloroform-d) δ 8.36 (dd, J = 6.9, 1.4 Hz, 1H), 7.93 (ddt, J = 7.6, 6.0, 1.6 Hz, 2H), 7.71 (dd, J = 8.1, 6.8 Hz, 1H), 7.25 (dt, J = 8.9, 0.9 Hz, 1H), 7.18 (dd, J = 9.3, 7.1 Hz, 1H), 7.10 (dd, J = 8.1, 1.0 Hz, 2H), 4.55 (qd, J = 7.8, 0.6 Hz, 1H), 3.06 (heptd, J = 7.0, 0.6 Hz, 2H), 1.50 (s, 1H), 1.25 (d, J = 6.8 Hz, 5H), 1.20 (d, J = 6.8 Hz, 6H), 1.03 (s, 9H). 13 C NMR (100 MHz, Benzene-d6) δ 148.48, 145.21, 137.93, 135.47, 134.61, 134.25, 130.85, 127.21, 126.77, 126.38, 125.79, 125.22, 124.52, 57.82, 29.03, 24.28, 22.15, 20.33.

[0062] Cat 5 structure is as follows:

[0063]

[0064] Synthesis Example 6, Preparation of Catalyst Cat 6

[0065] Zirconium tetrachloride 0.47g (2mmol) was weighed, 20mL anhydrous toluene was added, 3mL / 9mmol methyl magnesium bromide solution (3M) was slowly added at -40°C (using aluminum block as refrigerant), stirred for 2 hours. 0.63g 8-(2,6-i-Pr2-C6H3-N=CH)-quinoline ligand L4 (2mmol) was added, and the reaction was carried out at -40°C for 3 hours in the dark, and then the temperature was raised to room temperature and the reaction was continued for 6 hours. After the reaction was completed, the solvent was removed, toluene was added for extraction, and filtration was performed, and the filtrate was concentrated to obtain the product 0.72g, with a yield of 76%. NMR data 1 H NMR (400 MHz, Chloroform-d) δ 7.94 (ddt, J = 10.4, 8.3, 1.5 Hz, 1H), 7.27 - 7.14 (m, 1H), 7.12 - 7.05 (m, 1H), 3.11 - 2.96 (m, 1H), 1.52 (s, OH), 1.23 (dd, J = 19.9, 6.8 Hz, 4H), 1.04 (s, 3H). 13C NMR (100 MHz, Benzene-d6) δ 148.69, 145.09, 138.03, 135.44, 135.41, 133.86, 130.86, 127.21, 126.77, 126.39, 125.75, 125.24, 124.40, 57.66, 29.04, 24.28, 21.62, 20.29.

[0066] Cat 6 has the following structure:

[0067]

[0068] Example A1

[0069] Ethylene polymerization catalyzed by Cat 1 prepared by synthesis example 1 was carried out, including the following steps:

[0070] Into a 5L stainless steel autoclave which had been pre-evacuated and replaced with nitrogen, 2000 mL of cyclohexane was added at room temperature, mechanical stirring was started and maintained at 600 rpm, and temperature was raised. When the temperature reached 120 °C, ethylene was injected into the autoclave, and the ethylene pressure in the autoclave was set at 3.0 MPa. After reaching the set pressure, 30 mL of cyclohexane solution containing 20 μmol of Cat 1 and 8 mL of cocatalyst MAO (Al / Hf = 500) was injected into the autoclave through a high-pressure pump, and the polymerization started. During the reaction, the reaction temperature, ethylene pressure and stirring speed were kept constant. After 30 min, the reaction was completed, the gas in the autoclave was discharged through a vent valve, the reaction solution was neutralized with 5% wt hydrochloric acid in ethanol solution, and the polymer was obtained and washed with ethanol several times, vacuum dried to constant weight, and weighed to obtain 152 g of polymer, which was polyethylene.

[0071] The polymerization activity of the obtained polyethylene was calculated and GPC was measured, and the results were as follows: polymerization activity 1.52 x 10 7 g·mol -1 (Hf)h -1 , polymer M w = 3.23 x 10 5 g·mol -1 , M w / M n = 2.4, T m (polymer melting point) = 126.3 °C.

[0072] Example A2

[0073] Ethylene polymerization catalyzed by Cat 1 prepared by synthesis example 1, which was different from example A1 only in that the polymerization temperature was 100 °C, and 148 g of polymer (polyethylene) was obtained.

[0074] The polymerization activity was determined to be 1.48 x 10 7 g-mol -1 (Hf)h -1 , polymer M w = 3.42 x 10 5 g-mol -1 , M w / M n = 2.1, T m (polymer melting point) = 126.5°C.

[0075] Example A3

[0076] Cat 1 | MAO prepared using Synthesis Example 1 was used to catalyze ethylene polymerization, with the difference from Example Al being that the polymerization temperature was 130°C, and 138 g of polymer (polyethylene) was obtained.

[0077] The polymerization activity was determined to be 1.38 x 10 7 g-mol -1 (Hf)h -1 , polymer M w = 2.94 x 10 5 g-mol -1 , M w / M n = 3.2, T m (polymer melting point) = 126°C.

[0078] Example A4

[0079] Cat 1 | MAO prepared using Synthesis Example 1 was used to catalyze ethylene polymerization, with the difference from Example Al being that the polymerization temperature was 140°C, and 130 g of polymer was obtained.

[0080] The polymerization activity was determined to be 1.30 x 10 7 g-mol -1 (Hf)h -1 , polymer M w = 2.44 x 10 5 g-mol -1 , M w / M n = 6.4, T m (polymer melting point) = 123°C.

[0081] Example A5

[0082] Cat 1 | MAO prepared using Synthesis Example 1 was used to catalyze ethylene polymerization, with the difference from Example Al being that the polymerization reaction temperature was unchanged, and the amount of cocatalyst added was changed, with 16 mL of cocatalyst MAO (Al / Hf = 1000) being added, and 178 g of polymer was obtained.

[0083] The polymerization activity was determined to be 1.68 x 10 7 g-mol -1 (Hf)h -1 , polymer M w = 4.06 x 10 5 g-mol -1 , M w / M n = 3.0, T m (polymer melting point) = 130°C.

[0084] As can be seen from Examples Al to A4, Cat 1 | MAO catalyzes ethylene polymerization with a high catalytic activity (distributed between 1.30 x 10 7 g-mol -1 (Hf)h -1 ~ 1.52 x 10 7 g-mol -1 (Hf)h -1 ) in a temperature window of 100°C to 140°C; as can be seen from Example Al and Example A5, a high catalytic activity and a narrow molecular weight distribution can be achieved in Cat 1 | MAO catalysts with a ratio of both from 500:1 to 1000:1.

[0085] Example A6

[0086] Cat 2 | MAO prepared using Synthesis Example 2 was used to catalyze ethylene polymerization, with the only difference from Example Al being that the polymerization temperature was 120°C, and 20 μmol of Cat 2 was added as the main catalyst, and 142 g of polymer was obtained.

[0087] The polymerization activity was determined to be 1.42 x 10 7 g-mol -1 (Hf)h -1 , polymer M w = 3.56 x 10 5 g-mol -1 , M w / M n = 3.1, T m (polymer melting point) = 126°C.

[0088] Example A7

[0089] Cat 3 | MAO prepared using Synthesis Example 3 was used to catalyze ethylene polymerization, with the only difference from Example Al being that the polymerization temperature was 120°C, and 20 μmol of complex Cat 3 was added as the main catalyst, and 138 g of polymer was obtained.

[0090] The polymerization activity was determined to be 1.38 x 107 g mol -1 (Hf)h -1 , polymer M w = 3.16 x 10 5 g mol -1 , M w / M n = 3.1, T m (polymer melting point) = 124°C.

[0091] Example A8

[0092] Ethylene polymerization with Cat 4 | MAO prepared using synthesis example 4, with the only difference from example Al being that the polymerization temperature was 120°C, 20 μmol Cat 4 was added as the procatalyst, and 162 g of polymer was obtained.

[0093] The polymerization activity was determined to be 1.62 x 10 7 g mol -1 (Ti)h -1 , polymer M w = 2.42 x 10 5 g mol -1 , M w / M n = 2.2, T m (polymer melting point) = 128°C.

[0094] Example A9

[0095] Ethylene polymerization with Cat 5 | MAO prepared using synthesis example 5, with the only difference from example Al being that the polymerization temperature was 120°C, 20 μmol Cat 5 was added as the procatalyst, and 116 g of polymer was obtained.

[0096] The polymerization activity was determined to be 1.16 x 10 7 g mol -1 (Ti)h -1 , polymer M w = 2.64 x 10 5 g mol -1 , M w / M n = 3.8, T m (polymer melting point) = 133°C.

[0097] Example A10

[0098] Ethylene polymerization with Cat 6 | MAO prepared using synthesis example 6, with the only difference from example Al being that the polymerization temperature was 120°C, 20 μmol Cat 6 was added as the procatalyst, and 122 g of polymer was obtained.

[0099] Polymerization activity 1.22 x 10 7 g-mol -1 (Zr)h -1 , Polymer M w = 2.25 x 10 5 g-mol -1 , M w / M n = 3.8, T m (Polymer melting point) = 125°C.

[0100] As can be seen from Examples Al to A10, the quinoline skeleton [NN] bidentate metal catalysts provided in the present application have high polymerization activity in catalyzing ethylene polymerization, and Cat 4 has the best catalytic activity.

[0101] Example Bl

[0102] Cat 4 prepared using Synthesis Example 4 was used to catalyze ethylene / 1-octene polymerization, including the following steps:

[0103] At room temperature, 2000 mL of cyclohexane and 210 g of 1-octene were added to a 5 L stainless steel reactor which had been pre-evacuated and replaced with nitrogen, mechanical stirring was started and maintained at 600 rpm, and temperature was raised, and when the temperature reached 120°C, ethylene was injected into the reactor, the ethylene pressure in the reactor was set to 3.0 MPa, and after reaching the set pressure, 30 mL of cyclohexane solution containing Cat 4 (20 μmol) and co-catalyst MAO (Al / Hf = 500) (8 mL) was added to the reactor by a high-pressure pump, and the polymerization reaction started. During the reaction, the reaction temperature, ethylene pressure and stirring speed were kept constant. After 30 min, the reaction was completed, the gas in the reactor was discharged through a vent valve, the reaction solution was neutralized with 5% wt hydrochloric acid in ethanol solution, the polymer was obtained and washed with ethanol several times, and vacuum dried to constant weight, and weighed to obtain 136 g of polymer, which was an ethylene / 1-octene copolymer.

[0104] The polymerization activity of the obtained copolymer was calculated and GPC was measured, and the results were as follows: polymerization activity 1.36 x 10 7 g-mol -1 (Hf)h -1 , Polymer M w = 2.84 x 10 5 g-mol -1 , M w / M n = 2.3, 1-octene insertion rate 22.8 mol%.

[0105] Example Bl

[0106] Ethylene / 1-octene polymerization with Cat 4|MAO prepared as in synthesis example 4, the difference with example B1 is only that the polymerization temperature is 100°C, 20 μmol Cat 4 is added as procatalyst, and 103 g of polymer is obtained.

[0107] The polymerization activity is determined to be 1.03 x 10 6 g-mol -1 (Hf)h -1 , the polymer M w = 3.2 x 10 5 g-mol -1 , M w / M n = 2.0, the 1-octene incorporation is 25.6 mol%.

[0108] Example B3

[0109] Ethylene / 1-octene polymerization with Cat 4|MAO prepared as in synthesis example 4, the difference with example B1 is only that the polymerization temperature is 130°C, 20 μmol Cat 4 is added as procatalyst, and 100 g of polymer is obtained.

[0110] The polymerization activity is determined to be 1.0 x 10 7 g-mol -1 (Hf)h -1 , the polymer M w = 2.53 x 10 5 g-mol -1 , M w / M n = 2.6, the 1-octene incorporation is 19.5 mol%.

[0111] Example B4

[0112] Ethylene / 1-octene polymerization with Cat 4|MAO prepared as in synthesis example 4, the difference with example B1 is only that the polymerization temperature is 140°C, 20 μmol Cat 4 is added as procatalyst, and 89 g of polymer is obtained.

[0113] The polymerization activity is determined to be 0.89 x 10 7 g-mol -1 (Hf)h -1 , the polymer M w = 2.32 x 10 5 g-mol -1 , M w / M n = 3.0, T m (polymer melting point) = 92°C, the 1-octene incorporation is 10.9 mol%.

[0114] As can be seen from examples B1-B4, Cat 4jMAO catalyses the polymerization of ethylene with a high catalytic activity (ranging between 0.89 x 10 7 g-mol -1 (Hf)h -1 ~ 1.36 x 10 7 g-mol -1 (Hf)h -1 ) and a narrow molecular weight distribution (M w / M n ranging between 2.0 and 3.0).

[0115] Example B5

[0116] Cat 1jMAO was used to catalyse the polymerization of ethylene / 1-octene, prepared using synthesis example 1, with the only difference with example B1 being that the polymerization temperature was 120°C and 20 μmol of Cat 1 was added as the procatalyst, obtaining 78 g of polymer.

[0117] The polymerization activity was determined to be 0.78 x 10 7 g-mol -1 (Hf)h -1 , the polymer M w = 2.42 x 10 5 g-mol -1 , M w / M n = 2.6 and the 1-octene insertion rate was 14.6 mol%.

[0118] Example B6

[0119] Cat 2jMAO was used to catalyse the polymerization of ethylene / 1-octene, prepared using synthesis example 2, with the only difference with example B1 being that the polymerization temperature was 120°C and 20 μmol of Cat 2 was added as the procatalyst, obtaining 83 g of polymer.

[0120] The polymerization activity was determined to be 0.83 x 10 7 g-mol -1 (Hf)h -1 , the polymer M w = 2.32 x 10 5 g-mol -1 , M w / M n = 3.6 and the 1-octene insertion rate was 16.8 mol%.

[0121] Example B7

[0122] Ethylene / 1-octene polymerization with Cat 3|MAO prepared as in synthesis example 3, the only difference with example B1 being that the polymerization temperature was 120°C and 20 μmol Cat 3 was added as the procatalyst, gave 92 g of polymer.

[0123] The polymerization activity was determined to be 0.92 x 10 7 g-mol -1 (Hf)h -1 , the polymer M w = 2.66 x 10 5 g-mol -1 , M w / M n = 3.2, 1-octene insertion rate 17.2 mol%.

[0124] Example B8

[0125] Ethylene / 1-octene polymerization with Cat 5|MAO prepared as in synthesis example 5, the only difference with example B1 being that the polymerization temperature was 120°C and 20 μmol Cat 5 was added as the procatalyst, gave 68 g of polymer.

[0126] The polymerization activity was determined to be 0.68 x 10 7 g-mol -1 (Ti)h -1 , the polymer M w = 2.45 x 10 5 g-mol -1 , M w / M n = 3.2, 1-octene insertion rate 18.4 mol%.

[0127] Example B9

[0128] Ethylene / 1-octene polymerization with Cat 6|MAO prepared as in synthesis example 6, the only difference with example B1 being that the polymerization temperature was 120°C and 20 μmol Cat 6 was added as the procatalyst, gave 76 g of polymer.

[0129] The polymerization activity was determined to be 0.76 x 10 7 g-mol -1 (Zr)h -1 , the polymer M w = 2.51 x 10 5 g-mol -1 , M w / M n = 2.6, 1-octene insertion rate 20.6 mol%.

[0130] From Examples B1 to B9, it can be seen that the quinoline skeleton [NN] bidentate metal catalysts provided by the present application have high polymerization activity in the copolymerization of ethylene and α-olefins, and the molecular weight distribution of the copolymer is narrow and the insertion rate of α-olefin is high. At 140°C, the polymerization activity and the insertion rate of α-olefin are still high, which shows that the quinoline skeleton [NN] bidentate metal catalysts provided by the present application have good thermal stability.

[0131] Example B10

[0132] Cat 4 | MAO was used to catalyze ethylene / 1-octene polymerization, and the difference from Example B1 was that the amount of the cocatalyst added was changed, 16 mL of the cocatalyst MAO (Al / Hf=1000) was added, and 145 g of polymer was obtained.

[0133] The polymerization activity was 1.45 x 10 7 g·mol -1 (Zr)h -1 , the polymer M w = 2.85 x 10 5 g·mol -1 , M w / M n = 2.5, and the insertion rate of 1-octene was 19.8 mol%.

[0134] Example B11

[0135] Cat 4 | MAO was used to catalyze ethylene / 1-octene polymerization, and the difference from Example B1 was that the amount of the cocatalyst added was changed, 16 mL of the cocatalyst MAO (Al / Hf=1000) was added, and 145 g of polymer was obtained.

[0136] The polymerization activity was 1.45 x 10 6 g·mol -1 (Hf)h -1 , the polymer M w = 2.85 x 10 5 g·mol -1 , M w / M n = 2.5, and the insertion rate of 1-octene was 19.8 mol%.

[0137] Example B12

[0138] The Cat 4|MAO prepared by using the synthesis example 4 was used to catalyze ethylene / 1-octene polymerization, and the difference from the example B1 was only that the polymerization reaction temperature was unchanged, and the amount of the cocatalyst added was changed, 20 mL of the cocatalyst MAO (Al / Hf=2000) was added, and 162 g of the polymer was obtained.

[0139] The polymerization activity was 1.62x10 7 g·mol -1 (Hf)h -1 , the polymer M w =2.8x10 5 g·mol -1 , M w / M n =2.1, and the 1-octene insertion rate was 21.6 mol%.

[0140] As can be seen from the examples B1, B10-B12, the complex provided by the application can catalyze the copolymerization of ethylene and alpha-olefin when used as a main catalyst, and the ratio of the main catalyst to the cocatalyst MAO catalyst can be from 100 to 2000, and a higher polymerization activity can be obtained. It should be noted that the ratio of the complex provided by the application as a main catalyst to the cocatalyst MAO catalyst can also be selected outside the range of 100 to 2000.

[0141] Comparative example 1

[0142] The CGC catalyst [Me2Si(C5Me4)(N t Bu)]TiMe2 was used to catalyze ethylene / 1-octene polymerization, including the following steps:

[0143] At room temperature, 2000 mL of cyclohexane and 210 g of 1-octene were added to a 5 L stainless steel reaction kettle which had been pre-vacuumed and replaced with nitrogen, mechanical stirring was started and maintained at 600 rpm, and the temperature was started to be raised. When the temperature reached 120°C, ethylene was injected into the reaction kettle, and the ethylene pressure in the reaction kettle was set to 3.0 MPa. After reaching the set pressure, 30 min of pre-dissolution was performed, and then a 30 mL cyclohexane solution of the CGC catalyst [Me2Si(C5Me4)(N t Bu)]TiMe2 (20 μmol) and the cocatalyst MAO (Al / Ti=500) (8 mL) was added to the reaction kettle, and the polymerization reaction started. During the reaction, the reaction temperature, ethylene pressure and stirring speed were kept unchanged. After 30 min, the reaction was completed, the gas in the kettle was discharged through a vent valve, the reaction liquid was neutralized with a 5% wt hydrochloric acid acidified ethanol solution, the polymer was obtained and washed with ethanol several times, vacuum dried to constant weight, and weighed to obtain 90 g of the polymer, which was an ethylene / 1-octene copolymer.

[0144] The polymerization activity was calculated for the resulting copolymer and GPC was measured, with the following results: polymerization activity 0.9 x 10 7 g-mol -1 (Ti)h -1 , polymer M w = 2.32 x 10 5 g-mol -1 , M w / M n = 3.5, 1-octene insertion 10.6 mol%.

[0145] Finally, it should be noted that the above examples are merely intended to illustrate the technical solutions of the present application, and are not intended to limit the same; although the present application has been described in detail with reference to the foregoing examples, those of ordinary skill in the art will understand that they can still modify the technical solutions described in the foregoing examples, or make equivalent replacements for some or all of the technical features therein; and such modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A quinoline skeleton [NN] bidentate coordination metal catalyst, characterized in that, The structural formula is shown in equation (I): In formula (I), M is selected from any one of titanium, zirconium or hafnium; in formula (I), R1, R2 and R3 are selected from any one of fluorine, chlorine, bromine, iodine and alkyl groups, respectively.

2. The quinoline skeleton [NN] bidentate coordination metal catalyst according to claim 1, characterized in that, The quinoline ligand structure of the quinoline skeleton [NN] bidentate coordination metal catalyst is selected from any one of the structures shown in formula (II):

3. The method for preparing a quinoline skeleton [NN] bidentate coordination metal catalyst according to claim 1, characterized in that, Includes the following steps: Under a nitrogen atmosphere, 0.6-1.5 g of quinoline-8-carboxaldehyde was dissolved in 10-30 mL of ethanol solvent (ethanol molar concentration 0.2-1.0 mol / L), and 1.0-1.5 molar equivalents of aniline and 5-10 mg of p-toluenesulfonic acid were added. The reaction was carried out at room temperature for 3 hours. After removing the ethanol under reduced pressure, anhydrous methanol was added for extraction and filtration to obtain the quinoline-imine ligand. 1.0-1.2 molar equivalents of metal chloride MCl4 were dissolved in 10-50 mL of anhydrous solvent, and 4.0-6.0 molar equivalents of methyl magnesium bromide were added. The mixture was stirred at -20 to -50 °C for 2 hours under nitrogen protection. Then, 1 molar equivalent of the quinoline-imine ligand was added, and the mixture was stirred at -20 to -50 °C for 2 hours, followed by stirring at room temperature for 4 hours. The solvent was removed under reduced pressure, and the mixture was extracted with a good solvent. The filtrate was concentrated to obtain the quinoline skeleton [NN] bidentate coordinated metal catalyst.

4. The method for preparing a quinoline skeleton [NN] bidentate coordination metal catalyst according to claim 3, characterized in that, The anhydrous solvent is selected from any one of benzene, toluene, and xylene; the good solvent is selected from any one of n-hexane, cyclohexane, n-pentane, n-heptane, and toluene.

5. The method for preparing a quinoline skeleton [NN] bidentate coordination metal catalyst according to claim 3, characterized in that, The metal chloride MCl4 is selected from one of TiCl4, ZrCl4, and HfCl4.

6. The application of the quinoline skeleton [NN] bidentate coordination metal catalyst according to claim 1 in the preparation of polyolefins.

7. The application of the quinoline skeleton [NN] bidentate coordination metal catalyst according to claim 6 in the preparation of polyolefins, characterized in that, The olefin monomer in the polyolefin is one or more of ethylene, propylene, 1-butene, 1-hexene, 1-octene, styrene, and norbornene.

8. The application of the quinoline skeleton [NN] bidentate coordination metal catalyst according to claim 6 in the preparation of polyolefins, characterized in that, The quinoline skeleton [NN] bidentate coordination metal catalyst is used in combination with a co-catalyst to catalyze olefin polymerization. The co-catalyst is one or more of triphenylpentafluorophenylborone, triphenylmethyltetra(pentafluorophenyl)borate, alkylaluminum, and aluminoxane.

9. The application of the quinoline skeleton [NN] bidentate coordination metal catalyst according to claim 8 in the preparation of polyolefins, characterized in that, The alkylaluminum is trimethylaluminum, triethylaluminum, triisobutylaluminum, or tri-n-hexylaluminum; the aluminum oxane is methylaluminoxane, ethylaluminoxane, or isobutylaluminoxane.

10. The application of the quinoline skeleton [NN] bidentate coordination metal catalyst according to claim 8 in the preparation of polyolefins, characterized in that, In the olefin polymerization reaction, the polymerization temperature is 0-200℃, the polymerization pressure is 0.1-5MPa, and the polymerization solvent is one or more of toluene, xylene, n-hexane, and cyclohexane.

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