A high temperature resistant catalyst for the synthesis of polyolefin elastomers

Abstract

The application provides a high-temperature-resistant catalyst for synthesizing a polyolefin elastomer, which has the advantages of high activity, high-temperature resistance, high comonomer content in the polyolefin elastomer product, and stable structure, and the polyolefin elastomer prepared by the application has low melting point and good elongation performance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of polyolefin elastomer preparation, and particularly relates to a high-temperature-resistant catalyst for synthesizing polyolefin elastomer. BACKGROUND

[0002] Polyolefin materials are the most widely used and produced polymer materials at present. The introduction of alpha-olefins (1-butene, 1-hexene, 1-octene, etc.) in the polymerization reaction of ethylene not only reduces the density and crystallinity of the polymer, but also adjusts the melt index of the polymer and improves its processing performance. With the increase of the content of alpha-olefins, the material performance changes from polyolefin plastic to polyolefin elastomer (POE). The polyethylene segments in the POE molecules are divided into more and shorter crystalline regions (acting as plastic phase), which play the role of physical crosslinking; on the other hand, due to the long-chain branches in the polymer, the increase of the content of alpha-olefins leads to the formation of an amorphous rubber phase. The unique structure of POE makes the rubber have high elasticity at room temperature and can be plasticized at high temperature. This structure endows POE with excellent mechanical properties, good corrosion resistance and excellent rheological properties. In addition, POE has good affinity with polyolefin materials, effectively enhances the low-temperature toughness thereof, and has high cost performance, so it is widely used in automobile parts, wire and cable, mechanical packaging and other fields.

[0003] There are a large number of patents in the field of POE polymerization. At present, POE is mostly produced by using metallocene catalysis technology (CN1328580A, CN102190687A, CN1049849A, CN1166695C, WO1992000333A2, etc.) and solution polymerization process (CN1328580A, CN1049849A, US5132381A, CN1324370A, etc.).

[0004] With the further development of polyolefin elastomer catalytic system, a variety of novel polyolefin catalysts have been put forward. From 1987 to 2001, Fujita group developed a group IVB olefin polymerization catalyst of phenoxy imine ligand, namely FI catalyst. FI catalyst has developed rapidly in recent years because of its simple synthesis method, easy modification and high catalytic activity. In addition, FI catalyst can use alkyl aluminum as cocatalyst, which greatly reduces the catalytic cost based on the price consideration, and is very promising in the field of olefin copolymerization.

[0005] It is beneficial to carry out solution polymerization at high temperature (> 130℃) as reported in the literature [Heteroatom-Substituted Constrained-Geometry Complexes. Dramatic Substituent Effect on Catalyst Efficiency and Polymer Molecular Weight]. High temperature can increase the energy of monomer molecules, making them more likely to react. In addition, high temperature can also accelerate the reaction rate, thereby shortening the reaction time. Moreover, POE and OBC thermoplastic elastomers are easily swollen and agglomerated by solvents at low temperatures, which prevents the polymerization reaction from proceeding. Therefore, the solution polymerization of POE and OBC thermoplastic elastomers needs to be carried out at a higher temperature (120℃). Although the FI catalyst has high catalytic activity, it exhibits low activity at high temperatures when used for the production of polyolefin elastomers, resulting in low product yield and increasing production costs, which is not conducive to the mass production of polyolefin elastomers.

[0006] The conventional FI catalyst has high catalytic activity, but exhibits low activity at high temperatures when used for the production of polyolefin elastomers, which is not conducive to industrial production. Compared with the prior art, the present application greatly improves the high-temperature resistance of the catalyst by modifying the functional groups of the FI catalyst and utilizing the electrical properties and steric effects of the functional groups, ensuring that the catalyst can still maintain high activity at high temperatures. SUMMARY

[0007] To solve the above technical problems, the present application discloses a high-temperature-resistant polyolefin elastomer catalyst preparation method and its application. The catalyst has the advantages of high activity, high-temperature resistance, high comonomer content in the polyolefin elastomer product, and stable structure. The polyolefin elastomer prepared by the present application has a low melting point and good elongation performance.

[0008] To achieve the above-mentioned purposes, the present application adopts the following technical solutions:

[0009] The present application claims a high-temperature-resistant polyolefin elastomer catalyst for the synthesis of polyolefin elastomers. The high-temperature-resistant catalyst is composed of a main catalyst and a cocatalyst. The main catalyst has the following structure:

[0010]

[0011] wherein M is selected from Zr, Ti, Hf; R1is selected from alkyl, aryl, substituted aryl, heterocyclic aryl, substituted heterocyclic aryl, aroyl; X is selected from Cl, methyl; R2is selected from H, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, phenyl, 1-adamantyl; R3is selected from H, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, phenyl, alkoxy, 2-phenyl-2-propyl.

[0012] Preferably, the cocatalyst is selected from one of methylaluminoxane, modified methylaluminoxane, tris(pentafluorophenyl)boron compound, triisobutylaluminum, triethylaluminum, trimethylaluminum;

[0013] Preferably, the molar ratio of the procatalyst to the cocatalyst is 1:50-10000;

[0014] Preferably, the high-temperature-resistant catalyst is used in the synthesis of polyolefin elastomers, including: ethylene / α-olefin reaction is mainly carried out in an inert solvent, the high-temperature-resistant catalyst is prepared in proportion, the inert solvent and α-olefin are first added into the reaction system, and then the procatalyst and the cocatalyst are sequentially injected or uniformly mixed and injected into the reaction system in the form of homogeneous catalyst, and then the ethylene pressure is increased to make the ethylene fully contact with the reactants to perform ethylene / α-olefin copolymerization, the reaction conditions are as follows: temperature 25-200 ℃, pressure 0.1-10 MPa, time 5-60 min, and the concentration of the high-temperature-resistant catalyst is 0.1-100 μmol / L, calculated based on the liquid volume in the reactor;

[0015] Preferably, the α-olefin includes one of 1-butene, 1-hexene, and 1-octene;

[0016] Preferably, the inert solvent includes a linear alkane, an isomeric alkane, a cycloalkane, or an aralkane having 4-10 carbon atoms;

[0017] Preferably, the catalyst preparation solvent is preferably one of n-pentane, i-pentane, n-hexane, cyclohexane, n-heptane, i-heptane, n-octane, i-octane, n-decane, Isopar E, toluene, and xylene;

[0018] Preferably, the procatalyst is specifically selected from the following structures:

[0019] C1: M = Zr, R1= methylene, R2= t-butyl, R3= methyl, X = Cl;

[0020] C2: M = Zr, R1= methylene, R2= adamantyl, R3= methyl, X = Cl;

[0021] C3: M = Ti, R1= methylene, R2= t-butyl, R3= methyl, X = Cl;

[0022] C4: M = Ti, R1= methylene, R2= adamantyl, R3= methyl, X = Cl;

[0023] C5: M = Zr, R2= adamantyl, R3= methyl, X = Cl;

[0024] C6: M = Zr, R2= adamantyl, R3= ethyl, X = Cl;

[0025] C7: M = Zr, R2= adamantyl, R3= methoxy, X = Cl;

[0026] C8: M = Zr, R2= adamantyl, R3= methoxy, X = Cl;

[0027] C9: M = Zr, R2= adamantyl, R3= ethoxy, X = Cl;

[0028] C10: M = Zr, R2= adamantyl, R3= 2-phenyl-2-propyl, X = Cl;

[0029] Preferably, the catalyst is applied in a process for the preparation of a polyolefin elastomer, comprising the following steps:

[0030] (1) Catalyst preparation: a certain amount of the main catalyst and the cocatalyst are weighed and dissolved in water-removed toluene respectively to prepare two solutions for use;

[0031] (2) Before the reaction, the reactor is connected to the evaluation system, sealed and heated to 140°C, and the nitrogen atmosphere is replaced three times, and vacuum is maintained overnight. The next day, heat to 140°C under vacuum, fill with nitrogen, then vacuum, repeat three times, remove residual water, oxygen and oxygen-containing impurities, and ensure that the air has been replaced completely. Then use a vacuum pump to remove nitrogen and fill with ethylene, repeat three times to ensure that the reactor is filled with ethylene. Then set the temperature to the reaction temperature and cool through the condensation system;

[0032] (3) Under stirring conditions, inert solvent and α-olefin are sequentially injected into the reaction system, and after the temperature is stabilized to the reaction temperature, the main catalyst and cocatalyst solutions are injected respectively, the pressure is adjusted to the predetermined pressure value, and the reaction is carried out for a certain time. After the reaction, the inlet valve is closed, the ethylene pressure is removed, ethanol is added, and the reactor is cooled through the circulating condensation system;

[0033] (4) The contents of the reactor are precipitated in ethanol, the formed polymer precipitate is filtered and dried, vacuum dried overnight, and the obtained polymer is collected and weighed to calculate the activity.

[0034] (5) The polymer sample was pressed into 2mm test pieces in a hot press at 160℃, pressure 5MPa, and die pressing time 5min. After cooling, the tensile test samples were punched out and the performance test was carried out. Among them, the tensile properties were tested according to GB / T1040-2006, 5A type sample, and the tensile rate was 50mm / min.

[0035] The advantages of the present application are:

[0036] Industrial production of polyolefin is preferably carried out in a high temperature system, and the conventional FI catalyst exhibits lower activity at higher temperature, which is not conducive to industrial production. The present application modifies the functional group of the FI catalyst, which is resistant to high temperature and has high activity. The prepared polyolefin elastomer has high tensile strength and high tensile strain at break. DETAILED DESCRIPTION

[0037] In order to make the above features and advantages of the present application more obvious and easy to understand, the following examples are specifically described.

[0038] The method of the present application is a conventional method in the art unless otherwise specified.

[0039]

[0040]

[0041] The synthesis method of the ligand L1 is as follows: O, O'-methylene bis-hydroxylamine (CAS: 40770-44-3, US3714199A, 39.04mg, 0.50mmol) dissolved in 5mL ethanol solvent is added to 2-hydroxy-5-methyl-3-tert-butylbenzaldehyde (CAS: 41715-31-5, CN108727422A, 192.3mg, 1.00mmol) dissolved in 10mL ethanol solvent. The solution is stirred at 55℃ for 5 hours, and then cooled to room temperature. After filtration and precipitation, recrystallization is carried out with ethanol and n-hexane, washed with ethanol and dried under vacuum.

[0042] The characterization results of the ligand L1 are as follows: 1HNMR (400MHz, CDCl3) 8.18 (s, 2H), 7.37 (s, 2H), 7.08 (s, 2H), 5.82-5.84 (m, 4H), 2.36 (s, 6H), 1.40 (s, 18H).

[0043] The synthesis of ligand L2 was carried out by adding O,O'-methylene bis-hydroxylamine (CAS: 40770-44-3, US3714199A, 39.04 mg, 0.50 mmol) dissolved in 5 mL of ethanol solvent to 2-hydroxy-5-methyl-3-adamantylbenzaldehyde (CAS: 231963-91-0, Organic Syntheses (2005), 82, 34-42, 270.4 mg, 1.00 mmol) dissolved in 10 mL of ethanol solvent. The solution was stirred at 55 °C for 5 hours and then cooled to room temperature. After filtration and precipitation, recrystallization with ethanol and n-hexane, washing with ethanol and drying under vacuum.

[0044] The characterization results of ligand L2 are as follows:1H NMR (400 MHz, CDCI3) 8.28 (s, 2H), 7.37 (s, 2H), 7.08 (s, 2H), 5.84 (s, 1 H), 5.82 (s, 2H), 2.36 (s, 6H), 1.75-2.10 (m, 30H).

[0045] The synthesis of ligand L3 was carried out by adding 1,4-diaminooxybenzene (CAS: 1416776-50-5, 70.1 mg, 0.50 mmol) dissolved in 5 mL of ethanol solvent to 2-hydroxy-5-methyl-3-adamantylbenzaldehyde (CAS: 231963-91-0, Organic Syntheses (2005), 82, 34-42, 270.4 mg, 1.00 mmol) dissolved in 10 mL of ethanol solvent. The solution was stirred at 55 °C for 5 hours and then cooled to room temperature. After filtration and precipitation, recrystallization with ethanol and n-hexane, washing with ethanol and drying under vacuum.

[0046] The characterization results of ligand L3 are as follows:1H NMR (400 MHz, CDCI3) 8.28 (s, 2H), 7.37 (s, 2H), 7.08 (s, 2H), 6.64 (s, 4H), 5.84 (s, 2H), 2.36 (s, 6H), 1.75-2.10 (m, 30H).

[0047] The synthesis of ligand L4 was carried out by adding 1,4-diaminooxybenzene (CAS: 1416776-50-5, 70.1 mg, 0.50 mmol) dissolved in 5 mL of ethanol solvent to 2-hydroxy-5-ethyl-3-adamantylbenzaldehyde (284.4 mg, 1.00 mmol) dissolved in 10 mL of ethanol solvent. The solution was stirred at 55 °C for 5 hours and then cooled to room temperature. After filtration and precipitation, recrystallization with ethanol and n-hexane, washing with ethanol and drying under vacuum.

[0048] wherein 2-hydroxy-5-ethyl-3-adamantylbenzaldehyde was prepared in-house and prepared as follows: To a 500 mL round bottom flask was added p-ethylphenol (19.1 g, 0.156 mol), dichloromethane (150 mL), and 1-adamantanol (25.0 g, 0.164 mol) at room temperature. Concentrated sulfuric acid (9 mL) was added dropwise over 20 minutes with stirring and the stirring was continued for 30 minutes. After the stirring was complete, ice water (150 mL) was added slowly and the solution was neutralized with NaOH (2 M, ca. 160 mL) to produce a white slurry. The organic layer was extracted with dichloromethane and washed with brine (100 mL), volatiles were removed by rotary evaporation, and the product was heated to reflux in methanol (200 mL), cooled and filtered, and the product was extracted from the filter with methanol, volatiles were removed by rotary evaporation, and the product was dried under vacuum to give a solid product, 2-(1-adamantyl)-4-ethylphenol.

[0049] 2-(1-Adamantyl)-4-ethylphenol was characterized as follows:1H NMR (400 MHz, CDC13) 9.70 (s, 1H), 7.10 (s, 1H), 6.72-6.80 (m, 2H), 2.80-2.82 (m, 2H), 1.70-2.05 (m, 15H), 1.17-1.89 (m, 3H).

[0050] To a 500 mL round bottom flask was added the solid 2-(1-adamantyl)-4-ethylphenol (5.30 g, 0.021 mol) from the previous step, hexamethylenetetramine (5.80 g, 0.041 mol), and glacial acetic acid (100 mL) and a reflux condenser was attached to the flask. The stirred mixture was heated to 110 °C for 5 hours. The mixture was then cooled to 90 °C, water (150 mL) was added slowly, and the mixture was cooled to room temperature to form a suspension, the precipitate was collected by filtration, and the product was treated with methanol (50 mL) and stirred for 1 hour, washed with methanol three times, and dried under vacuum to give the product.

[0051] 2-hydroxy-5-ethyl-3-adamantylbenzaldehyde was characterized as follows:1H NMR (400 MHz, CDC13) 12.00 (s, 1H), 10.15 (s, 1H), 7.37 (s, 1H), 7.34 (s, 1H), 2.80-2.82 (m, 2H), 1.70-2.05 (m, 15H), 1.17-1.89 (m, 3H). Ligand L4 was characterized as follows:1H NMR (400 MHz, CDC13) 8.28 (s, 2H), 7.37 (s, 2H), 7.08 (s, 2H), 6.64 (s, 4H), 5.84 (s, 2H), 2.70-2.74 (m, 4H), 1.75-2.10 (m, 30H), 1.16-1.20 (m, 6H).

[0052] The synthesis of ligand L5 was carried out by adding 1,4-diaminoxybenzene (CAS: 1416776-50-5, 70.1 mg, 0.50 mmol) dissolved in 5 mL of ethanol solvent to 2-hydroxy-5-methoxy-3-adamantylbenzaldehyde (CAS: 278602-33-8, EP1013674A1, 286.4 mg, 1.00 mmol) dissolved in 10 mL of ethanol solvent. The solution was stirred at 55 °C for 5 hours, then cooled to room temperature. After filtration and precipitation, recrystallization with ethanol and n-hexane, washing with ethanol and drying under vacuum.

[0053] The characterization results of ligand L5 are as follows:1H NMR (400 MHz, CDCI3) 8.28 (s, 2H), 7.02 (s, 2H), 6.91 (s, 2H), 6.64 (s, 4H), 5.46 (s, 2H), 3.81 (s, 6H), 1.75-2.10 (m, 30H).

[0054] The synthesis of ligand L6 was carried out by adding 1,4-diaminoxy-2,3,5,6-tetrafluorobenzene (142.1 mg, 0.50 mmol) dissolved in 5 mL of ethanol solvent to 2-hydroxy-5-methoxy-3-adamantylbenzaldehyde (CAS: 278602-33-8, EP1013674A1, 286.4 mg, 1.00 mmol) dissolved in 10 mL of ethanol solvent. The solution was stirred at 55 °C for 5 hours, then cooled to room temperature. After filtration and precipitation, recrystallization with ethanol and n-hexane, washing with ethanol and drying under vacuum.

[0055] wherein 1,4-diaminoxy-2,3,5,6-tetrafluorobenzene was prepared in-house, the preparation process being as follows: NaH (36 mg, 1.5 mmol) was added to a solution of tetrafluororesorcinol (182.1 mg, 1 mmol) in 100 mL of anhydrous DMF (0.3 M). The mixture was stirred at room temperature for 1 hour. To the mixture was added 2,4,6-trimethylbenzenesulfonic acid azanide (CAS: 36016-40-7, 473.27 mg, 2.2 mmol), and the reaction mixture was stirred at room temperature for 12 hours. After completion, the mixture was cooled to 0 °C with water quenching, and the reaction mixture was extracted with ethyl acetate. The combined organic layers were dried with Na2S04, and the volatiles were removed by rotary evaporation, and the solid was dried under vacuum. The characterization results of 1,4-diaminoxy-2,3,5,6-tetrafluorobenzene are as follows:1H NMR (400 MHz, CDCI3) 1.50 (s, 4H).

[0056] The results of the characterization of ligand L6 are as follows:1H NMR (400 MHz, CDCI3) 8.28 (s, 2H), 7.02 (s, 2H), 6.91 (s, 2H), 5.46 (s, 2H), 3.81 (s, 6H), 1.75-2.10 (m, 30H).

[0057] The synthesis of ligand L7 was carried out by adding 1,4-diaminoxy-2,3,5,6- tetrafluorobenzene (142.1 mg, 0.50 mmol) dissolved in 5 mL of ethanol solvent to 2- hydroxy-5-ethoxy-3-adamantylbenzaldehyde (300.4 mg, 1.00 mmol) dissolved in 10 mL of ethanol solvent. The solution was stirred at 55°C for 5 hours and then cooled to room temperature. After filtration and precipitation, recrystallization was carried out with ethanol and n-hexane, washed with ethanol and dried under vacuum.

[0058] 2-Hydroxy-5-ethoxy-3-adamantylbenzaldehyde was prepared in-house according to the following procedure: Under an inert atmosphere of nitrogen, (24.91 g, 203.90 mmol) of phenetole and 30 ml of toluene were introduced into a 200 ml reactor. To the reactor, 20 mL of a toluene solution containing 1-adamantanol (15.52 g, 101.9 mmol) was added dropwise at 95°C and then stirred for 5.5 hours. After cooling the system to room temperature, the precipitate was washed with hexane and dried under vacuum to obtain solid 2-(1-adamantyl)-4-ethoxyphenol.

[0059] The results of the characterization of 2-(1-adamantyl)-4-ethoxyphenol are as follows:1H NMR (400 MHz, CDCI3) 9.30 (s, 1 H), 6.72-6.83 (m, 3H), 4.04-4.06 (m, 2H), 1.70-2.05 (m, 15H), 1.34-1.37 (m, 3H).

[0060] Under an inert atmosphere of nitrogen, a THF solution of 2-(1-adamantyl)-4- ethoxyphenol (12.97 g, 47.20 mmol) was slowly added to a 20 mL solution of ethyl magnesium bromide and 10 ml of THF in ethyl ether at 0°C for 15 minutes. Then, 150 mL of toluene was added and heated to 95°C to remove the ethyl ether and THF to obtain a white slurry. After cooling the slurry to 20°C, 3.43 g (114.30 mmol) of paraformaldehyde and 9.40 ml (67.50 mmol) of triethylamine were added and then stirred at 90°C for 30 minutes. Quenching was carried out by adding 32 mL of 18% hydrochloric acid. The organic layer was washed with 100 mL of water, 50 mL of aqueous sodium bicarbonate solution and 100 mL of aqueous sodium chloride solution, respectively, and then concentrated. The resulting product was purified by silica gel column chromatography to obtain 2-hydroxy-5-ethoxy-3-adamantylbenzaldehyde.

[0061] 2-hydroxy-5-ethoxy-3-adamantylbenzaldehyde was characterized as follows:1H NMR (400 MHz, CDC13) 12.30 (s, 1H), 10.20 (s, 1H), 6.72-6.83 (m, 3H), 4.04-4.06 (m, 2H), 1.70-2.05 (m, 15H), 1.34-1.37 (m, 3H).

[0062] Ligand L7 was characterized as follows:1H NMR (400 MHz, CDC13) 8.28 (s, 2H), 7.02 (s, 2H), 6.91 (s, 2H), 5.46 (s, 2H), 4.02-4.08 (m, 4H), 1.75-2.10 (m, 30H), 1.30-1.35 (m, 6H).

[0063] The synthesis of ligand L8 was performed by adding 1,4-diaminoxy-2,3,5,6- tetrafluorobenzene (142.1 mg, 0.50 mmol) dissolved in 5 mL of ethanol solvent to 2-hydroxy-5-(1-methyl-1-phenylethyl)-3-adamantylbenzaldehyde (CAS: 1338382-79-8, JP2011195583A, 374.5 mg, 1.00 mmol) dissolved in 10 mL of ethanol solvent. The solution was stirred at 55 °C for 5 hours and then cooled to room temperature. After filtration and precipitation, recrystallization was performed with ethanol and n-hexane, washed with ethanol and dried under vacuum.

[0064] Ligand L8 was characterized as follows:1H NMR (400 MHz, CDC13) 8.28 (s, 2H), 7.39 (s, 2H), 7.15-7.30 (m, 12H), 5.84 (s, 2H), 1.75-2.10 (m, 30H), 1.70 (s, 12H).

[0065] Ligand L9 is 2-(1,1-dimethylethyl)-6[(phenylimino)methyl]phenol with CAS 215033-50-4.

[0066] Example 1: The synthesis of C1 was performed as follows:

[0067] Under anhydrous and anaerobic conditions, 0.34 g of ligand L1 was dissolved in 30 mL THF in a 100 mL flask and stirred at -78 °C. After dropwise addition of 1.48 ml of n-butyllithium (1.55 mmol / ml of n-hexane solution), it was stirred at room temperature for 3 hours. At -78 °C, 0.23 g of zirconium tetrachloride was dissolved in 15 mL THF. After the ligand solution was added to the zirconium tetrachloride solution, it was stirred at room temperature for 2 hours, and then stirred under reflux for another 4 hours. After concentration under reduced pressure, the precipitated solid was washed with 50 ml of dichloromethane. The filtrate was concentrated again, and the resulting solid was dissolved in diethyl ether to obtain crystals by recrystallization, washed with hexane, and then dried in vacuum to obtain 0.32 g of compound C1.

[0068] Example 2: The synthesis process of C2 is as follows:

[0069] Under anhydrous and anaerobic conditions, 0.34 g of ligand L1 was dissolved in 30 mL THF in a 100 mL flask and stirred at -78 °C. After dropwise addition of 1.48 ml of n-butyllithium (1.55 mmol / ml of n-hexane solution), it was stirred at room temperature for 3 hours. At -78 °C, 0.23 g of zirconium tetrachloride was dissolved in 15 mL THF. After the ligand solution was added to the zirconium tetrachloride solution, it was stirred at room temperature for 2 hours, and then stirred under reflux for another 4 hours. After concentration under reduced pressure, the precipitated solid was washed with 50 ml of dichloromethane. The filtrate was concentrated again, and the resulting solid was dissolved in diethyl ether to obtain crystals by recrystallization, washed with hexane, and then dried in vacuum to obtain 0.32 g of compound C1.

[0070] Example 3: The synthesis process of C3 is as follows:

[0071] Under anhydrous and anaerobic conditions, 0.34 g of ligand L1 was dissolved in 30 mL THF in a 100 mL flask and stirred at -78 °C. After dropwise addition of 1.48 ml of n-butyllithium (1.55 mmol / ml of n-hexane solution), it was stirred at room temperature for 3 hours. At -78 °C, 0.23 g of zirconium tetrachloride was dissolved in 15 mL THF. After the ligand solution was added to the zirconium tetrachloride solution, it was stirred at room temperature for 2 hours, and then stirred under reflux for another 4 hours. After concentration under reduced pressure, the precipitated solid was washed with 50 ml of dichloromethane. The filtrate was concentrated again, and the resulting solid was dissolved in diethyl ether to obtain crystals by recrystallization, washed with hexane, and then dried in vacuum to obtain 0.32 g of compound C1.

[0072] Example 4: The synthesis process of C4 is as follows:

[0073] Under anhydrous and anaerobic conditions, 0.58 g of ligand L2 was dissolved in 30 mL THF in a 100 mL flask and stirred at -78 °C. After dropwise addition of 1.48 ml of n-butyllithium (1.55 mmol / ml of n-hexane solution), it was stirred at room temperature for 3 hours. At -78 °C, 0.19 g of titanium tetrachloride was dissolved in 15 mL of THF. After the ligand solution was added to the titanium tetrachloride solution, it was stirred at room temperature for 2 hours, and then stirred under reflux for 4 hours. After concentration under reduced pressure, the precipitated solid was washed with dichloromethane. The filtrate was concentrated again, the resulting solid was dissolved in diethyl ether, and crystals were obtained by recrystallization, washed with hexane, and then dried in vacuo to obtain 0.09 g of compound C4.

[0074] Example 5: The synthesis process of C5 is as follows:

[0075] Under anhydrous and anaerobic conditions, 0.58 g of ligand L2 was dissolved in 30 mL THF in a 100 mL flask and stirred at -78 °C. After dropwise addition of 1.48 ml of n-butyllithium (1.55 mmol / ml of n-hexane solution), it was stirred at room temperature for 3 hours. At -78 °C, 0.19 g of titanium tetrachloride was dissolved in 15 mL of THF. After the ligand solution was added to the titanium tetrachloride solution, it was stirred at room temperature for 2 hours, and then stirred under reflux for 4 hours. After concentration under reduced pressure, the precipitated solid was washed with dichloromethane. The filtrate was concentrated again, the resulting solid was dissolved in diethyl ether, and crystals were obtained by recrystallization, washed with hexane, and then dried in vacuo to obtain 0.09 g of compound C4.

[0076] Example 6: The synthesis process of C6 is as follows:

[0077] Under anhydrous and anaerobic conditions, 0.58 g of ligand L2 was dissolved in 30 mL THF in a 100 mL flask and stirred at -78 °C. After dropwise addition of 1.48 ml of n-butyllithium (1.55 mmol / ml of n-hexane solution), it was stirred at room temperature for 3 hours. At -78 °C, 0.19 g of titanium tetrachloride was dissolved in 15 mL of THF. After the ligand solution was added to the titanium tetrachloride solution, it was stirred at room temperature for 2 hours, and then stirred under reflux for 4 hours. After concentration under reduced pressure, the precipitated solid was washed with dichloromethane. The filtrate was concentrated again, the resulting solid was dissolved in diethyl ether, and crystals were obtained by recrystallization, washed with hexane, and then dried in vacuo to obtain 0.09 g of compound C4.

[0078] Example 7: The synthesis process of C7 is as follows:

[0079] Under anhydrous and anaerobic conditions, 0.68 g of ligand L5 was dissolved in 30 mL THF in a 100 mL flask and stirred at -78 °C. After dropwise addition of 1.48 ml of n-butyllithium (1.55 mmol / ml of n-hexane solution), it was stirred at room temperature for 3 hours. At -78 °C, 0.23 g of zirconium tetrachloride was dissolved in 15 mL of THF. After the ligand solution was added to the zirconium tetrachloride solution, it was stirred at room temperature for 2 hours, and then stirred under reflux for another 4 hours. After concentration under reduced pressure, the precipitated solid was washed with 50 ml of dichloromethane. The filtrate was concentrated again, and the resulting solid was dissolved in diethyl ether to obtain crystals by recrystallization, washed with hexane, and then dried in vacuum to obtain 0.44 g of compound C7.

[0080] Example 8: The synthesis process of C8 is as follows:

[0081] Under anhydrous and anaerobic conditions, 0.68 g of ligand L5 was dissolved in 30 mL THF in a 100 mL flask and stirred at -78 °C. After dropwise addition of 1.48 ml of n-butyllithium (1.55 mmol / ml of n-hexane solution), it was stirred at room temperature for 3 hours. At -78 °C, 0.23 g of zirconium tetrachloride was dissolved in 15 mL of THF. After the ligand solution was added to the zirconium tetrachloride solution, it was stirred at room temperature for 2 hours, and then stirred under reflux for another 4 hours. After concentration under reduced pressure, the precipitated solid was washed with 50 ml of dichloromethane. The filtrate was concentrated again, and the resulting solid was dissolved in diethyl ether to obtain crystals by recrystallization, washed with hexane, and then dried in vacuum to obtain 0.44 g of compound C7.

[0082] Example 9: The synthesis process of C9 is as follows:

[0083] Under anhydrous and anaerobic conditions, 0.68 g of ligand L5 was dissolved in 30 mL THF in a 100 mL flask and stirred at -78 °C. After dropwise addition of 1.48 ml of n-butyllithium (1.55 mmol / ml of n-hexane solution), it was stirred at room temperature for 3 hours. At -78 °C, 0.23 g of zirconium tetrachloride was dissolved in 15 mL of THF. After the ligand solution was added to the zirconium tetrachloride solution, it was stirred at room temperature for 2 hours, and then stirred under reflux for another 4 hours. After concentration under reduced pressure, the precipitated solid was washed with 50 ml of dichloromethane. The filtrate was concentrated again, and the resulting solid was dissolved in diethyl ether to obtain crystals by recrystallization, washed with hexane, and then dried in vacuum to obtain 0.44 g of compound C7.

[0084] Example 10: The synthesis process of C10 is as follows:

[0085] Anhydrous and oxygen-free conditions, 30 mL THF in a 100 mL flask dissolved 0.92 g ligand L8, and stirred at -78 °C. After adding 1.48 ml n-butyllithium (1.55 mmol / ml n-hexane solution), it was stirred at room temperature for 3 hours. At -78 °C, 0.23 g zirconium tetrachloride was dissolved in 15 mL THF. After adding the ligand solution to the zirconium tetrachloride solution, it was stirred at room temperature for 2 hours, and then stirred under reflux for another 4 hours. After concentration under reduced pressure, the precipitated solid was washed with 50 ml dichloromethane. The filtrate was concentrated again, the resulting solid was dissolved in diethyl ether, and crystals were obtained by recrystallization, washed with hexane, and then dried under vacuum to obtain 0.66 g of compound C10.

[0086] Comparative Example 1: describes the synthesis process of a conventional FI catalyst (or reference to a certain literature)

[0087] wherein the typical FI catalyst synthesis method refers to the work of Fujita et al. [JP20030316030]. The reaction steps are: 1.53 g of ligand L9 and 60 mL of THF are added to the reactor, dried and purged with argon, cooled to -78 °C and stirred. After adding 4.1 mL of n-butyllithium dropwise in 5 minutes, the temperature is slowly raised to room temperature, and stirring is continued at room temperature for 4 hours. At the same time, 0.70 g of zirconium tetrachloride is prepared at -78 °C in 30 mL of THF. 10 mL of THF is added to the reaction solution, and the mixture is slowly added to the zirconium tetrachloride solution. After addition, the temperature is slowly raised to room temperature. The reaction solution is stirred at room temperature for 2 hours, and then stirred under reflux for another 4 hours. The reaction solution is concentrated under reduced pressure, the precipitated solid is washed with 50 mL of dichloromethane, and filtered with a glass filter to remove insoluble matter. The filtrate is concentrated under reduced pressure, and the precipitated solid is dissolved in 30 ml of diethyl ether. The solution is left to stand at -20 °C under a nitrogen atmosphere for one day to precipitate yellow crystals. The solid is isolated by filtration, washed with hexane, and then dried under vacuum to obtain 0.79 g of compound of formula 10.

[0088]

[0089] The structural formulas of catalysts C1-C10 are as shown in formulas 11-20. Among them, the characterization results of catalyst C1 are as follows:

[0090] 1 H NMR (400 MHz, CDCl3) 8.20 (s, 2H), 7.37 (s, 2H), 7.08 (s, 2H), 5.77 (s, 2H), 2.36 (s, 6H), 1.42 (s, 18H).

[0091] Among them, the characterization results of catalyst C2 are as follows:

[0092] 1H NMR (400 MHz, CDC13) 8.20 (s, 2H), 7.37 (s, 2H), 7.08 (s, 2H), 5.77 (s, 2H), 2.36 (s, 6H), 2.05 (d, J = 7.53 Hz, 8H), 1.99 (d, J = 7.53 Hz, 4H), 1.83-1.91 (m, 6H), 1.73-1.79 (m, 12H).

[0093] The characterization results of catalyst C3 are as follows:

[0094] 1 H NMR (400 MHz, CDC13) 8.20 (s, 2H), 7.37 (s, 2H), 7.08 (s, 2H), 5.77 (s, 2H), 2.36 (s, 6H), 2.05 (d, J = 7.53 Hz, 8H), 1.99 (d, J = 7.53 Hz, 4H), 1.83-1.91 (m, 6H), 1.73-1.79 (m, 12H).

[0095] The characterization results of catalyst C4 are as follows:

[0096] 1 H NMR (400 MHz, CDC13) 8.20 (s, 2H), 7.37 (s, 2H), 7.08 (s, 2H), 5.77 (s, 2H), 2.36 (s, 6H), 2.05 (d, J = 7.53 Hz, 8H), 1.99 (d, J = 7.53 Hz, 4H), 1.83-1.91 (m, 6H), 1.73-1.79 (m, 12H).

[0097] The characterization results of catalyst C5 are as follows:

[0098] 1 H NMR (400 MHz, CDC13) 8.20 (s, 2H), 7.37 (s, 2H), 7.08 (s, 2H), 5.77 (s, 2H), 2.36 (s, 6H), 2.05 (d, J = 7.53 Hz, 8H), 1.99 (d, J = 7.53 Hz, 4H), 1.83-1.91 (m, 6H), 1.73-1.79 (m, 12H).

[0099] The characterization results of catalyst C6 are as follows:

[0100] 1H NMR (400 MHz, CDC13) 8.20 (s, 2H), 7.01 (s, 2H), 6.91 (s, 2H), 6.64 (s, 4H), 3.81 (s, 6H), 2.05 (d, J = 7.53 HZ, 8H), 1.99 (d, J = 7.53 HZ, 4H), 1.83-1.91 (m, 6H), 1.73-1.79 (m, 12H).

[0101] The characterization results of catalyst C7 are as follows:

[0102] 1 H NMR (400 MHz, CDC13) 8.20 (s, 2H), 7.01 (s, 2H), 6.91 (s, 2H), 6.64 (s, 4H), 3.81 (s, 6H), 2.05 (d, J = 7.53 HZ, 8H), 1.99 (d, J = 7.53 HZ, 4H), 1.83-1.91 (m, 6H), 1.73-1.79 (m, 12H).

[0103] The characterization results of catalyst C8 are as follows:

[0104] 1 H NMR (400 MHz, CDC13) 8.20 (s, 2H), 7.01 (s, 2H), 6.91 (s, 2H), 6.64 (s, 4H), 3.81 (s, 6H), 2.05 (d, J = 7.53 HZ, 8H), 1.99 (d, J = 7.53 HZ, 4H), 1.83-1.91 (m, 6H), 1.73-1.79 (m, 12H).

[0105] The characterization results of catalyst C9 are as follows:

[0106] 1 H NMR (400 MHz, CDC13) 8.20 (s, 2H), 7.01 (s, 2H), 6.91 (s, 2H), 6.64 (s, 4H), 3.81 (s, 6H), 2.05 (d, J = 7.53 HZ, 8H), 1.99 (d, J = 7.53 HZ, 4H), 1.83-1.91 (m, 6H), 1.73-1.79 (m, 12H).

[0107] The characterization results of catalyst C10 are as follows:

[0108] 1H NMR (400 MHz, CDC13) δ 8.20 (s, 2H), 7.39 (s, 2H), 7.16-7.34 (m, 10H), 7.10 (s, 2H), 2.05 (d, J = 7.53 Hz, 8H), 1.99 (d, J = 7.53 Hz, 4H), 1.83-1.91 (m, 6H), 1.73-1.79 (m, 12H), 1.30-1.38 (m, 6H), 1.69 (m, 12H).

[0109]

[0110]

[0111] Application Example 1: A 2L reactor was sealed and vacuumed overnight, then heated to 140°C, filled with nitrogen, then vacuumed, repeated three times to remove residual water, oxygen and oxygen-containing impurities, to ensure that the air has been replaced completely. Then the nitrogen was pumped out by vacuum pump, and filled with ethylene, repeated three times to ensure that the reactor was filled with ethylene. Then the temperature was set to 50°C, and the reactor was cooled by the condensation system. 1L of toluene and 200mL of octene-1 were injected into the reactor under stirring, and then 1 μmol of catalyst Cl in toluene solution and 5mL of methylaluminoxane in toluene solution were injected respectively after the temperature was stabilized at 50°C. The pressure was adjusted to 3MPa, and the reaction was carried out for 20 minutes. Then the valve of the inlet was closed, the ethylene pressure was removed, ethanol was added, and the reactor was cooled by the circulating condensation system. The product was precipitated in 2L of ethanol, and the formed polymer was filtered and dried under vacuum overnight. The white ethylene / 1-octene copolymer was collected, the reaction conditions are listed in Table 1, and the test results of the product are shown in Table 2.

[0112] Application Example 2: The same as application example 1, except that the reaction temperature was 75°C. The reaction conditions are listed in Table 1, and the data results are shown in Table 2.

[0113] Application Example 3: The same as application example 1, except that the reaction temperature was 100°C. The reaction conditions are listed in Table 1, and the data results are shown in Table 2.

[0114] Application Example 4: The same as application example 1, except that the reaction temperature was 130°C. The reaction conditions are listed in Table 1, and the data results are shown in Table 2.

[0115] Application Example 5: The same as application example 1, except that the reaction temperature was 135°C. The reaction conditions are listed in Table 1, and the data results are shown in Table 2.

[0116] Application Example 6: The same as application example 5, except that the amount of octene feed was increased to 250mL. The reaction conditions are listed in Table 1, and the data results are shown in Table 2.

[0117] Application Example 7: Same as Application Example 6 except that the procatalyst used was Catalyst C2. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0118] Application Example 8: Same as Application Example 6 except that the procatalyst used was Catalyst C3. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0119] Application Example 9: Same as Application Example 6 except that the procatalyst used was Catalyst C4. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0120] Application Example 10: Same as Application Example 6 except that the procatalyst used was Catalyst C5. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0121] Application Example 11 : Same as Application Example 6 except that the procatalyst used was Catalyst C6. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0122] Application Example 12: Same as Application Example 6 except that the procatalyst used was Catalyst C7. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0123] Application Example 13: Same as Application Example 6 except that the procatalyst used was Catalyst C8. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0124] Application Example 14: Same as Application Example 6 except that the procatalyst used was Catalyst C9. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0125] Application Example 15: Same as Application Example 6 except that the procatalyst used was Catalyst C10. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0126] Application Example 16: Same as Application Example 15 except that the reaction pressure was 4 MPa. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0127] Application Example 17: Same as Application Example 15 except that the reaction pressure was 5 MPa. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0128] Application Example 18: Same as Application Example 15 except that the reaction temperature was 140 °C. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0129] Application Example 19: Same as Application Example 15 except that the reaction temperature was 145 °C. The reaction conditions are listed in Table 1 and the data results are found in Table 2.

[0130] Application Example 20: Same as application example 19, except that the amount of ethylene charged is 300 mL. The reaction conditions are listed in Table 1, and the data results are shown in Table 2.

[0131] Application Example 21: Same as application example 19, except that the amount of ethylene charged is 400 mL. The reaction conditions are listed in Table 1, and the data results are shown in Table 2.

[0132] Application Comparative Example 1: The polymerization step and conditions are the same as application example 21, except that the catalyst is a typical FI catalyst (formula 10). The data results are shown in Table 2.

[0133] Application Comparative Example 2: Same as application comparative example 1, except that the catalyst is a typical FI catalyst (formula 10) and the reaction temperature is 50°C. The data results are shown in Table 2.

[0134] Table 1 Reaction conditions of examples and comparative examples

[0135]

[0136]

[0137] Table 2 Test results of copolymers of examples 1-21 and comparative examples 1

[0138]

[0139]

[0140] As shown in Table 2, the traditional FI catalysts used in application comparative examples 1-2 have high activity at low temperature, and the prepared polymers have good tensile properties, but the reaction activity is low at high temperature, the molecular weight is low, and the tensile strength is low; while the application examples 1-6 of the present application have high activity at low temperature, and still retain a certain activity as the temperature increases; after further modification of the functional groups, the prepared polymers have significantly improved properties; the application examples 19-21 of the present application have high activity at high temperature of 145°C, and the prepared polymers have high comonomer content, high toughness, and low melting point, etc.

[0141] The above only describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the present application should be included in the scope of the present application.

Claims

1. A high temperature resistant catalyst for use in the synthesis of polyolefin elastomers, characterized in that, The high-temperature-resistant catalyst is composed of a main catalyst and a cocatalyst, wherein the main catalyst has the following structure: ； M is selected from Zr, Ti and Hf; R1 is selected from alkyl, aryl, substituted aryl, heterocyclic aryl, substituted heterocyclic aryl and aroyl; X is selected from Cl and methyl; R2 is selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, phenyl and 1-adamantyl; and R3 is selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, phenyl, alkoxy and 2-phenyl-2-propyl.

2. The refractory catalyst of claim 1, wherein, The cocatalyst is selected from one of methylaluminoxane, modified methylaluminoxane, tris(pentafluorophenyl)boron compound, triisobutylaluminum, triethylaluminum and trimethylaluminum.

3. The refractory catalyst of claim 1, wherein, The molar ratio of the main catalyst to the cocatalyst is 1:50-10000.

4. Use of the refractory catalyst according to claim 1 for the synthesis of polyolefin elastomers, characterized by: First, inert solvent and alpha-olefin are added into the reaction system, then the high-temperature-resistant catalyst main catalyst and cocatalyst are sequentially injected or uniformly mixed and injected into the reaction system in the form of homogeneous catalyst, then the ethylene pressure is increased to make the reaction materials fully contact, and the ethylene / alpha-olefin copolymerization is carried out, the reaction conditions are as follows: temperature 25-200 DEG C, pressure 0.1-10 MPa, time 5-60 min, and the concentration of the high-temperature-resistant catalyst is 0.1-100 μmol / L based on the liquid volume in the reactor.

5. Use according to claim 4, characterized in that: The alpha-olefin includes one of 1-butene, 1-hexene and 1-octene.

6. Use according to claim 4, characterized in that: The inert solvent includes linear alkane, isomeric alkane, cycloalkane or aralkane having 4-10 carbon atoms.

7. Use according to claim 4, characterized in that: The catalyst preparation solvent includes one of n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isohexane, n-octane, isooctane, n-decane, Isopar E, toluene and xylene.

8. Use according to claim 4, characterized in that: The main catalyst is specifically selected from one of the following structures: C1: M=Zr, R1=methylene, R2=tert-butyl, R3=methyl, and X=Cl; C2: M=Zr, R1=methylene, R2=1-adamantyl, R3=methyl, and X=Cl; C3: M=Ti, R1=methylene, R2=tert-butyl, R3=methyl, and X=Cl; C4: M=Ti, R1=methylene, R2=1-adamantyl, R3=methyl, and X=Cl; C5: M=Zr, R1= R2 = 1-adamantyl, R3 = methyl, X = Cl; C6: M=Zr, R1= R2 = 1-adamantyl, R3 = ethyl, X = Cl; C7: M=Zr, R1= R2 = 1-adamantyl, R3 = methoxy, X = Cl; C8: M=Zr, R1= R2 = 1-adamantyl, R3 = methoxy, X = Cl; C9: M=Zr, R1= R2 = 1-adamantyl, R3 = ethoxy, X = Cl; C10: M=Zr, R1= R2 = 1-adamantyl, R3 = 2-phenyl-2-propyl, X = Cl.

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