Dihydroquinolinone skeleton-derived catalyst and use thereof

Abstract

The application discloses a dihydroquinolinone skeleton derived catalyst and application thereof, and belongs to the technical field of industrial catalysis. The catalyst has high thermal stability and easy solubility based on special structural design, has strong adaptability to a catalytic scene, and has high catalytic activity when applied to processes such as ethylene polymerization and ethylene-octene polymerization, and has high cost performance.

Description

Technical Field

[0001] This invention relates to the field of industrial catalysis technology, specifically to a dihydroquinoline ketone skeletal-derived catalyst and its applications. Background Technology

[0002] Polyolefins are a class of polymers obtained through the polymerization reaction of olefin monomers such as ethylene and propylene, and they occupy a dominant position in the world's plastics industry today.

[0003] Currently, most common polyolefin polymerization processes are carried out using ligand-based catalysts. However, different ligand catalysts have different steric hindrance and electron-donating effects, resulting in varying catalytic activities and effects in practical applications. On the other hand, most ligand-based catalysts are not ideal in terms of applicability, or have extremely low solubility, requiring a large amount of solvent for dissolution, leading to high application costs, or have poor high-temperature performance, making them unsuitable for some high-polymerization-temperature processes. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a dihydroquinolinone skeleton-derived catalyst. This catalyst, based on a special structural design, exhibits high thermal stability and easy solubility, strong adaptability to catalytic scenarios, and high catalytic activity in polyolefin preparation processes such as ethylene polymerization and ethylene-octene polymerization, resulting in a high cost-performance ratio.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

[0007]

[0008] Wherein, R1 is at least one of alkyl, cycloalkyl and aryl groups;

[0009] R2, R3, R4, R5, and R6 are each at least one of H, alkyl, cycloalkyl, aromatic, and heteroatom substituents;

[0010] R7 is at least one of alkyl, cycloalkyl, phenyl, substituted phenyl, and substituted naphthyl;

[0011] M is at least one of Zr, Ti and Cr;

[0012] X is any one of alkyl, aromatic, aromatic heterocyclic, halogen and nitrogen-containing groups, and n = 1 to 3;

[0013] B can be either a hydroxyl group or a heteroatom-substituted hydroxyl group.

[0014] The beneficial effects of this invention are that it provides a dihydroquinolinone skeleton-derived catalyst, which, based on a special structural design, has high thermal stability and easy solubility, strong adaptability to catalytic scenarios, and high catalytic activity in polyolefin preparation processes such as ethylene polymerization and ethylene-octene polymerization, resulting in high cost-effectiveness. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the preparation process of the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 1 described in the embodiments of the present invention.

[0016] Figure 2 This is a schematic diagram of the preparation process of the dihydroquinolineone skeleton-derived tetradentate phenol ether ligand 2 described in the embodiments of the present invention.

[0017] Figure 3 This is a schematic diagram of the preparation process of the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 3 described in the embodiments of the present invention.

[0018] Figure 4 This is a schematic diagram of the preparation process of the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 4 described in the embodiments of the present invention.

[0019] Figure 5 This is a schematic diagram of the preparation process of the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 5 described in the embodiments of the present invention. Detailed Implementation

[0020] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments and comparative examples. The purpose of this description is to provide a detailed understanding of the invention, not to limit its scope. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this invention. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this invention are commonly used reagents and instruments.

[0021] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0022] In this invention, numerical ranges are involved. Unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe features or characteristics, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0023] The present invention is further illustrated below with specific embodiments:

[0024] A dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

[0025]

[0026] Wherein, R1 is at least one of alkyl, cycloalkyl, and aryl groups;

[0027] R2, R3, R4, R5, and R6 are each at least one of H, alkyl, cycloalkyl, aromatic, and heteroatom substituents;

[0028] R7 is at least one of alkyl, cycloalkyl, phenyl, substituted phenyl, and substituted naphthyl;

[0029] M is at least one of Zr, Ti and Cr;

[0030] X is any one of alkyl, aromatic, aromatic heterocyclic, halogen and nitrogen-containing groups, and n = 1 to 3;

[0031] B can be any one of a hydroxyl group or a heteroatom-substituted hydroxyl group.

[0032] In some embodiments, the alkyl group includes at least one selected from methyl, ethyl, isopropyl, n-propyl, isobutyl, tert-butyl, and isopentyl.

[0033] In some embodiments, the cycloalkyl group includes at least one of cyclobutyl, cyclopentyl, and cyclohexyl.

[0034] In some embodiments, the aromatic group includes at least one of phenyl, substituted phenyl, naphthyl, and substituted naphthyl.

[0035] In some embodiments, the heteroatom substituent includes at least one selected from nitro, alkyloxy, cyano, ester, amino, hydroxy, trifluoromethyl, alkylthio, and alkyl-substituted acyl groups.

[0036] In some implementations, X is C 1～50 Alkyl, C 6～50 Aromatic group, C 6～50 Any one of aromatic heterocyclic groups, halogens, -N(RN)2, and -NCORC.

[0037] In some implementations, B is C. 2～20 Hydroxyl group, C 2～20 Any one of the heteroatoms can be substituted for the hydroxyl group.

[0038] The dihydroquinoline skeletal derivatized catalyst of this invention is based on dihydroquinoline ketone, constructs a tetradentate phenolic ether configuration, and sets a specific R7 coordinating group with a large steric hindrance effect, which can significantly improve the thermal stability of the catalyst. On the other hand, the R1 coordinating group is selected from flexible alkyl, cycloalkyl, or aromatic groups, which can not only improve the solvent solubility of the overall product, but also adjust the electronic properties of the product. Combined with the large steric hindrance group, the stability of the product is further improved, and the applicability of the overall product in various application scenarios is enhanced.

[0039] When applied to the preparation of polyolefin polymerization, the product not only exhibits high catalytic activity but also high catalytic selectivity, resulting in excellent overall application performance.

[0040] Specifically, in some embodiments, the dihydroquinoline ketone skeleton-derived catalyst has the following molecular structure:

[0041]

[0042] In some embodiments, the dihydroquinoline skeletal-derived catalyst has the following molecular structure:

[0043]

[0044] In some embodiments, the dihydroquinoline skeletal-derived catalyst has the following molecular structure:

[0045]

[0046] In some embodiments, the dihydroquinoline skeletal-derived catalyst has the following molecular structure:

[0047]

[0048] In some embodiments, the dihydroquinoline skeletal-derived catalyst has the following molecular structure:

[0049]

[0050] In some embodiments, the dihydroquinoline skeletal-derived catalyst has the following molecular structure:

[0051]

[0052] In some embodiments, the dihydroquinoline skeletal-derived catalyst has the following molecular structure:

[0053]

[0054] In some embodiments, the dihydroquinoline skeletal-derived catalyst has the following molecular structure:

[0055]

[0056] In some embodiments, the dihydroquinoline skeletal-derived catalyst has the following molecular structure:

[0057]

[0058] In some embodiments, the dihydroquinoline skeletal-derived catalyst has the following molecular structure:

[0059]

[0060] The present invention also provides a method for preparing the dihydroquinoline ketone skeleton-derived catalyst, comprising the following steps:

[0061] The dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand and metal complex are mixed and reacted in a solvent to obtain the dihydroquinolinone skeleton-derived catalyst.

[0062] In some embodiments, the molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand is as follows:

[0063]

[0064] In some embodiments, the molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand is as follows:

[0065]

[0066] In some embodiments, the molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand is as follows:

[0067]

[0068] In some embodiments, the molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand is as follows:

[0069]

[0070] In some embodiments, the molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand is as follows:

[0071]

[0072] In some embodiments, the metal complex includes at least one of ZrCl4, ZrBn4, HfCl4, TiCl4, HfBn4, and Ti(NMe2)4.

[0073] Specifically, in some embodiments, the molar ratio of the dihydroquinolinone skeleton-derived tetradentate phenol ether ligand to the metal complex is 1:(1-2).

[0074] In some embodiments, the solvent includes at least one selected from tetrahydrofuran, toluene, benzene, diethyl ether, ethylene glycol dimethyl ether, dichloromethane, and trichloromethane.

[0075] In some embodiments, the temperature during the mixing reaction is -80 to 120°C, and the time is 0.1 to 72 hours.

[0076] It should be noted that the dihydroquinoline ketone skeleton-derived catalyst described in this invention is not limited to obtaining it using the above-mentioned raw materials or reaction pathways. Those skilled in the art can also prepare it using other reaction raw materials and reaction pathways based on the product structure and generally known reaction mechanisms.

[0077] A specific embodiment of the present invention also provides a method for preparing polyolefins, comprising the following steps:

[0078] The olefin, the dihydroquinoline skeletal derivative catalyst described in this invention, and the co-catalyst are mixed and then subjected to a polymerization reaction to obtain the polyolefin.

[0079] In some embodiments, the olefin includes at least one of ethylene and α-olefin.

[0080] Specifically, the α-olefin includes at least one of 1-butene, propylene, 1-octene, and 1-hexene.

[0081] The dihydroquinoline skeletal-derived catalyst of this invention exhibits high structural controllability, good thermal stability and solubility, and maintains high catalytic activity above 140°C. It demonstrates high catalytic activity in reactions such as ethylene polymerization and the polymerization of ethylene with α-olefins. When applied to the homopolymerization of ethylene, the catalytic activity of this product can reach up to 2.7 × 10⁻⁶. 8 g poly / mol metal h; and in the copolymerization of ethylene and octene, its catalytic activity can reach as high as 3.12 × 10⁻⁶. 8 g poly / mol metal h, the molar insertion rate of octene can reach up to 28.2%, and the overall application effect is excellent.

[0082] Specifically, in some embodiments, when the olefin includes ethylene and α-olefin, the concentration of the α-olefin is 0.01 to 50 mol / L.

[0083] In some embodiments, the cocatalyst includes an alkylaluminum cocatalyst.

[0084] Specifically, the alkylaluminum cocatalyst includes at least one of the following: modified ethylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylethoxyaluminum, diethylaluminum chloride, diethylaluminum chloride, trioctylaluminum, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, modified ethylaluminoxane, and modified octylaluminoxane.

[0085] In some embodiments, the molar ratio of the dihydroquinolinone skeleton-derived catalyst to the co-catalyst is 1:(1 to 10000).

[0086] In some embodiments, the polymerization reaction is carried out at a temperature of 20–200°C, for a time of 0.01–120 h, and at a pressure of 0.1–20 MPa.

[0087] The present invention is further illustrated below with specific embodiments, which should not be construed as limiting the scope of protection claimed by the present invention:

[0088] Unless otherwise specified, all materials used in the embodiments and comparative examples are commercially available products.

[0089] Example 1

[0090] An embodiment of the dihydroquinolineone skeleton-derived catalyst and its application described in this invention, wherein the molecular structure of the dihydroquinolineone skeleton-derived catalyst is as follows:

[0091]

[0092] ICP and elemental analysis are as follows: Measured (calculated) C: 72.19 (72.27); H: 7.65 (7.88); Zr: 7.02 (7.13).

[0093] The preparation method of the dihydroquinolinone skeleton-derived catalyst includes the following steps: 1 mmol of dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 1 is dissolved in 15 mL of anhydrous tetrahydrofuran, cooled to -78°C, and 2.5 M n-butyllithium solution (2.2 mmol) is added dropwise. The solution is slowly raised to room temperature and stirred for 2 h to obtain a reaction solution. The reaction solution is transferred to a tetrahydrofuran solution of ZrCl4 (1.0 mmol) that has been cooled to -30°C using a syringe. The reaction is maintained at a low temperature for 1 h, and then slowly raised to room temperature and continued for 24 h. The resulting mixture is treated to remove tetrahydrofuran, 10 mL of toluene is added, and the mixture is filtered to remove insoluble matter. The volatile components in the filtrate are removed under vacuum. The crude product is recrystallized from dichloromethane / n-hexane (volume ratio 1:5) to obtain the dihydroquinolinone skeleton-derived catalyst, denoted as M1 (664 mg, yield 52%).

[0094] The molecular structure of the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 1 is as follows:

[0095]

[0096] The dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 1 was prepared in-house, and the steps are as follows: Figure 1 As shown, it includes the following steps:

[0097] In a 100 mL Shrek tube, 5-hydroxy-2,3-dihydro-1H-quinoline-4-one (10 mmol), potassium carbonate (20 mmol), and 20 mL of acetone were added, followed by potassium iodide (10 mmol). The mixture was stirred at room temperature for 12 h. After the TLC reaction was complete, 2-ethylhexyl bromide (10 mmol) was added to the resulting mixture, and the mixture was heated under reflux for 12 h. After the TLC reaction was complete, the reaction was quenched with water, and the mixture was extracted three times with ethyl acetate and evaporated to dryness to obtain the crude product.

[0098] The crude product was dried and then added to a 100 mL Shrek tube. 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. Two equivalents of phenyl magnesium bromide solution were added, and the mixture was slowly heated to room temperature and stirred for 12 h. Then, 10 mL of 1 M hydrochloric acid was added to the resulting reaction solution, and the reaction was stopped after stirring for 2 h. 10 mL of ethyl acetate was added to the reaction solution. The organic phase was washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The solution was purified by column chromatography to obtain a yellow solid, dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 1 (2.79 g, 80% yield). The NMR data of dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 1 are as follows: 1 HNMR(CDCl3,400MHz): δ7.48-7.45(m,2H),7.43-7.40(m,2H),7.11(t,1H),6.72(dd,1H),6.56(dd,1H),6.15(t,1H),4. 17(d,1H), 4.07(d,1H),3.89(s,3H),3.48(m,1H),3.29(m,1H),1.80-1.72(m,1H),1.45-1.29(m,8H),0.91-0.88(m,6H).

[0099] Example 2

[0100] An embodiment of the dihydroquinolineone skeleton-derived catalyst and its application described in this invention, wherein the molecular structure of the dihydroquinolineone skeleton-derived catalyst is as follows:

[0101]

[0102] ICP and elemental analysis are as follows: Measured (calculated) C: 76.41 (76.59); H: 8.45 (8.62); Zr: 7.33 (7.36).

[0103] The preparation method of the dihydroquinolinone skeleton-derived catalyst includes the following steps: ZrCl4 (1.0 mmol) is dispersed in 5 mL of toluene, cooled to -30°C, and 3M methyl magnesium bromide diethyl ether solution (4.0 mmol) is added dropwise. After stirring for 5 min, 10 mL of toluene solution containing dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 1 (1.0 mmol) is added to the solution. The reaction is carried out at room temperature for 2 h. The insoluble matter is removed by filtration, and the volatile components in the filtrate are removed under vacuum. The crude product is recrystallized from dichloromethane / n-hexane (volume ratio of 1:3) to obtain the dihydroquinolinone skeleton-derived catalyst, denoted as M2 (507 mg, yield 40%).

[0104] The source of the dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 1 is the same as in Example 1.

[0105] Example 3

[0106] An embodiment of the dihydroquinolineone skeleton-derived catalyst and its application described in this invention, wherein the molecular structure of the dihydroquinolineone skeleton-derived catalyst is as follows:

[0107]

[0108] ICP and elemental analysis are as follows: Measured (calculated) C: 70.82 (70.98); H: 7.22 (7.25); Zr: 7.69 (7.81).

[0109] The preparation method of the dihydroquinolineone skeleton-derived catalyst differs from that in Example 1 only in that the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 1 is replaced with an equimolar amount of dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 2, and the resulting product is denoted as M3 (0.721 g, yield 62%).

[0110] The molecular structure of the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 2 is as follows:

[0111]

[0112] The dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 2 was prepared in-house, and the steps are as follows: Figure 2 As shown, it includes the following steps:

[0113] In a 100 mL Shrek tube, 10 mmol of 5-hydroxy-2,3-dihydro-1H-quinoline-4-one, 20 mmol of potassium carbonate, and 20 mL of acetone were added, followed by 10 mmol of potassium iodide. The mixture was stirred at room temperature for 12 h. After the TLC reaction was complete, the reaction mixture was evaporated to dryness. 5 mol% Pd2dba3, 10 mol% P(Tol)3, 11.5 mol of potassium carbonate, and 5 mL of toluene were added to the Shrek tube, and the mixture was heated to reflux. After the TLC reaction was complete, the reaction was quenched with water, and the mixture was extracted three times with ethyl acetate. The crude product was then evaporated to dryness.

[0114] The crude product was dried and then added to a 100 mL Shrek tube. 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. Two equivalents of phenylmagnesium bromide were added, and the mixture was slowly heated to room temperature and stirred for 12 h. Then, 10 mL of 1 M hydrochloric acid was added to the resulting reaction solution, and the reaction was stopped after stirring for 2 h. 10 mL of ethyl acetate was added to the reaction solution. The organic phase was washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The solution was purified by column chromatography to obtain a white solid, dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 2 (4.54 g, 50% yield). The NMR data of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 2 are as follows: 1 HNMR(CDCl3,400MHz): δ7.49(dd,2H),7.39-7.36(m,4H),7.23-7.19(m,4H),7.00(dd,2H),6.97 (d,2H), 6.82-6.80(m,2H), 5.82(dt,2H), 4.51(d,2H), 2.30(q,2H),1.38(s,36H),1.23(s,18H).

[0115] Example 4

[0116] An embodiment of the dihydroquinolineone skeleton-derived catalyst and its application described in this invention, wherein the molecular structure of the dihydroquinolineone skeleton-derived catalyst is as follows:

[0117]

[0118] ICP and elemental analysis are as follows: Measured (calculated) C: 75.62 (75.69); H: 8.02 (8.05); Zr: 8.05 (8.10).

[0119] The preparation method of the dihydroquinolineone skeleton-derived catalyst differs from that in Example 2 only in that the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 1 is replaced with an equimolar amount of dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 2, and the resulting product is denoted as M4 (0.584 g, yield 52%).

[0120] The source of the dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 2 is the same as in Example 3.

[0121] Example 5

[0122] An embodiment of the dihydroquinolineone skeleton-derived catalyst and its application described in this invention, wherein the molecular structure of the dihydroquinolineone skeleton-derived catalyst is as follows:

[0123]

[0124] ICP and elemental analysis are as follows: Measured (calculated) C: 68.92 (68.98); H: 6.22 (6.28); Zr: 8.83 (8.88).

[0125] The preparation method of the dihydroquinolineone skeleton-derived catalyst differs from that in Example 1 only in that the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 1 is replaced with an equimolar amount of dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 3, and the resulting product is denoted as M5 (0.492 g, yield 48%).

[0126] The molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 3 is as follows:

[0127]

[0128] The dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 3 was prepared in-house, and the steps are as follows: Figure 3 As shown, it includes the following steps:

[0129] In a 100 mL Shrek tube, 10 mmol of 5-hydroxy-2,3-dihydro-1H-quinoline-4-one, 20 mmol of potassium carbonate, and 20 mL of acetone were added, followed by 10 mmol of potassium iodide. The mixture was stirred at room temperature for 12 h. After the TLC reaction was complete, 10 mmol of bromohexane was added to the resulting mixture, and the mixture was heated under reflux for 12 h. After the TLC reaction was complete, the reaction was quenched with water, and the mixture was extracted three times with ethyl acetate and evaporated to dryness to obtain the crude product.

[0130] The crude product was dried and then added to a 100 mL Shrek tube. 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. Two equivalents of phenyl magnesium bromide solution were added, and the mixture was slowly heated to room temperature and stirred for 12 h. Then, 10 mL of 1 M hydrochloric acid was added to the resulting reaction solution, and the reaction was stopped after stirring for 2 h. 10 mL of ethyl acetate was added to the reaction solution. The organic phase was washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The solution was purified by column chromatography to obtain a white solid dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 3 (4.54 g, 50% yield). The NMR data of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 1 are as follows: 1HNMR(CDCl3,400MHz): δ7.49(dd,2H),7.39-7.36(m,4H),7.23-7.19(m,4H),7.00(dd,2H),6.97 (d,2H), 6.82-6.80(m,2H), 5.82(dt,2H), 4.51(d,2H), 2.30(q,2H),1.38(s,36H),1.23(s,18H).

[0131] Example 6

[0132] An embodiment of the dihydroquinolineone skeleton-derived catalyst and its application described in this invention, wherein the molecular structure of the dihydroquinolineone skeleton-derived catalyst is as follows:

[0133]

[0134] ICP and elemental analysis are as follows: Measured (calculated) C: 74.21 (74.27); H: 7.09 (7.15); Zr: 9.23 (9.25).

[0135] The preparation method of the dihydroquinolineone skeleton-derived catalyst differs from that in Example 2 only in that the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 1 is replaced with an equimolar amount of dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 3, and the resulting product is denoted as M6 (0.541 g, yield 55%).

[0136] The source of the dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 3 is the same as in Example 5.

[0137] Example 7

[0138] An embodiment of the dihydroquinolineone skeleton-derived catalyst and its application described in this invention, wherein the molecular structure of the dihydroquinolineone skeleton-derived catalyst is as follows:

[0139]

[0140] ICP and elemental analysis are as follows: Measured (calculated) C: 71.99 (72.01); H: 6.52 (6.58); Zr: 6.90 (6.92).

[0141] The preparation method of the dihydroquinolineone skeleton-derived catalyst differs from that in Example 1 only in that the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 1 is replaced with an equimolar amount of dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 4, and the resulting product is denoted as M7 (0.749 g, yield 56%).

[0142] The molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 4 is as follows:

[0143]

[0144] The dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 4 was prepared in-house, and the steps are as follows: Figure 4 As shown, it includes the following steps:

[0145] In a 100 mL Shrek tube, 10 mmol of 5-hydroxy-2,3-dihydro-1H-quinoline-4-one, 20 mmol of potassium carbonate, and 20 mL of acetone were added, followed by 10 mmol of potassium iodide. The mixture was stirred at room temperature for 12 h. After the TLC reaction was complete, 10 mmol of 5-bromo-1-(2-ethylhexyl)-1H-indole was added to the resulting mixture. After the TLC reaction was complete, the reaction was quenched with water, and the mixture was extracted three times with ethyl acetate and evaporated to dryness to obtain the crude product.

[0146] The crude product was dried and then added to a 100 mL Shrek tube. 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. Two equivalents of phenylmagnesium bromide were added, and the mixture was slowly heated to room temperature and stirred for 12 h. Then, 10 mL of 1 M hydrochloric acid was added to the resulting reaction solution, and the reaction was stopped after stirring for 2 h. 10 mL of ethyl acetate was added to the reaction solution. The organic phase was washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The solution was purified by column chromatography to obtain a white solid dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 4 (3.83 g, yield 45%). The NMR data of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 4 are as follows: 1 HNMR(CDCl3,400MHz): δ7.98(dd,2H),7.91(d,2H),7.49-7.43(m,6H),7.39-7.36(m,4H ),7.26-7.22(m,6H),7.11(dd,2H),6.75(d,2H),6.55(dd,2H),5.83(td,2H),4.61(dd,2 H), 4.28(dd,2H), 4.19(t,4H),4.06(q,2H),3.79(q,2H),2.84-2.78(m,2H),2.31(q,2H) ),1.86-1.80(m,2H),1.41-1.28(m,16H),1.14(d,6H),1.09(d,6H),0.91-0.88(m,12H).

[0147] Example 8

[0148] An embodiment of the dihydroquinolineone skeleton-derived catalyst and its application described in this invention, wherein the molecular structure of the dihydroquinolineone skeleton-derived catalyst is as follows:

[0149]

[0150] ICP and elemental analysis are as follows: Measured (calculated) C: 76.17 (76.19); H: 7.22 (7.26); Zr: 7.11 (7.14).

[0151] The preparation method of the dihydroquinolineone skeleton-derived catalyst differs from that in Example 2 only in that the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 1 is replaced with an equimolar amount of dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 4, and the resulting product is denoted as M8 (0.523 g, yield 41%).

[0152] The source of the dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 4 is the same as in Example 7.

[0153] Example 9

[0154] An embodiment of the dihydroquinolineone skeleton-derived catalyst and its application described in this invention, wherein the molecular structure of the dihydroquinolineone skeleton-derived catalyst is as follows:

[0155]

[0156] ICP and elemental analysis are as follows: Measured (calculated) C: 70.79 (70.80); H: 7.15 (7.17); Zr: 7.90 (7.91).

[0157] The preparation method of the dihydroquinolinone skeleton-derived catalyst differs from that in Example 1 only in that the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 1 is replaced with an equimolar amount of dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 5, and the resulting product is denoted as M9 (0.690 g, yield 60%).

[0158] The molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 5 is as follows:

[0159]

[0160] The dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 5 was prepared in-house, and the steps are as follows: Figure 5 As shown, it includes the following steps:

[0161] In a 100 mL Shrek tube, 5-hydroxy-2,3-dihydro-1H-quinoline-4-one (10 mmol), potassium carbonate (20 mmol), and 20 mL of acetone were added, followed by potassium iodide (10 mmol). The mixture was stirred at room temperature for 12 h. After the TLC reaction was complete, n-butane (10 mmol) was added to the resulting mixture. After the TLC reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate and evaporated to dryness to obtain the crude product.

[0162] The crude product was dried and then added to a 100 mL Shrek tube. 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. Two equivalents of phenylmagnesium bromide were added, and the mixture was slowly heated to room temperature and stirred for 12 h. Then, 10 mL of 1 M hydrochloric acid was added to the resulting reaction solution, and the reaction was stopped after stirring for 2 h. 10 mL of ethyl acetate was added to the reaction solution. The organic phase was washed with saturated sodium bicarbonate and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The solution was purified by column chromatography to obtain a white solid dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 5 (3.33 g, 77% yield). The NMR data of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand 5 are as follows: 1 HNMR(CDCl3,400MHz): δ7.42(dd,2H),7.34(dt,4H),7.29-7.26(m,6H),7.15(ddd,2H),6.96(d,2H),6.59(dd,2H),6.14(t,2H)4.17(q,4H),4. 03-4.01(m,4H),3.33(t,4H),3.03-2.98(m,2H),1.93-1.88(m,4H),1. 61(q,4H),2.30(q,2H),1.47-1.35(m,22H),1.28(d,12H),0.95(t,6H).

[0163] Example 10

[0164] An embodiment of the dihydroquinolineone skeleton-derived catalyst and its application described in this invention, wherein the molecular structure of the dihydroquinolineone skeleton-derived catalyst is as follows:

[0165]

[0166] ICP and elemental analysis are as follows: Measured (calculated) C: 75.51 (75.56); H: 7.93 (7.97); Zr: 8.14 (8.20).

[0167] The preparation method of the dihydroquinolineone skeleton-derived catalyst differs from that in Example 2 only in that the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 1 is replaced with an equimolar amount of dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand 5, and the resulting product is denoted as M10 (0.433 g, yield 39%).

[0168] The source of the dihydroquinolinone skeleton-derived tetradentate phenol ether ligand 5 is the same as in Example 9.

[0169] Example 1

[0170] To verify the effectiveness of the dihydroquinoline ketone framework-derived catalyst described in this invention, the products from each embodiment were used together as catalysts for the homopolymerization reaction of ethylene. The specific steps are as follows:

[0171] The reactor equipped with a mechanical stirrer was heated to 170°C and evacuated for 1 hour using a vacuum pump. Ethylene gas was then introduced into the reactor until the pressure reached 1 bar. An IsoparE solution of modified methylaluminoxane (MMAO-7) as a co-catalyst and 0.2 μmol of M1–M10 obtained in each example were added to the reactor as the main catalyst (Al / M = 800). After the addition was complete, the ethylene gas pressure was increased to 3 MPa, and the temperature was raised to 170°C with stirring for 10 minutes to initiate the polymerization reaction. After the polymerization reaction was completed, the residual ethylene gas was quickly released, the reactor was opened, and the solid-liquid mixture was poured into a 1:1 volume ratio solution of 3M hydrochloric acid and ethanol. The mixture was stirred, filtered, and dried in a vacuum oven at 60°C for 12 hours to obtain a polymer sample. The catalytic activity of the catalyst and the properties of the product were analyzed using GC and GPC. The results are shown in Table 1 below.

[0172] Meanwhile, a control group was set up, which used the M7 catalyst in CN117964652A to perform the same treatment and statistics as described above, as shown in Table 1.

[0173] Table 1

[0174] Test Results Yield (g) Catalyst activity (10 6 g poly / mol metal h)]]> <![CDATA[M w ]]> PDI Example 1 3.2 99 96000 2.2 Example 2 3.5 105 112000 1.9 Example 3 5.4 161 163000 1.82 Example 4 6.0 180 188000 1.74 Example 5 4.2 126 132200 2.1 Example 6 4.8 144 150000 2.02 Example 7 8.2 246 202000 1.6 Example 8 9.0 270 215000 1.54 Example 9 7.7 231 198000 1.73 Example 10 7.9 237 202000 1.7 Control group 1 2.9 87 92100 1.97

[0175] The test results show that the dihydroquinolinone skeleton-derived catalyst provided by this invention can efficiently catalyze the polymerization of ethylene. This is attributed to the modification of the N-substitution site, which improves its solubility in nonpolar solvents. The catalyst also exhibits excellent thermal stability, maintaining good catalytic activity at 170°C, and this effect can be achieved with a relatively small amount of co-catalyst (less than 1000 compared to the main catalyst). Among these, the product obtained in Example 8 showed the highest catalytic activity in ethylene polymerization, reaching 2.7 × 10⁻⁶. 8 g poly / mol metal The resulting polymer had a molecular weight as high as 215,000 g / mol. However, under the same testing conditions, a similar M7 catalyst prepared in the prior art CN117964652A showed significantly lower catalytic activity at 170°C compared to the product described in this invention, with an activity of only 0.87 × 10⁻⁶. 8 g poly / mol metal h, the polymer molecular weight is only 92100 g / mol.

[0176] Example 2

[0177] To verify the effectiveness of the dihydroquinoline ketone skeleton-derived catalyst described in this invention, the products from each embodiment were used together as catalysts for the polymerization of ethylene and 1-octene. The specific steps are as follows:

[0178] The reactor equipped with mechanical stirring was heated to 200°C and evacuated for 1 hour using a vacuum pump. The temperature was then lowered to 170°C, and ethylene gas was introduced into the reactor until the pressure reached 1 bar. An IsoparE solution of modified methylaluminoxane (MMAO-7) as a co-catalyst, 0.3 μmol of M1–M10 obtained in each example as the main catalyst (Al / M = 800), and a 0.275 mol / L IsoparE solution of 1-octene were added to the reactor. After the addition was complete, the ethylene gas pressure was increased to 3 MPa, and the temperature was raised to 170°C with stirring for 10 minutes to initiate the polymerization reaction. After the polymerization reaction was completed, the residual ethylene gas was quickly released, the reactor was opened, and the solid-liquid mixture was poured into a 1:1 volume ratio solution of 3M hydrochloric acid and ethanol. The mixture was stirred, filtered, and dried in a vacuum oven at 60°C for 12 hours to obtain a polymer sample. GC and GPC were used to analyze the catalytic activity of the catalyst and the properties of the product. High-temperature carbon spectroscopy was used to confirm the insertion rate of 1-octene. The results are shown in Table 1 below.

[0179] Meanwhile, a control group was set up, and the same treatment and statistics were performed using the catalyst in M8 catalyst of CN117964652A, as shown in Table 2.

[0180] Table 2

[0181]

[0182]

[0183] As shown in Table 2, the dihydroquinolinone skeletal-derived catalyst provided by this invention can also efficiently catalyze the polymerization reaction of ethylene and 1-octene. This catalyst maintains good catalytic activity at 170°C, with a maximum copolymerization activity of 3.12 × 10⁻⁶. 8 g poly / mol metal The copolymer achieved a maximum molecular weight of 232,000 g / mol and a maximum 1-octene insertion rate of 28.2%, resulting in a polymer molecular weight as high as 251,000 g / mol. In contrast, under the same test conditions, the M8 catalyst in the existing product CN117964652A exhibited significantly lower catalytic activity at 170 °C, only 1.02 × 10⁻⁶. 8 g poly / mol metal The 1-octene insertion rate was only 12.7%, and the molecular weight of the catalyzed product was only 99200 g / mol, further indicating that the catalyst described in this invention has a better catalytic effect than existing similar products.

[0184] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A dihydroquinolinone skeleton-derived catalyst, characterized in that, Its molecular structure is as follows: Wherein, R1 is at least one of alkyl, cycloalkyl, and aryl groups; R2, R3, R4, R5, and R6 are each at least one of H, alkyl, cycloalkyl, aromatic, and heteroatom substituents; R7 is at least one of alkyl, cycloalkyl, phenyl, substituted phenyl, and substituted naphthyl; M is at least one of Zr, Ti and Cr; X is any one of alkyl, aromatic, aromatic heterocyclic, halogen and nitrogen-containing groups, and n = 1 to 3; B can be either a hydroxyl group or a heteroatom-substituted hydroxyl group.

2. The dihydroquinoline skeletal-derived catalyst according to claim 1, characterized in that, The alkyl group includes at least one selected from methyl, ethyl, isopropyl, n-propyl, isobutyl, tert-butyl, and isopentyl, and / or the cycloalkyl group includes at least one selected from cyclobutyl, cyclopentyl, and cyclohexyl, and / or the aromatic group includes at least one selected from phenyl, substituted phenyl, naphthyl, and substituted naphthyl.

3. The dihydroquinoline skeletal-derived catalyst as described in claim 1, characterized in that, The heteroatom substituents include at least one selected from nitro, alkyloxy, cyano, ester, amino, hydroxy, trifluoromethyl, alkylthio, and alkyl-substituted acyl groups.

4. The dihydroquinoline skeletal-derived catalyst according to claim 1, characterized in that, X is C 1～50 Alkyl, C 6～50 Aromatic group, C 6～50 Any one of aromatic heterocyclic groups, halogens, -N(RN)2, and -NCORC, and / or, wherein B is C. 2～20 Hydroxyl groups and C 2～20 Any one of the heteroatoms can be substituted for the hydroxyl group.

5. The dihydroquinoline skeletal-derived catalyst as described in claim 1, characterized in that, The dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

6. The dihydroquinoline skeletal-derived catalyst according to claim 1, characterized in that, The dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

7. The dihydroquinoline skeletal-derived catalyst according to claim 1, characterized in that, The dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

8. The dihydroquinoline skeletal-derived catalyst according to claim 1, characterized in that, The dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

9. The dihydroquinoline skeletal-derived catalyst according to claim 1, characterized in that, The dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

10. The dihydroquinolinone skeleton-derived catalyst according to claim 1, characterized in that, The dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

11. The dihydroquinolinone skeleton-derived catalyst according to claim 1, characterized in that, The dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

12. The dihydroquinoline skeletal-derived catalyst according to claim 1, characterized in that, The dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

13. The dihydroquinoline skeletal-derived catalyst according to claim 1, characterized in that, The dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

14. The dihydroquinoline skeletal-derived catalyst according to claim 1, characterized in that, The dihydroquinolinone skeleton-derived catalyst has the following molecular structure:

15. The method for preparing the dihydroquinoline skeletal-derived catalyst according to any one of claims 1 to 14, characterized in that, Includes the following steps: The dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand and metal complex are mixed and reacted in a solvent to obtain the dihydroquinolinone skeleton-derived catalyst.

16. The method for preparing the dihydroquinoline skeletal-derived catalyst as described in claim 15, characterized in that, The molecular structure of the dihydroquinolineone skeleton-derived tetradentate phenolic ether ligand is as follows: Alternatively, the molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand is as follows: Alternatively, the molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand is as follows: Alternatively, the molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand is as follows: Alternatively, the molecular structure of the dihydroquinolinone skeleton-derived tetradentate phenolic ether ligand is as follows:

17. The method for preparing the dihydroquinoline skeletal-derived catalyst as described in claim 15, characterized in that, The metal complex includes at least one of ZrCl4, ZrBn4, HfCl4, TiCl4, HfBn4 and Ti(NMe2)4, and / or the solvent includes at least one of tetrahydrofuran, toluene, benzene, diethyl ether, ethylene glycol dimethyl ether, dichloromethane and trichloromethane.

18. A method for preparing a polyolefin, characterized in that, Includes the following steps: The olefin, the dihydroquinoline skeletal derivative catalyst according to any one of claims 1 to 14, and the co-catalyst are mixed and then subjected to a polymerization reaction to obtain the polyolefin.

19. The method for preparing the polyolefin as described in claim 18, characterized in that, The olefins include at least one of ethylene and α-olefins.

20. The method for preparing the polyolefin as described in claim 18, characterized in that, The polymerization reaction is carried out at a temperature of 20–200°C, for a time of 0.01–120 h, and at a pressure of 0.1–20 MPa.

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