Preparation method of phosphite antioxidant P-EPQ

Abstract

The invention discloses a preparation method of a phosphite antioxidant P-EPQ, and relates to the technical field of antioxidants. The preparation method comprises the following steps: sequentially weighing biphenyl and phosphorus trichloride, adding into a reaction flask, stirring and dissolving at room temperature, adding a catalyst A, stirring and heating, controlling the internal temperature to be 70-76 DEG C, condensing and refluxing phosphorus trichloride, reacting for a certain time, stopping the reaction, and distilling to obtain a product which is an intermediate 4, 4 '-biphenyl bis-phosphine dichloride; the method comprises the following steps: transferring an intermediate 4, 4 '-biphenyl bis-dichlorophosphine into a three-neck flask, filling a mixed solution of 2, 4-di-tert-butylphenol and a catalyst B into a constant-pressure dropping funnel, dropwise adding the mixed solution into a reaction flask, keeping the temperature for reaction after the dropwise addition is completed, adding a solvent into a reaction solution after the reaction is stopped, raising the internal temperature, stirring and dissolving, carrying out suction filtration on the solution in the reaction flask, and drying to obtain the 2, 4'-biphenyl bis-dichlorophosphine. And carrying out negative pressure rotary evaporation on the filtrate to remove the solvent, wherein the distilled product is the target product P-EPQ. The preparation method of the antioxidant P-EPQ provided by the invention has relatively high yield.

Description

Technical Field

[0001] This application relates to the field of antioxidant technology, and in particular to a method for preparing a phosphite antioxidant P-EPQ. Background Technology

[0002] Antioxidants are chemical substances that can resist or slow down oxidation reactions. They are widely used in petroleum, chemical, food, and pharmaceutical industries to improve the stability of substances and delay or prevent oxidation reactions. In polymer materials, antioxidants are mainly used to inhibit and slow down the oxidative degradation process of polymers, thereby improving the thermal stability of polymers and extending their service life. There are many types of antioxidants, which can be divided into chain-terminating antioxidants and quenching antioxidants according to their mechanism of action. Chain-terminating antioxidants can react with free radicals to form non-free radical substances, thereby terminating the oxidation chain reaction; quenching antioxidants can quench excited polymer molecules, restoring them to the ground state and preventing photo-oxidation reactions.

[0003] P-EPQ, or tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenyl diphosphite, is a commonly used chain-terminated antioxidant with good thermal stability and antioxidant properties. P-EPQ is a phosphite antioxidant with a diphosphate ester structure and a high relative molecular mass of 1035, making it one of the few phosphite antioxidants with CP bonds. Its high relative molecular mass gives it good compatibility, low volatility, good hydrolysis resistance, and high thermal stability. Furthermore, its high thermogravimetric temperature (TGA) of 350℃ can improve color yellowing under high-temperature processing and stabilize the melt flow index. It is suitable for use with polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyamide, polystyrene, polypropylene, ABS resin, etc.

[0004] However, in the existing technology, the yield of antioxidant P-EPQ is generally low, resulting in high production costs and limiting the development and application of antioxidant P-EPQ in certain fields. Therefore, it is necessary to provide a method for preparing antioxidant P-EPQ to improve its production yield. Summary of the Invention

[0005] To improve the yield of antioxidant P-EPQ, this application provides a method for preparing phosphite antioxidant P-EPQ.

[0006] The preparation method of the phosphite antioxidant P-EPQ provided in this application adopts the following technical solution: A method for preparing a phosphite antioxidant P-EPQ includes the following steps: S1. Nitrogen gas is introduced to replace the air in the reaction flask. After replacement, biphenyl and phosphorus trichloride are weighed and added to the reaction flask in sequence. After dissolving by stirring at room temperature, catalyst A is added, and the mixture is stirred and heated. The temperature inside the flask is controlled at 70-76℃. The phosphorus trichloride is refluxed and the generated hydrogen chloride gas is introduced into a buffer flask. The reaction is stopped after 6-8 hours. The unreacted phosphorus trichloride is distilled off under negative pressure at 70-90℃. After distillation, the intermediate 4,4'-biphenylbisphosphine chloride is obtained. The reaction formula is as follows: S2. Purge the air from the reaction flask with nitrogen. After purging, transfer the 4,4'-biphenylbisphosphine chloride obtained in S1 to the reaction flask. Weigh out 2,4-di-tert-butylphenol and catalyst B sequentially, and stir to dissolve at room temperature. Set the external temperature of the oil bath to 120-130℃ and begin adding the mixture of 2,4-di-tert-butylphenol and catalyst B dropwise into the reaction flask, controlling the dropping rate to prevent the temperature inside the reaction flask from rising too quickly. After the addition is complete, maintain the internal temperature at 106-110℃ and continue the reaction. After a certain reaction time, stop the reaction and begin post-processing. Add a certain amount of solvent to the reaction solution, heat to 75-85℃ and stir to dissolve. After 30-50 minutes, cool to room temperature. Filter the solution in the reaction flask, and then evaporate the solvent from the filtrate under negative pressure. The product after distillation is the target product P-EPQ. The reaction formula is as follows: The catalyst A is aluminum trichloride; Catalyst B is modified γ-alumina supported triethylamine.

[0007] Preferably, the molar ratio of biphenyl, phosphorus trichloride and catalyst A in S1 is 1:(3.5-4.0):(2.5-3).

[0008] Preferably, the molar ratio of 2,4-di-tert-butylphenol in S2 to 4,4'-biphenylbisphosphine chloride obtained in S1 is 1:(0.2-0.4).

[0009] Preferably, the weight ratio of 2,4-di-tert-butylphenol to catalyst B in S2 is 1:(1.5-2).

[0010] Preferably, the reaction time in S2 is 2-4 hours.

[0011] Preferably, the solvent in S2 is one of toluene and xylene; the solid-liquid ratio of 2,4-di-tert-butylphenol to the solvent is 1:(1.5-2)g / mL.

[0012] By adopting the above technical solution, biphenyl is reacted with phosphorus trichloride under the action of a catalyst to generate the intermediate 4,4'-biphenylbisphosphine chloride. The intermediate 4,4'-biphenylbisphosphine chloride then undergoes an esterification reaction with 2,4-di-tert-butylphenol under the action of a catalyst to generate the antioxidant P-EPQ. In the reaction process, aluminum trichloride is used as the catalyst in the first step, and modified γ-alumina supported triethylamine is used as the catalyst in the second step. The catalyst has high reactivity and good stability, which effectively promotes the reaction and improves the yield of antioxidant P-EPQ.

[0013] Preferably, the preparation method of the modified γ-alumina supported triethylamine catalyst includes the following steps: T1. Weigh γ-alumina powder and ammonium bicarbonate and place them in a reaction vessel. Add deionized water and stir for 20-30 minutes. After sealing, place the reaction vessel in an oven for hydrothermal treatment. After filtration, washing and drying, the treated material is calcined at 600-700℃ for 4-6 hours to obtain rod-shaped γ-alumina precursor. T2. Weigh the rod-shaped γ-alumina precursor prepared in T1, add an appropriate amount of methyltriethoxysilane and mix evenly, add 65% HNO3 solution and knead evenly, extrude the material into strips on an extruder, and dry the strip material at 120-130℃ for 8-10h; calcine the dried sample at 600-700℃ for 4-6h to obtain the γ-alumina support. T3. Place the γ-alumina support in the solvent ethanol, add triethylamine, stir and mix for 6-10 h, and then dry at 90-110 °C to obtain the modified γ-alumina supported triethylamine catalyst.

[0014] Preferably, the weight ratio of γ-alumina powder to ammonium bicarbonate in T1 is 1:(1.6-1.9).

[0015] Preferably, the weight ratio of the rod-shaped γ-alumina precursor, methyltriethoxysilane, and HNO3 in T2 is 1:(0.1-0.5):(0.7-0.9).

[0016] Preferably, the weight ratio of the γ-alumina carrier, triethylamine, and ethanol in T3 is 1:(1-2):(20-40).

[0017] By adopting the above technical solution, using γ-alumina powder and ammonium bicarbonate as raw materials and employing hydrothermal technology, rod-shaped γ-alumina supports were successfully prepared. Through the action of methyltriethoxysilane and nitric acid, the hydrophilicity and adhesion of the alumina surface were enhanced. Modified γ-alumina supported triethylamine catalyst was prepared using this alumina as a support, which effectively improved the catalytic activity and stability of the triethylamine catalyst, thereby effectively improving the reaction efficiency and yield of antioxidant P-EPQ.

[0018] In summary, this application includes at least one of the following beneficial technical effects: 1. By adopting the above technical solution, biphenyl is reacted with phosphorus trichloride under the action of a catalyst to generate the intermediate 4,4'-biphenylbisphosphine chloride; the intermediate 4,4'-biphenylbisphosphine chloride then undergoes an esterification reaction with 2,4-di-tert-butylphenol under the action of a catalyst to generate the antioxidant P-EPQ. In the reaction process, aluminum trichloride is used as the catalyst in the first step, and modified γ-alumina supported triethylamine is used as the catalyst in the second step. The catalyst has high reactivity and good stability, which effectively promotes the reaction and improves the yield of antioxidant P-EPQ. Detailed Implementation

[0019] The present application will be further described in detail below with reference to the embodiments.

[0020] Preparation Example Preparation Example 1 T1. Weigh 10g of γ-alumina powder and 16g of ammonium bicarbonate and place them in a polytetrafluoroethylene liner of a high-pressure autoclave. Add deionized water (60% of the liner volume) and stir for 20min. After sealing, place the autoclave in an oven for hydrothermal treatment. After filtration, washing and drying, the treated material is calcined in a muffle furnace at 600℃ for 6h to obtain rod-shaped γ-alumina precursor. T2. Weigh 10g of the rod-shaped γ-alumina precursor prepared by T1, add 1g of methyltriethoxysilane and mix evenly, add 7g of 65% HNO3 solution and knead evenly, extrude on a twin-screw extruder, and place the resulting strip material in an oven to dry at 120℃ for 10h; place the dried sample in a muffle furnace and calcine at 600℃ for 6h to obtain the γ-alumina support; T3. Place 1g of the γ-alumina support prepared by T2 in 20g of ethanol, add 1g of triethylamine, stir and mix for 6h, and then dry at 90℃ to obtain the modified γ-alumina supported triethylamine catalyst.

[0021] Preparation Example 2 T1. Weigh 10g of γ-alumina powder and 16g of ammonium bicarbonate and place them in a polytetrafluoroethylene liner of a high-pressure autoclave. Add deionized water (60% of the liner volume) and stir for 25 minutes. After sealing, place the autoclave in an oven for hydrothermal treatment. After filtration, washing and drying, the treated material is calcined in a muffle furnace at 650℃ for 5 hours to obtain rod-shaped γ-alumina precursor. T2. Weigh 10g of the rod-shaped γ-alumina precursor prepared by T1, add 1g of methyltriethoxysilane and mix well, add 7g of 65% HNO3 solution and knead well, extrude on a twin-screw extruder, and place the resulting strip material in an oven to dry at 125℃ for 9h; place the dried sample in a muffle furnace to calcine at 600℃ for 6h to obtain the γ-alumina support; T3. Place 1g of the γ-alumina support prepared by T2 into 20g of ethanol, add 1g of triethylamine, stir and mix for 8h, and then dry at 100℃ to obtain the modified γ-alumina supported triethylamine catalyst.

[0022] Preparation Example 3 T1. Weigh 10g of γ-alumina powder and 16g of ammonium bicarbonate and place them in a polytetrafluoroethylene liner of a high-pressure autoclave. Add deionized water (60% of the liner volume) and stir for 30 minutes. After sealing, place the autoclave in an oven for hydrothermal treatment. After filtration, washing and drying, the treated material is calcined in a muffle furnace at 700℃ for 4 hours to obtain rod-shaped γ-alumina precursor. T2. Weigh 10g of the rod-shaped γ-alumina precursor prepared by T1, add 1g of methyltriethoxysilane and mix well, add 7g of 65% HNO3 solution and knead well, extrude on a twin-screw extruder, and place the resulting strip material in an oven to dry at 130℃ for 8h; place the dried sample in a muffle furnace to calcine at 600℃ for 6h to obtain the γ-alumina support; T3. Place 1g of the γ-alumina support prepared by T2 into 20g of ethanol, add 1g of triethylamine, stir and mix for 10h, and then dry at 110℃ to obtain the modified γ-alumina supported triethylamine catalyst.

[0023] Preparation Example 4 The difference between Preparation Example 4 and Preparation Example 1 is that the mass of γ-alumina powder used in Preparation Example 4 in T1 is 10g and the mass of ammonium bicarbonate is 17.5g.

[0024] Preparation Example 5 The difference between Preparation Example 5 and Preparation Example 1 is that the mass of γ-alumina powder used in Preparation Example 5 in T1 is 10g and the mass of ammonium bicarbonate is 19g.

[0025] Preparation Example 6 The difference between Preparation Example 6 and Preparation Example 1 is that the mass of γ-alumina powder used in Preparation Example 6 in T1 is 10g and the mass of ammonium bicarbonate is 14g.

[0026] Preparation Example 7 The difference between Preparation Example 7 and Preparation Example 1 is that the mass of γ-alumina powder used in Preparation Example 7 in T1 is 10g and the mass of ammonium bicarbonate is 21g.

[0027] Preparation Example 8 The difference between Preparation Example 8 and Preparation Example 1 is that in Preparation Example 8, the mass of the rod-shaped γ-alumina precursor used in T2 was 10g, the mass of methyltriethoxysilane was 3g, and the mass of HNO3 with a mass fraction of 65% was 8g.

[0028] Preparation Example 9 The difference between Preparation Example 9 and Preparation Example 1 is that in Preparation Example 9, the mass of the rod-shaped γ-alumina precursor used in T2 was 10g, the mass of methyltriethoxysilane was 5g, and the mass of HNO3 with a mass fraction of 65% was 9g.

[0029] Preparation Example 10 The difference between Preparation Example 10 and Preparation Example 1 is that in Preparation Example 10, the mass of the rod-shaped γ-alumina precursor used in T2 was 10 g, the mass of methyltriethoxysilane was 0.5 g, and the mass of HNO3 with a mass fraction of 65% was 5 g.

[0030] Preparation Example 11 The difference between Preparation Example 11 and Preparation Example 1 is that in Preparation Example 11, the mass of the rod-shaped γ-alumina precursor used in T2 was 10 g, the mass of methyltriethoxysilane was 6 g, and the mass of HNO3 with a mass fraction of 65% was 9 g.

[0031] Preparation Example 12 The difference between Preparation Example 12 and Preparation Example 1 is that the mass of the rod-shaped γ-alumina support used in Preparation Example 12 in T3 is 1 g, the mass of triethylamine is 1.5 g, and the mass of ethanol is 30 g.

[0032] Preparation Example 13 The difference between Preparation Example 13 and Preparation Example 1 is that the mass of the rod-shaped γ-alumina support used in Preparation Example 13 in T3 is 1g, the mass of triethylamine is 2g, and the mass of ethanol is 40g.

[0033] Preparation Example 14 The difference between Preparation Example 14 and Preparation Example 1 is that the mass of the rod-shaped γ-alumina support used in Preparation Example 14 in T3 is 1 g, the mass of triethylamine is 0.5 g, and the mass of ethanol is 10 g.

[0034] Preparation Example 15 The difference between Preparation Example 15 and Preparation Example 1 is that the mass of the rod-shaped γ-alumina support used in Preparation Example 15 in T3 is 1g, the mass of triethylamine is 3g, and the mass of ethanol is 50g. Example

[0035] Example 1 S1. Install a mechanical stirrer, thermometer, nitrogen port, and condenser in a 500mL three-necked flask and heat it in an oil bath. Purge the air in the reaction flask with nitrogen. After the purging is complete, weigh out 44g of biphenyl and 150g of phosphorus trichloride and add them to the reaction flask. Stir and dissolve them at room temperature, then add 101g of catalyst A, aluminum trichloride. Stir and heat the flask, controlling the temperature inside the flask to 70-76℃. Reflux the phosphorus trichloride and introduce the generated hydrogen chloride gas into a buffer flask. Stop the reaction after 7 hours. Distill the reaction solution under negative pressure at 70℃ to remove the unreacted phosphorus trichloride. After distillation, the intermediate 4,4'-biphenyl bisphosphine chloride is obtained. S2. Install a mechanical stirrer, thermometer, nitrogen inlet, and constant pressure low-liquid funnel on a 1L three-necked flask, and heat in an oil bath; purge the air from the reaction flask with nitrogen. After purging, transfer 163.2g of 4,4'-biphenylbisphosphine chloride obtained from S1 to the reaction flask, and then weigh out 215g of... 2,4-Di-tert-butylphenol and 380g of triethylamine supported on γ-alumina modified by catalyst B obtained in Preparation Example 1 were dissolved in a beaker by stirring at room temperature. The external temperature of the oil bath was set to 120°C, and the mixture of 2,4-di-tert-butylphenol and triethylamine supported on γ-alumina modified by catalyst B was added dropwise to the reaction flask. The dropping rate was controlled to prevent the temperature inside the reaction flask from rising too quickly. After the addition was completed, the internal temperature was controlled at 106-110°C and the reaction was maintained for 2 hours. After the reaction was completed, 400mL of toluene solvent was added to the reaction solution, and the temperature was raised to 80°C and stirred to dissolve. After 30 minutes, the temperature was lowered to room temperature. The solution in the reaction flask was filtered by suction, and the solvent was removed by rotary evaporation of the filtrate under negative pressure at 110°C. The product after distillation was the target product P-EPQ.

[0036] Example 2 S1. Install a mechanical stirrer, thermometer, nitrogen port, and condenser in a 500mL three-necked flask and heat it in an oil bath. Purge the air in the reaction flask with nitrogen. After the air is replaced, weigh 44g of biphenyl and 150g of phosphorus trichloride into the reaction flask. Stir and dissolve the biphenyl at room temperature, then add 101g of catalyst A (aluminum trichloride). Stir and heat the flask, controlling the temperature inside the flask to 70-76℃. Reflux the phosphorus trichloride and introduce the generated hydrogen chloride gas into a buffer flask. Stop the reaction after 6 hours. Distill the reaction solution under negative pressure at 80℃ to remove the unreacted phosphorus trichloride. After distillation, the intermediate 4,4'-biphenyl bisphosphine chloride is obtained. S2. Install a mechanical stirrer, thermometer, nitrogen inlet, and constant pressure low-liquid funnel on a 1L three-necked flask, and heat in an oil bath; purge the air from the reaction flask with nitrogen. After purging, transfer 163.2g of 4,4'-biphenylbisphosphine chloride obtained from S1 to the reaction flask, and then weigh out 215g of... 2,4-Di-tert-butylphenol and 380g of triethylamine supported on γ-alumina modified by catalyst B obtained in Preparation Example 1 were dissolved in a beaker by stirring at room temperature. The external temperature of the oil bath was set to 125°C, and the mixture of 2,4-di-tert-butylphenol and triethylamine supported on γ-alumina modified by catalyst B was added dropwise to the reaction flask. The dropping rate was controlled to prevent the temperature inside the reaction flask from rising too quickly. After the addition was completed, the internal temperature was controlled at 106-110°C and the reaction was maintained for 3 hours. After the reaction was completed, 322.5mL of toluene solvent was added to the reaction solution, and the temperature was raised to 75°C and stirred to dissolve. After 40 minutes, the temperature was lowered to room temperature. The solution in the reaction flask was filtered by suction, and the solvent was removed by rotary evaporation of the filtrate under negative pressure at 115°C. The product after distillation was the target product P-EPQ.

[0037] Example 3 S1. Install a mechanical stirrer, thermometer, nitrogen port, and condenser in a 500mL three-necked flask and heat it in an oil bath. Purge the air in the reaction flask with nitrogen. After the air is replaced, weigh 44g of biphenyl and 150g of phosphorus trichloride into the reaction flask. Stir and dissolve the biphenyl at room temperature. Add 101g of catalyst A, aluminum trichloride, stir and heat. Control the temperature in the flask to 70-76℃. Reflux the phosphorus trichloride and introduce the generated hydrogen chloride gas into a buffer flask. Stop the reaction after 7 hours. Distill the reaction solution under negative pressure at 90℃ to remove the unreacted phosphorus trichloride. After distillation, obtain the intermediate 4,4'-biphenyl bisphosphine chloride. S2. Install a mechanical stirrer, thermometer, nitrogen inlet, and constant pressure low-liquid funnel on a 1L three-necked flask, and heat in an oil bath; purge the air from the reaction flask with nitrogen. After purging, transfer 163.2g of 4,4'-biphenylbisphosphine chloride obtained from S1 to the reaction flask, and then weigh out 215g of... 2,4-Di-tert-butylphenol and 380g of triethylamine supported on γ-alumina modified by catalyst B obtained in Preparation Example 1 were dissolved in a beaker by stirring at room temperature. The external temperature of the oil bath was set to 130°C, and the mixture of 2,4-di-tert-butylphenol and triethylamine supported on γ-alumina modified by catalyst B was added dropwise to the reaction flask. The dropping rate was controlled to prevent the temperature inside the reaction flask from rising too quickly. After the addition was completed, the internal temperature was controlled at 106-110°C and the reaction was maintained for 4 hours. After the reaction was completed, 430mL of xylene solvent was added to the reaction solution, and the temperature was raised to 85°C and stirred to dissolve. After 50 minutes, the temperature was lowered to room temperature. The solution in the reaction flask was filtered by suction, and the solvent was removed by rotary evaporation of the filtrate under negative pressure at 120°C. The product after distillation was the target product P-EPQ.

[0038] Example 4 The difference between Example 4 and Example 1 is that in Example 4, the mass of biphenyl used in S1 is 44g, the mass of phosphorus trichloride is 137g, and the mass of aluminum trichloride is 94.6g.

[0039] Example 5 The difference between Example 5 and Example 1 is that in Example 5, the mass of biphenyl used in S1 is 44g, the mass of phosphorus trichloride is 156.5g, and the mass of aluminum trichloride is 114g.

[0040] Example 6 The difference between Example 6 and Example 1 is that in Example 6, the mass of biphenyl used in S1 is 44g, the mass of phosphorus trichloride is 120g, and the mass of aluminum trichloride is 88g.

[0041] Example 7 The difference between Example 7 and Example 1 is that in Example 7, the mass of biphenyl used in S1 is 44g, the mass of phosphorus trichloride is 170g, and the mass of aluminum trichloride is 120g.

[0042] Example 8 The difference between Example 8 and Example 1 is that in Example 8, the mass of 2,4-di-tert-butylphenol used in S2 is 215 g, the mass of 4,4'-biphenylbisphosphine chloride is 108.8 g, and the mass of catalyst B modified with γ-alumina and supported triethylamine obtained in Preparation Example 1 is 322.5 g.

[0043] Example 9 The difference between Example 9 and Example 1 is that in Example 9, the mass of 2,4-di-tert-butylphenol used in S2 is 215 g, the mass of 4,4'-biphenylbisphosphine chloride is 217.6 g, and the mass of catalyst B modified with γ-alumina and supported triethylamine obtained in Preparation Example 1 is 430 g.

[0044] Example 10 The difference between Example 10 and Example 1 is that in Example 10, the mass of 2,4-di-tert-butylphenol used in S2 is 215g, the mass of 4,4'-biphenylbisphosphine chloride is 63g, and the mass of catalyst B modified with γ-alumina supported triethylamine obtained in Preparation Example 1 is 270g.

[0045] Example 11 The difference between Example 11 and Example 1 is that in Example 11, the mass of 2,4-di-tert-butylphenol used in S2 is 215g, the mass of 4,4'-biphenylbisphosphine chloride is 272g, and the mass of catalyst B modified with γ-alumina supported triethylamine obtained in Preparation Example 1 is 480g.

[0046] Example 12 The difference between Example 12 and Example 1 is that the catalyst B used in S2 in Example 12 comes from Preparation Example 2 and has a mass of 380g.

[0047] Example 13 The difference between Example 13 and Example 1 is that the catalyst B used in S2 of Example 13 is from Preparation Example 3, with a mass of 380g.

[0048] Example 14 The difference between Example 14 and Example 1 is that the catalyst B used in S2 of Example 14 comes from Preparation Example 4 and has a mass of 380g.

[0049] Example 15 The difference between Example 15 and Example 1 is that the catalyst B used in S2 of Example 15 is from Preparation Example 5, with a mass of 380g.

[0050] Example 16 The difference between Example 16 and Example 1 is that the catalyst B used in S2 of Example 16 comes from Preparation Example 6 and has a mass of 380g.

[0051] Example 17 The difference between Example 17 and Example 1 is that the catalyst B used in S2 of Example 17 is from Preparation Example 7, with a mass of 380g.

[0052] Example 18 The difference between Example 18 and Example 1 is that the catalyst B used in S2 of Example 18 comes from Preparation Example 8 and has a mass of 380g.

[0053] Example 19 The difference between Example 19 and Example 1 is that the catalyst B used in S2 of Example 19 comes from Preparation Example 9 and has a mass of 380g.

[0054] Example 20 The difference between Example 20 and Example 1 is that the catalyst B used in S2 of Example 20 is from Preparation Example 10, with a mass of 380g.

[0055] Example 21 The difference between Example 21 and Example 1 is that the catalyst B used in S2 of Example 21 is from Preparation Example 11, with a mass of 380g.

[0056] Example 22 The difference between Example 22 and Example 1 is that the catalyst B used in S2 of Example 22 is from Preparation Example 12, with a mass of 380g.

[0057] Example 23 The difference between Example 23 and Example 1 is that the catalyst B used in S2 of Example 23 is from Preparation Example 13, with a mass of 380g.

[0058] Example 24 The difference between Example 24 and Example 1 is that the catalyst B used in S2 of Example 24 is from Preparation Example 14, with a mass of 380g.

[0059] Example 25 The difference between Example 25 and Example 1 is that the catalyst B used in S2 of Example 25 is from Preparation Example 15, with a mass of 380g.

[0060] Comparative Example Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the catalyst B used in S2 of Comparative Example 1 is unmodified triethylamine with a mass of 380g.

[0061] Performance testing 1. The product mass of antioxidant P-EPQ obtained in Examples 1-25 was measured and its yield was calculated. The results are shown in Table 1.

[0062] The specific test results are as follows: Table 1 Performance Test Results Detection object Product mass / g Product yield / % Detection object Product mass / g Product yield / % Example 1 250.2 93 Example 14 251.8 93.6 Example 2 248.3 92.3 Example 15 250.7 93.2 Example 3 247.2 91.9 Example 16 238.1 88.5 Example 4 243.4 90.5 Example 17 239.7 89.1 Example 5 245.9 91.4 Example 18 251.2 93.4 Example 6 226.8 84.3 Example 19 249.4 92.7 Example 7 230.8 85.8 Example 20 237.0 88.1 Example 8 245.6 91.3 Example 21 239.1 88.9 Example 9 247.7 92.1 Example 22 252.6 93.9 Example 10 228.4 84.9 Example 23 250.7 93.2 Example 11 231.1 85.9 Example 24 240.2 89.3 Example 12 250.4 93.1 Example 25 241.3 89.7 Example 13 249.1 92.6 Comparative Example 1 226 84 As can be seen from the test results of Examples 1-3, the preparation method of antioxidant P-EPQ provided in this application can effectively improve the yield of antioxidant P-EPQ, and the yield of antioxidant P-EPQ can reach up to 93.9%.

[0063] The test results of Examples 1, 4, 5, 6, and 7 show that when the molar ratio of biphenyl, phosphorus trichloride, and catalyst A aluminum trichloride is 1:(3.5-4.0):(2.5-3) when preparing antioxidant P-EPQ, a higher yield of antioxidant P-EPQ can be obtained. However, when the ratio of biphenyl, phosphorus trichloride, and catalyst A aluminum trichloride is outside this range, the yield of antioxidant P-EPQ decreases significantly.

[0064] The test results of Examples 1, 8, 9, 10, and 11 show that when the molar ratio of 2,4-di-tert-butylphenol to 4,4'-biphenylbisphosphine chloride obtained in S1 is 1:(0.2-0.4), and the weight ratio of 2,4-di-tert-butylphenol to triethylamine supported on γ-alumina modified by catalyst B is 1:(1.5-2), a high yield of antioxidant P-EPQ can be obtained.

[0065] The test results of Examples 1, 12, and 13 show that the modified γ-alumina-supported triethylamine and its preparation method provided in this application can effectively improve the yield of antioxidant P-EPQ when used in the preparation of antioxidant P-EPQ. The test results of Comparative Example 1 show that when unmodified ordinary triethylamine is used as catalyst B in this application, the yield of antioxidant P-EPQ is significantly lower.

[0066] The test results of Examples 1, 14, 15, 16, and 17 show that when the mass ratio of γ-alumina powder to ammonium bicarbonate used in the preparation of modified γ-alumina-supported triethylamine is 1:(1.6-1.9), the obtained modified γ-alumina-supported triethylamine can achieve a high yield of antioxidant P-EPQ. However, when the mass ratio of γ-alumina powder to ammonium bicarbonate is outside this range, the yield of antioxidant P-EPQ decreases significantly.

[0067] The test results from Examples 1, 18, 19, 20, and 21 show that when the mass ratio of rod-shaped γ-alumina precursor, methyltriethoxysilane, and HNO3 used in the preparation of modified γ-alumina supported triethylamine is 1:(0.1-0.5):(0.7-0.9), the obtained modified γ-alumina supported triethylamine can achieve a high yield of antioxidant P-EPQ. However, when the mass ratio of rod-shaped γ-alumina precursor, methyltriethoxysilane, and HNO3 is outside this range, the yield of antioxidant P-EPQ decreases significantly.

[0068] The test results of Examples 1, 22, 23, 24, and 25 show that when the weight ratio of γ-alumina support, triethylamine, and ethanol used in the preparation of modified γ-alumina supported triethylamine is 1:(1-2):(20-40), the modified γ-alumina supported triethylamine can obtain antioxidant P-EPQ with a high yield. However, when the mass ratio of γ-alumina support, triethylamine, and ethanol is outside this range, the yield of antioxidant P-EPQ decreases significantly.

[0069] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A method for preparing a phosphite antioxidant P-EPQ, characterized in that: Includes the following steps: S1. Nitrogen gas is introduced to replace the air in the reaction flask. After replacement, biphenyl and phosphorus trichloride are weighed and added to the reaction flask in sequence. After dissolving by stirring at room temperature, catalyst A is added, and the mixture is stirred and heated. The temperature inside the flask is controlled at 70-76℃. The phosphorus trichloride is refluxed and the generated hydrogen chloride gas is introduced into a buffer flask. The reaction is stopped after 6-8 hours. The unreacted phosphorus trichloride is distilled off under negative pressure at 70-90℃. After distillation, the intermediate 4,4'-biphenylbisphosphine chloride is obtained. The reaction formula is as follows: S2. Purge the air from the reaction flask with nitrogen. After purging, transfer the 4,4'-biphenylbisphosphine chloride obtained in S1 to the reaction flask. Weigh out 2,4-di-tert-butylphenol and catalyst B sequentially, and stir to dissolve at room temperature. Set the external temperature of the oil bath to 120-130℃ and begin adding the mixture of 2,4-di-tert-butylphenol and catalyst B dropwise into the reaction flask, controlling the dropping rate to prevent the temperature inside the reaction flask from rising too quickly. After the addition is complete, maintain the internal temperature at 106-110℃ and continue the reaction. After a certain reaction time, stop the reaction and begin post-processing. Add a certain amount of solvent to the reaction solution, heat to 75-85℃ and stir to dissolve. After 30-50 minutes, cool to room temperature. Filter the solution in the reaction flask, and then evaporate the solvent from the filtrate under negative pressure. The product after distillation is the target product P-EPQ. The reaction formula is as follows: The catalyst A is aluminum trichloride; Catalyst B is modified γ-alumina supported triethylamine.

2. The method for preparing the phosphite antioxidant P-EPQ according to claim 1, characterized in that: The molar ratio of biphenyl, phosphorus trichloride and catalyst A in S1 is 1:(3.5-4.0):(2.5-3).

3. The method for preparing the phosphite antioxidant P-EPQ according to claim 1, characterized in that: The molar ratio of 2,4-di-tert-butylphenol in S2 to 4,4'-biphenylbisphosphine chloride obtained in S1 is 1:(0.2-0.4).

4. The method for preparing the phosphite antioxidant P-EPQ according to claim 1, characterized in that: The weight ratio of 2,4-di-tert-butylphenol to catalyst B in S2 is 1:(1.5-2).

5. The method for preparing the phosphite antioxidant P-EPQ according to claim 1, characterized in that: The reaction time described in S2 is 2-4 hours.

6. The method for preparing the phosphite antioxidant P-EPQ according to claim 1, characterized in that: The solvent mentioned in S2 is one of toluene and xylene; the solid-liquid ratio of 2,4-di-tert-butylphenol to the solvent is 1:(1.5-2)g / mL.

7. The method for preparing the phosphite antioxidant P-EPQ according to claim 1, characterized in that: The preparation method of the modified γ-alumina supported triethylamine catalyst includes the following steps: T1. Weigh γ-alumina powder and ammonium bicarbonate and place them in a reaction vessel. Add deionized water and stir for 20-30 minutes. After sealing, place the reaction vessel in an oven for hydrothermal treatment. After filtration, washing and drying, the treated material is calcined at 600-700℃ for 4-6 hours to obtain rod-shaped γ-alumina precursor. T2. Weigh the rod-shaped γ-alumina precursor prepared in T1, add an appropriate amount of methyltriethoxysilane and mix evenly, add 65% HNO3 solution and knead evenly, extrude the material into strips on an extruder, and dry the strip material at 120-130℃ for 8-10h; calcine the dried sample at 600-700℃ for 4-6h to obtain the γ-alumina support. T3. Place the γ-alumina support in the solvent ethanol, add triethylamine, stir and mix for 6-10 h, and then dry at 90-110 °C to obtain the modified γ-alumina supported triethylamine catalyst.

8. The method for preparing the phosphite antioxidant P-EPQ according to claim 7, characterized in that: The weight ratio of γ-alumina powder to ammonium bicarbonate in T1 is 1:(1.6-1.9).

9. The method for preparing the phosphite antioxidant P-EPQ according to claim 7, characterized in that: The weight ratio of the rod-shaped γ-alumina precursor, methyltriethoxysilane, and HNO3 in T2 is 1:(0.1-0.5):(0.7-0.9).

10. The method for preparing the phosphite antioxidant P-EPQ according to claim 7, characterized in that: The weight ratio of the γ-alumina carrier, triethylamine, and ethanol in T3 is 1:(1-2):(20-40).

Images