WO2024119744A1 - 亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法 - Google Patents

亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法 Download PDF

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WO2024119744A1
WO2024119744A1 PCT/CN2023/098548 CN2023098548W WO2024119744A1 WO 2024119744 A1 WO2024119744 A1 WO 2024119744A1 CN 2023098548 W CN2023098548 W CN 2023098548W WO 2024119744 A1 WO2024119744 A1 WO 2024119744A1
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reaction
butyl
pentaerythritol
methylphenyl
tert
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倪阳
李旭锋
关俊涛
鱼海龙
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浙江万盛股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
    • C09K15/322—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus

Definitions

  • the invention relates to a method for synthesizing bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, a high-efficiency phosphite antioxidant.
  • antioxidants are a class of chemical substances that can delay or inhibit the oxidation process of polymers when they are present in small amounts in polymer systems. They can delay the deterioration of materials, products and supplies during storage and use, and are therefore also called "anti-aging agents". Generally, they are used in small amounts and are mostly substances with reducing properties. The general requirements for antioxidants are small amounts, high efficiency, low prices, and no adverse consequences.
  • Phosphite antioxidants can decompose polymer peroxide compounds to prevent their cracking and induce thermal oxidation degradation of polymers. They are also called “peroxide decomposers” and are usually used in combination with primary antioxidants to have a good synergistic effect. They can significantly improve the high-temperature processing stability of polymers, inhibit the color and melt index changes during polymer processing, and improve the color and melt index stability of plastic products. Currently, the most widely used general-purpose phosphite antioxidant in the domestic and foreign markets is antioxidant 168.
  • Antioxidant 626, Antioxidant 9228 and Antioxidant Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite are representative high-performance phosphite antioxidants containing spiro rings. Compared with the above general phosphite antioxidants, they have a unique spiro ring structure and higher antioxidant activity. They can be widely used in the mid-to-high-end formulations of general-purpose plastics and engineering plastics with harsh processing conditions.
  • the structural formulas of Antioxidants 626, 9228 and PEP-36 are as follows:
  • Pentaerythritol phosphite antioxidant bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, chemical name bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
  • Bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is a high-efficiency phosphite antioxidant variety developed by Asahi Denka Co., Ltd. in Japan from the late 1980s to the early 1990s. Molecular formula: C35H54O6P2, molecular weight 632.75, melting point 235-240°C, flash point 380.5°C, trade name PEP-36.
  • the product is antioxidant
  • the agent is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
  • Patents US 5137950 and US 5308901 also report this type of method and propose a method in which a trialkylamine in an amount equal to the molar amount of HCl generated by the reaction is added to promote the substitution reaction between the intermediate and BHT.
  • Pentaerythritol dichlorophosphate synthetic route can be directly synthesized by pentaerythritol dichlorophosphate, and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and synthesis technique is simple. Reaction raw materials pentaerythritol dichlorophosphate is the intermediate when synthesizing many phosphorus-containing dispiro compounds, and synthesis technology is more mature. The biggest shortcoming of this route is that the purification and storage of pentaerythritol dichlorophosphate are very inconvenient.
  • Pentaerythritol dichlorophosphate is generally synthesized by phosphorus trichloride and pentaerythritol, and because the reactive site is many, product is more assorted, and pentaerythritol dichlorophosphate is very easy to hydrolyze and deteriorate, and purification difficulty is large.
  • the phosphite synthesis route is to use phosphite (triethyl phosphite, triphenyl phosphite, etc.), pentaerythritol, and 2,6-di-tert-butyl-4-methylphenol as raw materials to synthesize the antioxidant bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
  • phosphite triethyl phosphite, triphenyl phosphite, etc.
  • pentaerythritol and 2,6-di-tert-butyl-4-methylphenol
  • 2,6-di-tert-butyl-4-methylphenol 2,6-di-tert-butyl-4-methylphenol
  • the phosphite synthesis route uses a short time to synthesize bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, mild conditions, and the product does not contain acid, and the equipment requirements are low.
  • the reactant triethyl phosphite is more than 5 times higher than phosphorus trichloride as an industrial raw material, and the amount used is large, and the production cost is high. It can be used for laboratory synthesis, but it is difficult to use in industrial production.
  • Phosphorus trichloride synthesis route is actually a "one-pot" synthesis route.
  • the characteristic of the one-pot reaction is that the intermediate product is not separated.
  • the process of each step of the one-pot method is relatively simple and the number of reaction steps cannot be too many. It is generally suitable for the synthesis reaction of simple and cheap raw materials to synthesize complex molecules in a few steps, especially for reactions where some intermediates are unstable or difficult to separate. Since the reaction omits the loss and consumption of the intermediate product separation process, the yield is generally ideal.
  • This route is formally based on such considerations.
  • Phosphorus trichloride, pentaerythritol and 2,6-tert-butyl-4-methylphenol are used as raw materials, and the two-step reaction is purified once.
  • the reaction equation is as follows:
  • He Hailong et al. disclosed a method for synthesizing an antioxidant bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite in patent CN1948319A.
  • Pentaerythritol, phosphorus trichloride and BHT are used as raw materials.
  • the antioxidant bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite was synthesized in a proton solvent (toluene, xylene, etc.), and the catalyst was an ion exchange resin (among which D301 and D370 weak base resins have the best effect). The reaction adopts an uninterrupted two-step reaction.
  • the first step is to synthesize pentaerythritol dichlorodiphosphite, and the reaction is carried out at 50-100°C for 2 to 10 hours.
  • the second step is the synthesis of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
  • the amount of BHT added is 2 to 4 times the molar number of pentaerythritol, and the reaction is carried out at 80-120°C for 8 to 24 hours, and the yield is between 43.8% and 67.5%.
  • He Liming et al. disclosed a method for synthesizing an antioxidant bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite in patent CN102206234A.
  • the antioxidant bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite was synthesized using pentaerythritol, phosphorus trichloride and BHT as raw materials and liquid amine substances (triethylamine, piperidine, etc.) as catalysts.
  • the material molar ratio of pentaerythritol: PCl: BHT is 1:2-2.2:2-5.
  • the first step of the reaction is carried out at 50-120° C. for 2-10 hours.
  • the second step of the reaction is carried out at 80-130° C. for 8-24 hours.
  • the post-reaction treatment is first washed with isopropanol (the mass ratio of isopropanol to product is 4-15:1), then washed with n-hexane (the mass ratio of n-hexane to product is 2-5:1), and finally dried at 80-130° C.
  • the yield is between 51.4% and 70.5%.
  • the phosphorus trichloride synthesis route is a two-step reaction, the intermediate product is not separated and purified (the intermediate product pentaerythritol dichlorodiphosphite is unstable and difficult to purify), and the synthesis is carried out directly.
  • the solvent can be evaporated, and a relatively pure product can be synthesized by washing with solvents such as methanol or isopropanol.
  • this method will produce a large amount of hydrochloric acid and has high requirements for equipment, the synthesis process is simple, and the raw materials are all relatively cheap reagents commonly used in industry. The cost is low and it can be applied to large-scale industrial production.
  • Zhang Xiuxiu et al. disclosed an industrial production method of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite in patent CN109503663 A.
  • 2,6-di-tert-butyl-4-methylphenol, sodium methoxide and organic solvent are used in a primary reactor to prepare 2,6-di-tert-butyl-4-methylphenol sodium salt, and pentaerythritol dichlorophosphite solution is prepared in a secondary reactor with pentaerythritol, phosphorus trichloride and organic solvent.
  • the 2,6-di-tert-butyl-4-methylphenol sodium salt prepared in the primary reactor is then added to the secondary reactor to prepare a bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite reaction solution, and then the bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite product is obtained through centrifugal impurity removal, freeze crystallization separation, centrifugal desolventization and drying.
  • the molar ratio of 2,6-di-tert-butyl-4-methylphenol to sodium methoxide is 1:1.1-1.4, the reaction temperature is 60-80°C, the pressure is 200-500kPa, and the reaction time is 1-2h.
  • the molar ratio of pentaerythritol to phosphorus trichloride is 1:1-1.5, the reaction temperature is 0-10°C, the pressure is -10--0.5kPa, and after the dropwise addition is completed, the heat preservation reaction time is 0.5-3h.
  • the reaction temperature is 60-80°C, the reaction pressure is 200-500kPa, and the reaction time is 1.0-1.5h.
  • the purity of the bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite product is above 98.5%, and the yield is 90-92%.
  • the object of the present invention is to provide a method for synthesizing a highly efficient phosphite antioxidant bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite with a high yield and with fewer steps and using safe raw materials as much as possible, which is conducive to the industrial production of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
  • the present invention provides a simple and efficient synthesis method, using pentaerythritol, phosphorus trichloride, and BHT as raw materials, using tripropylamine as a catalyst in the first step of the reaction and using xylene as a reaction solvent, and using a mixture of tripropylamine and tributylamine mixed in a certain proportion as an acid-binding agent in the second step of the reaction and using xylene as a reaction solvent, and synthesizing a mixture of a high-efficiency and high-yield new phosphite compound having a spirocyclic structure by a "one-pot method".
  • the reaction equation is as follows:
  • the synthesis method of the highly efficient phosphite antioxidant bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite specifically comprises the following steps:
  • step 2) After the reaction of step 1) is completed, BHT raw material is directly added to the system, and tripropylene glycol as an acid binding agent is added dropwise.
  • the amine-tributylamine mixture is subjected to the second step reaction, and the reaction is detected to be complete by HPLC sampling and analysis.
  • the reaction liquid is post-treated to obtain the target product.
  • step 1) the mass ratio of pentaerythritol to tripropylamine catalyst is 30-80:1, preferably 40-50:1; the mass ratio of pentaerythritol to phosphorus trichloride is 1:1.2-3, preferably 1:1.5-2.
  • step 1) when phosphorus trichloride is added dropwise under normal pressure, the temperature of the mixed solution in the reactor is 65-75° C., and after the addition is completed, the reaction temperature is maintained at 75-85° C.; the first step reaction time of step 1) is 1.5-2.5 hours.
  • the reaction solvent is xylene, which may contain ortho, meta and para isomers in any proportion.
  • the mass ratio of pentaerythritol to the reaction solvent is 1:8-30, preferably 1:12-18.
  • the mass ratio of the BHT raw material in step 2) to the pentaerythritol in step 1) is 2 to 6:1, preferably 4 to 5:1.
  • the mass ratio of the acid-binding agent tripropylamine-tributylamine mixture in step 2) to the pentaerythritol in step 1) is 1.5 to 5:1, preferably 2 to 3:1.
  • the amount of tributylamine is 10 to 100 parts by mass, preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and further preferably 40 to 60 parts by mass, based on 100 parts by mass of tripropylamine. If the amount of tributylamine is less than 10 parts by mass or more than 100 parts by mass, the reaction efficiency is low and the yield is poor.
  • step 2 when the acid binding agent is added dropwise in step 2), the temperature of the mixed solution in the reactor is 75-85° C., and after the addition is completed, the reaction temperature is controlled above 145° C. to reach a reflux state; the second step reaction time of step 2) is 2.5-5 hours.
  • the post-treatment process of the reaction solution in step 2) is: cooling to 125-135° C. for filtration, adding diatomaceous earth to the filtrate and stirring for 5-20 minutes at a temperature keeping warm, filtering again, and then performing reduced pressure distillation to completely remove the solvent, that is, the treatment is completed.
  • the present invention has the following beneficial effects: the present invention is effective in treating bis(2,6-di-tert-butyl-4-methyl
  • the synthesis of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite was studied in depth, and as a result, a new process for synthesizing bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite by first alcohol and then phenol (containing an acid-binding agent) was found.
  • the second step reaction (the reaction of pentaerythritol dichlorodiphosphite and 2,6-di-tert-butyl-4-methylphenol) can be regulated to be carried out efficiently, thereby greatly improving the yield and shortening the reaction time at the same time, and improving the purity of the product, which is conducive to the industrial production of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
  • FIG1 is a P31 (CDCl3) spectrum of the target obtained in Example 1;
  • FIG2 is a C13 (CDCl3) spectrum of the target obtained in Example 1;
  • FIG3 is an infrared spectrum of the target obtained in Example 1.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • a stirrer, a nitrogen inlet pipe, a thermometer, a distillation tube and a stopcock (for sampling) are installed on a five-mouth 1000ml flask, and a water quantitative receiver and a cooling tube are installed at the front end of the distillation tube.
  • the above device is used as a reaction device.
  • Pentaerythritol (13.6g) as a raw material, xylene (200.0g) as a solvent, and tripropylamine (0.3g) as a catalyst are added to the above flask.
  • Phosphorus trichloride (27.4g) as a raw material is added dropwise at normal pressure and a temperature of 70°C.
  • the system maintains a reaction temperature of 80°C, while removing the generated hydrogen chloride from the system, while carrying out the first step reaction.
  • the first step reaction is terminated when the raw material is less than 1% by HPLC analysis, and the first step reaction time is 2.0 hours.
  • the second step reaction is terminated when the raw material is less than 1% by HPLC analysis, and the second step reaction time is 4.0 hours.
  • the temperature is lowered to 130°C for filtration, diatomaceous earth (5.0g) is added to the filtrate and stirred at 130°C for 10 minutes, filtered again, and then vacuum distilled to completely remove the solvent, thereby manufacturing the target product bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, with a yield of 93%, and the purity detection is according to the liquid chromatography method introduced in Yang Teng's master's thesis [Study on the Synthesis Process of Antioxidant PEP-36 and Dodecylphenol] at Tianjin University of Science and Technology, which is 99.3%.
  • Example 1 The identification of the target bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite obtained in Example 1 was performed using nuclear magnetic resonance and infrared, and the identification results were as follows: the P31 (CDCl3) spectrum of the product is shown in Figure 1, and the chemical shifts of the phosphite compound are 122.58ppm and 122.51ppm, showing a double peak.
  • the C13 (CDCl3) spectrum is shown in Figure 2, and the chemical shifts of the mixture of the phosphite compound as the main component are 21.17ppm, 31.83ppm, 31.86ppm, 35.31ppm, 36.24ppm, 36.28ppm, 36.32ppm, 63.75ppm, 63.78ppm, 63.94ppm, 127.20ppm, 132.26ppm, 143.08ppm, 143.11ppm, 148.85ppm, and 148.96ppm.
  • the infrared spectrum is shown in FIG3 , wherein 671 cm -1 , 688 cm -1 , 711 cm -1 , 736 cm -1 , 767 cm -1 , 783 cm -1 , and 833 cm -1 are bending vibration peaks of benzene ring, and 2918 cm -1 and 2956 cm -1 are CH stretching vibration peaks.
  • Example 2-6 and Comparative Examples 1-3 repeat Example 1, except that "the mass ratio of tripropylamine/tributylamine is adjusted, wherein the total mass of tripropylamine/tributylamine remains unchanged", and the second step reaction time data recorded when the raw material is less than 1% by HPLC analysis in the second step reaction of Examples 2-6 and Comparative Examples 1-3 are summarized in Table 1. The correspondingly changed reaction conditions and the final experimental results are listed in Table 1.
  • the total reaction time is the reaction time of the first step plus the reaction time of the first step. It can be seen that the ratio of tripropylamine/tributylamine has a significant effect on the product yield and purity.
  • Example 2 The operation steps of Comparative Examples 4-6 are repeated in Example 1, except that the temperature of the second step reaction is adjusted as shown in Table 2. The correspondingly changed reaction conditions and the final experimental results are listed in Table 2. It can be seen that the change in reaction temperature has a significant effect on the yield and purity.
  • the experimental data show that the new process of the invention greatly improves the yield of the synthesis reaction and the purity of the obtained product and shortens the reaction time.

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Abstract

本发明公开了亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，它使用季戊四醇、三氯化磷、BHT作为原料，使用三丙胺作为催化剂在反应溶剂中完成第一步反应，反应后料液直接进入下一步，向体系中加入BHT作为原料，并滴加作为缚酸剂的三丙胺-三丁胺混合物，进行第二步反应，反应后料液经后处理得到具有螺环结构的高效亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯。本发明的方法通过改变缚酸剂以及溶剂的种类，可以调控第二步骤反应高效率进行，从而能够同时大幅度提升产率以及缩短反应时间，并提高了产品的纯度，有利于实现双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的工业化生产。

Description

亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法 技术领域
本发明涉及高效亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法。
背景技术
能延缓或阻止氧化或自动氧化过程的物质称为抗氧剂，它是一类化学物质，当其在聚合物体系中仅少量存在时，就可延缓或抑制聚合物氧化过程的进行，能延缓物料、制品和用品在储藏和使用时的变质从而又被称为“防老剂”。一般用量较小，大都是具有还原性能的物质。对抗氧剂的一般要求是用量小，效率高，价格便宜，且无不良后果。
亚磷酸酯类抗氧剂具有分解聚合物过氧化合物，防止其裂解诱发聚合物热氧降解，又称“过氧化物分解剂”，通常和主抗氧剂配合使用，具有很好的协同作用。从而可以显著提高聚合物的高温加工稳定性，抑制聚合物加工时的色泽和熔融指数变化，改善塑料制品的色泽以及熔融指数稳定性。目前在国内外市场上，使用量比较大的通用型亚磷酸酯抗氧剂的代表品种为抗氧剂168。
抗氧剂626，抗氧剂9228以及抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯(PEP-36)为代表性的含有螺环的高性能亚磷酸酯抗氧剂，与以上的通用亚磷酸酯抗氧剂相比，因其具有螺环独特结构，抗氧活性更高，可以广泛应用于加工条件较为苛刻的通用塑料和工程塑料的中高端配方。抗氧剂626、9228以及PEP-36的结构式如下：
具有螺环独特结构的三种典型高效亚磷酸酯抗氧剂
季戊四醇亚磷酸酯抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯，化学名双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯。双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯是日本旭电化公司20世纪80年代末至90年代初开发的高效亚磷酸酯抗氧剂品种，分子式：C35H54O6P2，分子量632.75，熔点235-240℃，闪点380.5℃，商品名为PEP-36。
文献或专利中抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成有三种工艺路线：(1)二氯二亚磷酸季戊四醇酯合成路线；(2)亚磷酸酯酯交换法合成路线；(3)三氯化磷合成路线。
(1)二氯二亚磷酸季戊四醇酯合成路线:二氯二亚磷酸季戊四醇酯合成路线是早期合成的路线。由二氯二亚磷酸季戊四醇酯在催化剂作用下与2，6-二叔丁基-4-甲基苯酚反应生成，反应方程式如下所示：
二氯二亚磷酸季戊四醇酯的酯化反应合成路线
Hobbs等在专利EP0356688A中公开了双螺环亚磷酸酯类化合物的合成方法，以季戊四醇、三氯化磷和受阻酚为原料，催化剂选用液体叔胺。先用季戊四醇与三氯化磷合成二氯二亚磷酸季戊四醇酯中间体，中间体分离提纯后与受阻酚类化合物反应合成了一系列双螺环亚磷酸酯类化合物。若受阻酚为2，6-二叔丁基-4-甲基苯酚，则产物为抗氧 剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯。
专利US 5137950与US 5308901也报道了这一类方法，并提出中间体与BHT取代反应时，添加与反应生成HCl等摩尔量的三烷基胺来促进的方法。
二氯二亚磷酸季戊四醇酯合成路线可由二氯二亚磷酸季戊四醇酯直接合成双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯，合成工艺简单。反应原料二氯二亚磷酸季戊四醇酯是合成许多含磷双螺环化合物时的中间体，合成技术比较成熟。该路线最大的缺点是二氯二亚磷酸季戊四醇酯的提纯与贮存十分不方便。二氯二亚磷酸季戊四醇酯一般由三氯化磷与季戊四醇合成，由于反应活性位点多，产物比较杂，且二氯二亚磷酸季戊四醇酯极易水解变质，提纯难度大。
(2)亚磷酸酯酯交换法合成路线:亚磷酸酯合成路线是由亚磷酸酯(亚磷酸三乙酯、亚磷酸三苯酯等)、季戊四醇、2，6-二叔丁基-4-甲基苯酚作为原料合成抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯。以亚磷酸三乙酯为例，反应方程式如下所示。
亚磷酸酯酯交换法合成路线
张丽芳等以季戊四醇、P(OCH2CH3)3和2，6-二叔丁基-4-甲基苯酚为原料合成了抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯。通过考察物料配比、反应温度、反应时间等条件对产率的影响，最佳工艺条件为n(季戊四醇):n(亚磷酸三乙酯):n(BHT)＝1.0:2.12:2.04，催化剂选用无水K2CO3，反应先在130-140℃下反应2h，再调节反应温度至170-180℃反应4h，产率在87％左右。
Larke等在专利US 7342060中报道了以季戊四醇、P(OPh)3、受阻酚为原料，合成一系列亚磷酸酯类化合物。先将季戊四醇与P(OPh)3反应生成中间体二苯基季戊四醇二亚磷酸酯，反应产生的副产物苯酚通过减压蒸馏方式除去，中间体与受阻酚反应生成亚磷酸酯类抗氧剂。若受阻酚为BHT，则产物为抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯。
亚磷酸酯合成路线合成双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯所用时间短，条件温和，产物不含酸，对设备要求低。但是反应物亚磷酸三乙酯作为工业原料比三氯化磷高5倍以上，且使用量较大，生产成本较高。可以作为实验室合成使用，但是用于工业生产难度较大。
三氯化磷合成路线：三氯化磷合成路线实际上是一种“一锅法”合成路线。一锅法反应的特点是中间产物不分离。一锅法每步的过程比较简单且反应步数不能太多，一般适用于简单便宜的原料几步合成结构复杂的分子的合成反应，尤其对某些中间体不稳定或分离困难的反应尤其适用。由于反应略去了中间产物分离过程的损失与消耗，产率一般较为理想。该路线正式基于这样的考虑，以三氯化磷、季戊四醇与2，6-叔丁基-4-甲基苯酚为原料，两步反应一次提纯，反应方程式如下：
三氯化磷合成路线
何海龙等在专利CN1948319A中公开了一种抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法。以季戊四醇、三氯化磷和BHT为原料，在非极性非 质子溶剂(甲苯、二甲苯等)溶剂中合成了抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯，催化剂采用离子交换树脂(其中D301、D370型号弱碱型树脂效果最好)。反应采取不间断的两步反应，第一步反应合成二氯二亚磷酸季戊四醇酯，在50-100℃下反应2～10h。第二步反应为双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成，BHT加入量为季戊四醇摩尔数的2～4倍，在80-120℃下反应8～24h，产率在43.8％～67.5％之间。
贺黎明等在专利CN102206234A中公开了一种抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法。以季戊四醇、三氯化磷和BHT为原料，以液体胺类物质(三乙胺、哌啶等)为催化剂，合成了抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯。采用物料摩尔比例季戊四醇:PCl:BHT＝1:2～2.2:2～5，第一步反应50～120℃下反应2～10h，第二步反应在80～130℃下反应8～24h，反应后处理先用异丙醇洗涤(异丙醇与产物质量比4～15:1)，再用正己烷洗涤(正己烷与产物质量比2～5:1)，最后在80～130℃下烘干，收率在51.4％～70.5％之间。
Donald等在专利US8278490中公开了一种亚磷酸酯类抗氧剂的“一锅法”合成路线。先将季戊四醇、受阻酚与催化剂季铵盐类化合物加入到体系中，滴加三氯化磷进行反应。先在79～81℃反应2h，然后升温至140～142℃反应12h。副产物HCl由碱塔吸收。若受阻酚选用BHT，则反应得到产物为抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯。
三氯化磷合成路线虽然是两步反应，但是中间产物不进行分离提纯(中间产物二氯二亚磷酸季戊四醇酯不稳定，提纯难度也较大)，直接进行合成，合成后可以蒸出溶剂，用甲醇或异丙醇等溶剂洗涤等手段可以合成较为纯净的产品。该方法虽然反应会产生大量的盐酸对设备要求较高，但合成工艺简单，且原料都是工业上常用的较为便宜的试剂， 成本低，可以适用于大规模的工业生产。
杨腾在天津科技大学的硕士学位论文【抗氧剂PEP-36与十二烷基酚合成工艺研究】中公开了一种先醇后酚(含缚酸剂)工艺，特点是使用甲苯作为溶剂，以及第二步酯化反应使用过量三乙胺作为缚酸剂，反应温度为125℃，时间为12小时，最高收率为70.9％，纯度为98％以上。
张秀秀等在专利CN109503663 A公开了一种双(2，6-二叔丁基-4-甲基苯基)季戊四醇亚磷酸酯的工业化生产方法。2，6-二叔丁基-4-甲基苯酚、甲醇钠和有机溶剂一级反应釜中制得2，6-二叔丁基-4-甲基酚钠盐，季戊四醇、三氯化磷和有机溶剂在二级反应釜中制得二氯二亚磷酸季戊四醇酯溶液，再将一级反应釜中制得的2，6-二叔丁基-4-甲基酚钠盐加入到二级反应釜中制得双(2，6-二叔丁基-4-甲基苯基)季戊四醇亚磷酸酯反应液，再经过离心除杂、冷冻结晶分离、离心脱溶、干燥得到双(2，6-二叔丁基-4-甲基苯基)季戊四醇亚磷酸酯产品。第一步反应2,6-二叔丁基-4-甲基苯酚和甲醇钠的摩尔比为1:1.1～1.4，反应温度为60～80℃，压强为200～500kPa，反应时间为l～2h。第二步反应季戊四醇与三氯化磷的摩尔比为1:1～1.5，反应温度为0～10℃，压强为-10～-0.5kPa，滴加完毕后，保温反应时间为0.5～3h。第三步反应温度为60～80℃，反应压强为200～500kPa，反应时间为1.0～1.5h。双(2，6-二叔丁基-4-甲基苯基)季戊四醇亚磷酸酯产品纯度为98.5％以上，收率为90～92％。
综上所述，对于现存的双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的各种合成工艺，步骤少的产率都偏低以及反应时间过长，而步骤多的，则使用了甲醇钠等危险有机金属化合物(具有腐蚀性、可自燃性)作为原料，使工艺复杂化，不利于工业化生产。
发明内容
针对现有技术存在的上述技术问题，本发明的目的在于提供步骤少且尽量使用安全原料的高收率的合成高效亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的方法，有利于实现双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的工业化生产。
本发明提供一种简便高效的合成方法，使用季戊四醇、三氯化磷、BHT作为原料，反应的第一步骤使用三丙胺作为催化剂搭配二甲苯作为反应溶剂，而且反应的第二步骤使用三丙胺和三丁胺按照一定比例混合而成的混合物作为缚酸剂并搭配使用二甲苯作为反应溶剂，高效率高收率的“一锅法”合成具有螺环结构的高效新型亚磷酸酯化合物的混合物。反应方程式如下：
本发明的高效率高收率的“一锅法”合成方法
本发明采用的具体技术方案如下：
所述的高效亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，具体包括以下步骤：
1)在反应器中加入季戊四醇、反应溶剂和三丙胺催化剂，在常压下滴加三氯化磷，进行升温反应，且反应过程中通入氮气将生成的氯化氢除去到体系外，通过HPLC取样分析检测反应进程；
2)步骤1)反应结束后，直接向体系中加入BHT原料，并滴加作为缚酸剂的三丙 胺-三丁胺混合物，进行第二步反应，通过HPLC取样分析检测反应至结束，反应后料液经后处理得到目标产物。
进一步地，步骤1)中，所述季戊四醇与三丙胺催化剂的质量比为30～80:1，优选为40～50:1；所述季戊四醇与三氯化磷的质量比为1:1.2～3，优选为1:1.5～2。
进一步地，步骤1)中，在常压下滴加三氯化磷时反应器中混合液的温度为65～75℃，滴加完毕后保持反应温度75～85℃；步骤1)的第一步反应时间为1.5～2.5小时。
进一步地，步骤1)中所述反应溶剂为二甲苯，可以包含任意的比例邻、间、对三种异构体。季戊四醇与反应溶剂的质量比为1:8～30，优选为1:12～18。
进一步地，步骤2)中的BHT原料与步骤1)中的季戊四醇质量之比为2～6:1，优选为4～5：1。
进一步地，步骤2)中的缚酸剂三丙胺-三丁胺混合物与步骤1)中的季戊四醇质量之比为1.5～5:1，优选为2～3:1。
进一步地，步骤2)中的缚酸剂三丙胺-三丁胺混合物中，以三丙胺用量为100质量份计，三丁胺的用量为10～100质量份，优选为20～80质量份、更优选为30～70质量份，更进一步优选为40～60质量份。三丁胺的配合量如果低于10质量份或高于100质量份，则反应效率低收率差。
进一步地，步骤2)中滴加缚酸剂时反应器中混合液的温度为75～85℃，滴加完毕后反应温度控制在145℃以上，达到回流状态；步骤2)的第二步反应时间为2.5～5小时。
进一步地，步骤2)中反应液的后处理过程为：降温至125～135℃进行过滤，在滤液中加入硅藻土并保温搅拌5～20分钟，再次进行过滤，然后进行减压蒸馏以便于完全脱除溶剂，即处理完成。
相较于现有技术，本发明取得的有益效果是：本发明对双(2，6-二叔丁基-4-甲基 苯基)季戊四醇二亚磷酸酯的合成进行了深入研究，结果发现了用于合成双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的新的先醇后酚(含缚酸剂)工艺，通过改变缚酸剂以及溶剂的种类，可以调控第二步骤反应(二氯二亚磷酸季戊四醇酯和2，6-二叔丁基-4-甲基苯酚的反应)高效率进行，从而能够同时大幅度提升产率以及缩短反应时间，并且提高了产品的纯度，有利于实现双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的工业化生产。
附图说明
图1为实施例1所得目标物的P31(CDCl3)谱图；
图2为实施例1所得目标物的C13(CDCl3)谱图；
图3为实施例1所得目标物的红外谱图。
具体实施方式
下面结合具体实施例对本发明作进一步说明，但本发明的保护范围并不限于此。
实施例1：
在五口的1000ml烧瓶上安装搅拌机、氮气导入管、温度计、精馏管和旋塞(取样用)，再在精馏管的前端安装水分定量接收器、冷却管，使用上述装置作为反应装置。在上述烧瓶中加入作为原料的季戊四醇(13.6g)，作为溶剂的二甲苯(200.0g)、作为催化剂的三丙胺(0.3g)，在常压以及温度70℃下，滴加作为原料的三氯化磷(27.4g)。滴加完毕后，体系保持反应温度80℃，一边将生成氯化氢除去到体系外，一边进行第一步骤反应。用HPLC分析出原料低于1％的时候结束第一步骤反应，第一步骤反应时长为2.0小时。使用PTFE软管在液面以下通入氮气并进行搅拌操作以便于脱除残余的氯化氢气体。之后，向体系中加入BHT(57.3g)，并在常压以及温度80℃下，滴加作为缚酸剂的三丙胺和三丁胺的混合物(质量比三丙胺/三丁胺＝100/50，总计33.0g)。添加完毕 后，体系逐步升温至回流(>＝145℃)，进行第二步骤反应。用HPLC分析出原料低于1％的时候结束第二步骤反应，第二步骤反应时长为4.0小时。之后，降温至130℃进行过滤，在滤液中加入硅藻土(5.0g)在130℃搅拌10分钟，再次进行过滤，然后进行减压蒸馏以便于完全脱除溶剂，从而制造作为目标物的双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯，收率为93％，纯度检测是按照杨腾在天津科技大学的硕士学位论文【抗氧剂PEP-36与十二烷基酚合成工艺研究】中介绍的液相色谱法，为99.3％。
实施例1所得目标物双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的鉴定使用核磁和红外进行，鉴定结果为：产物的P31(CDCl3)谱图为图1，亚磷酸酯化合物的化学位移为122.58ppm、122.51ppm，呈现双重峰。C13(CDCl3)谱图为图2，作为主要成分亚磷酸酯化合物的混合物的化学位移为21.17ppm、31.83ppm、31.86ppm、35.31ppm、36.24ppm、36.28ppm、36.32ppm、63.75ppm、63.78ppm、63.94ppm、127.20ppm、132.26ppm、143.08ppm、143.11ppm、148.85ppm、148.96ppm。红外谱图为图3所示，其中671cm-1、688cm-1、711cm-1、736cm-1、767cm-1、783cm-1、833cm-1为苯环的弯曲振动峰，2918cm-1、2956cm-1为C-H伸缩振动峰。
实施例2-6、比较例1-3：
实施例2-6以及比较例1-3的操作步骤重复实施例1，不同之处仅在于“调整改变三丙胺/三丁胺的质量比例，其中三丙胺/三丁胺的投料总质量维持不变”，另外实施例2-6以及比较例1-3第二步骤反应中用HPLC分析出原料低于1％的时候记录的第二步骤反应时长数据，一并汇总于表1中。相应改变的反应条件以及最终得到的实验结果列于表1中。
如表1所示，其中反应总时长是第一步骤反应时长加第一步骤反应时长。可见三丙胺/三丁胺的比例对产品收率和纯度有明显影响。
表1.叔胺缚酸剂成分比例对合成得到的产品收率和纯度的影响
比较例4-6：
比较例4-6的操作步骤重复实施例1，不同之处仅在于“调整第二步骤反应的温度，如表2所示”，相应改变的反应条件以及最终得到的实验结果列于表2中。可见反应温度的改变对产率和纯度有明显影响。
表2.叔胺缚酸剂成分比例对合成得到的产品收率和纯度的影响

*用HPLC分析发现原料高于始终1％，20个小时结束了反应。
综上实验数据所述，发明的新工艺大幅度提高了合成反应的收率和所得产品的纯度以及缩短了反应时间。
本说明书所述的内容仅仅是对发明构思实现形式的列举，本发明的保护范围不应当被视为仅限于实施例所陈述的具体形式。

Claims (10)

  1. 亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，其特征在于其方法过程为：使用季戊四醇、三氯化磷、BHT作为原料，使用三丙胺作为催化剂在反应溶剂中完成第一步反应，反应后料液直接进入下一步，向体系中加入BHT作为原料，并滴加作为缚酸剂的三丙胺-三丁胺混合物，进行第二步反应，反应后料液经后处理得到具有螺环结构的高效亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯；反应式如下：
  2. 如权利要求1所述的亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，其特征在于具体包括以下步骤：
    1)在反应器中加入季戊四醇、反应溶剂和三丙胺催化剂，在常压下滴加三氯化磷，进行升温反应，且反应过程中通入氮气将生成的氯化氢除去到体系外，通过HPLC取样分析检测反应进程；
    2)步骤1)反应结束后，直接向体系中加入BHT原料，并滴加作为缚酸剂的三丙胺-三丁胺混合物，进行第二步反应，通过HPLC取样分析检测反应至结束，反应后料液经后处理得到目标产物。
  3. 如权利要求2所述的亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，其特征在于步骤1)中，所述季戊四醇与三丙胺催化剂的质量比为30～80:1，优选为40～50:1；所述季戊四醇与三氯化磷的质量比为1:1.2～3，优选为1:1.5～2。
  4. 如权利要求2所述的亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，其特征在于步骤1)中，在常压下滴加三氯化磷时反应器中混合液的温度为65～75℃，滴加完毕后保持反应温度75～85℃；步骤1)的第一步反应时间为1.5～2.5小时。
  5. 如权利要求2所述的亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，其特征在于步骤1)中所述反应溶剂为二甲苯，季戊四醇与反应溶剂的质 量比为1:8～30，优选为1:12～18。
  6. 如权利要求2所述的亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，其特征在于步骤2)中的BHT原料与步骤1)中的季戊四醇质量之比为2～6:1，优选为4～5：1。
  7. 如权利要求2所述的亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，其特征在于步骤2)中的缚酸剂三丙胺-三丁胺混合物与步骤1)中的季戊四醇质量之比为1.5～5:1，优选为2～3:1。
  8. 如权利要求2所述的亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，其特征在于步骤2)中的缚酸剂三丙胺-三丁胺混合物中，以三丙胺用量为100质量份计，三丁胺的用量为10～100质量份，优选为20～80质量份、更优选为30～70质量份，更进一步优选为40～60质量份。
  9. 如权利要求2所述的亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，其特征在于步骤2)中滴加缚酸剂时反应器中混合液的温度为75～85℃，滴加完毕后反应温度控制在145℃以上，达到回流状态；步骤2)的第二步反应时间为2.5～5小时。
  10. 如权利要求2所述的亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法，其特征在于步骤2)中反应液的后处理过程为：降温至125～135℃进行过滤，在滤液中加入硅藻土并保温搅拌5～20分钟，再次进行过滤，然后进行减压蒸馏以便于完全脱除溶剂，即处理完成。
PCT/CN2023/098548 2022-12-09 2023-06-06 亚磷酸酯类抗氧剂双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯的合成方法 WO2024119744A1 (zh)

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Publication number Priority date Publication date Assignee Title
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1040372A (zh) * 1988-07-25 1990-03-14 博格-华纳特殊化学品有限公司 3，9-二磷杂螺十一烷及其制备方法
CN101418018A (zh) * 2007-10-26 2009-04-29 中国石油化工股份有限公司 一种季戊四醇双亚磷酸酯抗氧剂的制备方法
US20110021839A1 (en) * 2009-07-24 2011-01-27 Dover Chemical Corporation Phase transfer catalyst for synthesis of pentaerythritol diphosphites
CN105949243A (zh) * 2016-05-12 2016-09-21 营口市风光化工有限公司 一种亚磷酸酯类抗氧剂9228的制备方法
CN108707167A (zh) * 2018-07-05 2018-10-26 营口风光新材料股份有限公司 一种耐高温抗氧剂s-9228的合成方法
CN109232652A (zh) * 2018-11-16 2019-01-18 锦州英诺威科技服务有限公司 一种双(2,4-二枯基苯基)季戊四醇二亚磷酸酯的制备方法
CN109503663A (zh) * 2018-12-25 2019-03-22 萧县新秀新材料有限公司 一种双(2,6-二叔丁基-4-甲基苯基)季戊四醇亚磷酸酯的工业化生产方法
CN111747986A (zh) * 2020-07-09 2020-10-09 上海石化西尼尔化工科技有限公司 一种新型耐高温亚磷酸酯抗氧剂st-636及其制备方法和应用
CN115974924A (zh) * 2022-12-09 2023-04-18 浙江万盛股份有限公司 亚磷酸酯类抗氧剂双（2，6-二叔丁基-4-甲基苯基）季戊四醇二亚磷酸酯的合成方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1040372A (zh) * 1988-07-25 1990-03-14 博格-华纳特殊化学品有限公司 3，9-二磷杂螺十一烷及其制备方法
CN101418018A (zh) * 2007-10-26 2009-04-29 中国石油化工股份有限公司 一种季戊四醇双亚磷酸酯抗氧剂的制备方法
US20110021839A1 (en) * 2009-07-24 2011-01-27 Dover Chemical Corporation Phase transfer catalyst for synthesis of pentaerythritol diphosphites
CN105949243A (zh) * 2016-05-12 2016-09-21 营口市风光化工有限公司 一种亚磷酸酯类抗氧剂9228的制备方法
CN108707167A (zh) * 2018-07-05 2018-10-26 营口风光新材料股份有限公司 一种耐高温抗氧剂s-9228的合成方法
CN109232652A (zh) * 2018-11-16 2019-01-18 锦州英诺威科技服务有限公司 一种双(2,4-二枯基苯基)季戊四醇二亚磷酸酯的制备方法
CN109503663A (zh) * 2018-12-25 2019-03-22 萧县新秀新材料有限公司 一种双(2,6-二叔丁基-4-甲基苯基)季戊四醇亚磷酸酯的工业化生产方法
CN111747986A (zh) * 2020-07-09 2020-10-09 上海石化西尼尔化工科技有限公司 一种新型耐高温亚磷酸酯抗氧剂st-636及其制备方法和应用
CN115974924A (zh) * 2022-12-09 2023-04-18 浙江万盛股份有限公司 亚磷酸酯类抗氧剂双（2，6-二叔丁基-4-甲基苯基）季戊四醇二亚磷酸酯的合成方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TENG YANG: "Study on the Synthesis of Antioxidants of PEP-36 and Dodecyl Phenol", CHINA MASTER’S THESIS, 1 December 2014 (2014-12-01), XP093178744 *
巩晓君等 (GONG, XIAOJUN ET AL.): "离子交换树脂催化合成抗氧剂PEP-36 (Non-official translation: Synthesis of Antioxidant PEP-36 by Catalysis of Ion-exchange Resin)", 石油化工 (PETROCHEMICAL TECHNOLOGY), vol. 34, 31 December 2005 (2005-12-31) *

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