CN115974924B - Synthesis method of phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite - Google Patents

Synthesis method of phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Download PDF

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CN115974924B
CN115974924B CN202211580001.9A CN202211580001A CN115974924B CN 115974924 B CN115974924 B CN 115974924B CN 202211580001 A CN202211580001 A CN 202211580001A CN 115974924 B CN115974924 B CN 115974924B
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pentaerythritol
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tripropylamine
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CN115974924A (en
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倪阳
李旭锋
关俊涛
鱼海龙
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Zhejiang Wansheng Co ltd
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    • 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
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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    • 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
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    • 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

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Abstract

The invention discloses a method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, which uses pentaerythritol, phosphorus trichloride and BHT as raw materials, uses tripropylamine as a catalyst to complete a first-step reaction in a reaction solvent, directly enters a next step of reaction feed liquid, adds BHT as the raw material into a system, and drops tripropylamine-tributylamine mixture as an acid binding agent for a second-step reaction, and obtains the high-efficiency phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite with a spiro structure through post-treatment of the reaction feed liquid. The method can regulate and control the reaction in the second step to be carried out with high efficiency by changing the types of the acid binding agent and the solvent, thereby greatly improving the yield and shortening the reaction time, improving the purity of the product and being beneficial to realizing the industrial production of the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

Description

Synthesis method of phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite
Technical Field
The invention relates to a method for synthesizing high-efficiency phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
Background
Substances which retard or prevent oxidation or autoxidation processes are known as antioxidants, which are chemical substances which, when present in small amounts in a polymer system, retard or inhibit the progress of the oxidation process of the polymer and retard the deterioration of materials, articles and articles during storage and use, and are therefore also known as "antioxidants". Generally, the amount of the catalyst is small, and most of the catalyst is a substance with reducing property. The general requirement for the antioxidant is that the dosage is small, the efficiency is high, the price is low, and no adverse effect exists.
Phosphite antioxidants have the advantages of decomposing polymer peroxide compounds and preventing the polymer peroxide compounds from being decomposed to induce the polymer to be degraded by thermal oxygen, are also called as peroxide decomposers, and are usually matched with main antioxidants for use, so that the phosphite antioxidants have good synergistic effect. Thereby remarkably improving the high-temperature processing stability of the polymer, inhibiting the change of the color and the melt index of the polymer during processing and improving the color and the melt index stability of the plastic product. At present, the representative variety of the general phosphite antioxidant with relatively large usage amount is antioxidant 168 in the markets at home and abroad.
Antioxidant 626, antioxidant 9228 and antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (PEP-36) are representative high-performance phosphite antioxidants containing spiro rings, compared with the general phosphite antioxidants, the antioxidant has a unique structure of spiro rings, has higher antioxidant activity, and can be widely applied to middle-high end formulas of general plastics and engineering plastics with more severe processing conditions. The structural formulas of antioxidants 626, 9228 and PEP-36 are as follows:
three typical high-efficiency phosphite antioxidants with spiro unique structures
Pentaerythritol phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, the chemical name bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is a highly effective phosphite antioxidant variety developed from the end of the 80 th to the beginning of the 90 th year of the 20 th century of the japanese electric company, and has the formula: C35H54O6P2, molecular weight 632.75, melting point 235-240 ℃, flash point 380.5 ℃, and trade name PEP-36.
The synthesis of antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite in literature or patents has three process routes: (1) a synthetic route of pentaerythritol dichloro-diphosphite; (2) a phosphite ester exchange method synthetic route; (3) a phosphorus trichloride synthesis route.
(1) The synthesis route of the pentaerythritol dichloro-diphosphite is an early synthesis route. The catalyst is prepared by reacting pentaerythritol dichloro-diphosphite with 2, 6-di-tert-butyl-4-methylphenol under the action of the catalyst, and the reaction equation is shown as follows:
esterification reaction synthetic route of pentaerythritol dichloro-diphosphite
Hobbs et al in patent EP0356688A disclose a process for synthesizing a bisspirocyclic phosphite compound using pentaerythritol, phosphorus trichloride and hindered phenol as raw materials, and a liquid tertiary amine as a catalyst. Firstly, pentaerythritol and phosphorus trichloride are used for synthesizing a pentaerythritol dichloro-diphosphite intermediate, and the intermediate is separated and purified and then reacts with hindered phenol compounds to synthesize a series of double-spiro phosphite compounds. If the hindered phenol is 2, 6-di-tert-butyl-4-methylphenol, the product is the antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
Patents US 5137950 and US 5308901 also report this class of processes and propose a process in which when an intermediate is reacted with BHT substitution, trialkylamine is added in an amount equimolar to the reaction to HCl.
The synthetic route of the pentaerythritol dichloro-diphosphite can directly synthesize the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite from the pentaerythritol dichloro-diphosphite, and the synthetic process is simple. The reaction raw material pentaerythritol dichloro-diphosphite is an intermediate for synthesizing a plurality of phosphorus-containing double spiro compounds, and the synthesis technology is mature. The greatest disadvantage of this route is that the purification and storage of pentaerythritol dichlorodiphosphite are very inconvenient. The pentaerythritol dichloro-diphosphite is generally synthesized from phosphorus trichloride and pentaerythritol, and the product is relatively miscellaneous due to a plurality of reactive sites, and the pentaerythritol dichloro-diphosphite is extremely easy to hydrolyze and deteriorate, and has great purification difficulty.
(2) The phosphite ester exchange process is to synthesize antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite with phosphite ester (triethyl phosphite, triphenyl phosphite, etc.), pentaerythritol and 2, 6-di-tert-butyl-4-methylphenol as material. Taking triethyl phosphite as an example, the reaction equation is shown below.
Phosphite ester exchange method synthetic route
Zhang Lifang and the like are prepared from pentaerythritol, P (OCH) 2 CH 3 ) 3 And 2, 6-di-tert-butyl-4-methylphenol are used as raw materials to synthesize the antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. By examining the influence of the conditions such as material proportion, reaction temperature, reaction time and the like on the yield, the optimal process condition is that n (pentaerythritol): n (triethyl phosphite): n (BHT) =1.0:2.12:2.04, and the catalyst is anhydrous K 2 CO 3 The reaction is firstly carried out for 2 hours at 130-140 ℃, then the reaction temperature is regulated to 170-180 ℃ for 4 hours, and the yield is about 87%.
Larke et al in patent US 7342060 report that pentaerythritol, P (OPh) 3 And synthesizing a series of phosphite ester compounds by taking hindered phenol as a raw material. Pentaerythritol and P (OPh) 3 The intermediate diphenyl pentaerythritol diphosphite is generated by the reaction, the byproduct phenol generated by the reaction is removed by a reduced pressure distillation mode, and the intermediate reacts with hindered phenol to generate phosphite antioxidants. If the hindered phenol is BHT, the product is antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
The phosphite synthesis route has short synthesis time, mild condition, no acid in the product and low requirement on equipment for synthesizing bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. But the reactant triethyl phosphite is used as an industrial raw material which is more than 5 times higher than phosphorus trichloride, and has larger usage amount and higher production cost. Can be used as laboratory synthesis, but has great difficulty in industrial production.
The synthetic route of phosphorus trichloride: the phosphorus trichloride synthesis route is actually a one-pot synthesis route. The one-pot reaction is characterized in that the intermediate product is not separated. The one-pot method has simple process and not too many reaction steps, is generally suitable for the synthesis reaction of synthesizing molecules with complex structures by a plurality of steps of simple and cheap raw materials, and is particularly suitable for the unstable or difficult separation reaction of certain intermediates. The yield is generally desirable because the reaction omits the loss and consumption of the intermediate product separation process. The route is formally based on the consideration that phosphorus trichloride, pentaerythritol and 2, 6-tertiary butyl-4-methylphenol are taken as raw materials, and the two-step reaction is carried out for one-time purification, wherein the reaction equation is as follows:
synthetic route of phosphorus trichloride
He Hailong et al in patent CN1948319A disclose a process for the synthesis of antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. The antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is synthesized by taking pentaerythritol, phosphorus trichloride and BHT as raw materials in a nonpolar aprotic solvent (toluene, xylene and the like), and ion exchange resin (wherein D301 and D370 weak base type resin has the best effect) is adopted as a catalyst. The reaction adopts two uninterrupted steps, the first step of reaction synthesizes pentaerythritol dichloro-diphosphite, and the reaction is carried out for 2 to 10 hours at the temperature of 50 to 100 ℃. The second step is the synthesis of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, the addition of BHT is 2-4 times of the mole number of pentaerythritol, the reaction is carried out for 8-24 hours at 80-120 ℃, and the yield is 43.8-67.5%.
He Liming et al in patent CN102206234A disclose a process for the synthesis of antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. The antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is synthesized by taking pentaerythritol, phosphorus trichloride and BHT as raw materials and taking liquid amine substances (triethylamine, piperidine and the like) as catalysts. The method comprises the steps of adopting pentaerythritol to PCl and BHT=1:2-2.2:2-5, reacting for 2-10 h at 50-120 ℃ in the first step, reacting for 8-24 h at 80-130 ℃ in the second step, washing with isopropanol (the mass ratio of isopropanol to the product is 4-15:1), washing with normal hexane (the mass ratio of normal hexane to the product is 2-5:1) in the post-reaction treatment, and finally drying at 80-130 ℃ to obtain the product with the yield of 51.4-70.5%.
Donald et al in patent US8278490 disclose a "one pot" synthetic route to phosphite antioxidants. Firstly, pentaerythritol, hindered phenol and a catalyst quaternary ammonium salt compound are added into a system, and phosphorus trichloride is added dropwise for reaction. Firstly, reacting for 2 hours at 79-81 ℃, then heating to 140-142 ℃ for reacting for 12 hours. The byproduct HCl is absorbed by the caustic tower. If the hindered phenol is BHT, the reaction product is antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
Although the phosphorus trichloride synthesis route is a two-step reaction, the intermediate product is not separated and purified (the intermediate product pentaerythritol dichlorophosphite is unstable and the purification difficulty is high), the phosphorus trichloride synthesis route is directly synthesized, the solvent can be distilled off after the synthesis, and the purer product can be synthesized by means of washing with solvents such as methanol or isopropanol and the like. The method can produce a large amount of hydrochloric acid to have higher equipment requirement, but has simple synthesis process, and the raw materials are cheap reagents commonly used in industry, so the method has low cost and can be suitable for large-scale industrial production.
Yang Teng in the university of Tianjin's university of science and technology, the research on the synthesis process of antioxidant PEP-36 and dodecylphenol, a process of alcohol-first and phenol-second (containing acid-binding agent) is disclosed, which is characterized in that toluene is used as solvent, and in that the second esterification reaction uses excess triethylamine as acid-binding agent, the reaction temperature is 125 ℃, the time is 12 hours, the highest yield is 70.9%, and the purity is more than 98%.
Zhang Xiuxiu et al in patent CN 109503663A disclose a process for the commercial production of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite. Preparing 2, 6-di-tert-butyl-4-methylphenol, sodium methoxide and organic solvent into a first-stage reaction kettle, preparing pentaerythritol dichloro-diphosphite pentaerythritol ester solution from pentaerythritol, phosphorus trichloride and organic solvent in a second-stage reaction kettle, adding the 2, 6-di-tert-butyl-4-methylphenol sodium salt prepared in the first-stage reaction kettle into a second-stage reaction kettle to prepare bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite ester reaction liquid, and performing centrifugal impurity removal, freezing crystallization separation, centrifugal desolventizing and drying to obtain a bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite ester product. The first step of reaction is that the mol ratio of 2, 6-di-tert-butyl-4-methylphenol to sodium methoxide is 1:1.1-1.4, the reaction temperature is 60-80 ℃, the pressure is 200-500 kPa, and the reaction time is l-2 h. The mole ratio of pentaerythritol to phosphorus trichloride in the second step is 1:1-1.5, the reaction temperature is 0-10 ℃, the pressure is minus 10 to minus 0.5kPa, and the heat preservation reaction time is 0.5-3 h after the dripping is finished. The third step of reaction is at 60-80 deg.c and 200-500 kPa for 1.0-1.5 hr. The purity of the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite ester product is more than 98.5 percent, and the yield is 90-92 percent.
In summary, for the existing various synthesis processes of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, the steps are low in yield and long in reaction time, and the steps are more, dangerous organic metal compounds (such as sodium methoxide and the like, which have corrosiveness and pyrophoricity) are used as raw materials, so that the process is complicated, and the industrial production is not facilitated.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide a method for synthesizing high-efficiency phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite with few steps and high yield by using safe raw materials as much as possible, which is beneficial to realizing the industrial production of the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
The invention provides a simple and efficient synthesis method, which uses pentaerythritol, phosphorus trichloride and BHT as raw materials, wherein tripropylamine is used as a catalyst and xylene is used as a reaction solvent in the first step of the reaction, and a mixture formed by mixing tripropylamine and tributylamine according to a certain proportion is used as an acid binding agent and xylene is used as a reaction solvent in the second step of the reaction, so that a mixture of high-efficiency novel phosphite compounds with spiro structures is synthesized by a 'one-pot method' with high efficiency and high yield. The reaction equation is as follows:
the high-efficiency and high-yield one-pot synthesis method of the invention
The invention adopts the following specific technical scheme:
the synthesis method of the high-efficiency phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite specifically comprises the following steps:
1) Adding pentaerythritol, a reaction solvent and a tripropylamine catalyst into a reactor, dropwise adding phosphorus trichloride under normal pressure, carrying out a heating reaction, introducing nitrogen in the reaction process to remove generated hydrogen chloride out of the system, and detecting the reaction progress through HPLC sampling analysis;
2) After the reaction of the step 1) is finished, directly adding a BHT raw material into the system, dropwise adding a tripropylamine-tributylamine mixture serving as an acid binding agent, performing a second-step reaction, sampling, analyzing and detecting the reaction to the end through HPLC, and performing post-treatment on the reacted feed liquid to obtain a target product.
Further, in the step 1), the mass ratio of the pentaerythritol to the tripropylamine catalyst is 30-80:1, preferably 40-50:1; the mass ratio of the pentaerythritol to the phosphorus trichloride is 1:1.2-3, preferably 1:1.5-2.
Further, in the step 1), when phosphorus trichloride is dropwise added under normal pressure, the temperature of the mixed solution in the reactor is 65-75 ℃, and the reaction temperature is kept at 75-85 ℃ after the dropwise addition is completed; the first reaction time of the step 1) is 1.5 to 2.5 hours.
Further, the reaction solvent in step 1) is xylene, and may contain ortho, meta, and para three isomers in any ratio. The mass ratio of pentaerythritol to the reaction solvent is 1:8-30, preferably 1:12-18.
Further, the mass ratio of the BHT raw material in the step 2) to the pentaerythritol in the step 1) is 2-6:1, preferably 4-5: 1.
further, the mass ratio of the tripropylamine-tributylamine mixture of the acid-binding agent in the step 2) to the pentaerythritol in the step 1) is 1.5-5:1, preferably 2-3:1.
Further, the amount of tripropylamine in the acid-binding agent tripropylamine-tributylamine mixture in step 2) is 10 to 100 parts by mass, preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, still more preferably 40 to 60 parts by mass, based on 100 parts by mass of tripropylamine. If the amount of tributylamine to be blended is less than 10 parts by mass or more than 100 parts by mass, the reaction efficiency is low and the yield is poor.
Further, when the acid binding agent is dropwise added in the step 2), the temperature of the mixed solution in the reactor is 75-85 ℃, and the reaction temperature is controlled to be more than 145 ℃ after the completion of dropwise addition, so that the reflux state is achieved; the second reaction time of the step 2) is 2.5-5 hours.
Further, the post-treatment process of the reaction liquid in the step 2) is as follows: cooling to 125-135 deg.c, filtering, adding diatomite into the filtrate, stirring for 5-20 min, filtering again, and vacuum distilling to eliminate solvent completely.
Compared with the prior art, the invention has the following beneficial effects: the invention carries out intensive research on the synthesis of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and results show that the novel alcohol-before-phenol (containing acid binding agent) process for synthesizing the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite can regulate and control the high efficiency of the second-step reaction (the reaction of pentaerythritol dichloro-diphosphite and 2, 6-di-tert-butyl-4-methylphenol) by changing the types of the acid binding agent and the solvent, thereby greatly improving the yield and shortening the reaction time, improving the purity of the product and being beneficial to realizing the industrial production of the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
Drawings
FIG. 1 is a graph of P31 (CDCl 3) of the target obtained in example 1;
FIG. 2 is a graph of C13 (CDCl 3) spectrum of the target product obtained in example 1;
FIG. 3 is an infrared spectrum of the target obtained in example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1:
a1000 ml flask having five ports was equipped with a stirrer, a nitrogen inlet pipe, a thermometer, a rectifying pipe and a cock (for sampling), and a moisture quantitative receiver and a cooling pipe were further installed at the front end of the rectifying pipe, and the above-mentioned apparatus was used as a reaction apparatus. Pentaerythritol (13.6 g) as a raw material, xylene (200.0 g) as a solvent, tripropylamine (0.3 g) as a catalyst, and phosphorus trichloride (27.4 g) as a raw material were added dropwise to the flask at a temperature of 70℃under normal pressure. After the completion of the dropwise addition, the reaction temperature of the system was maintained at 80℃and the first-stage reaction was carried out while removing the hydrogen chloride formed outside the system. The first step reaction was terminated when less than 1% of the starting material was analyzed by HPLC, and the first step reaction time was 2.0 hours. A PTFE hose is used to introduce nitrogen below the liquid surface and stirring operation is performed to remove residual hydrogen chloride gas. Thereafter, BHT (57.3 g) was added to the system, and a mixture of tripropylamine and tributylamine (mass ratio tripropylamine/tributylamine=100/50, total 33.0 g) was added dropwise as an acid-binding agent at normal pressure and a temperature of 80 ℃. After the addition was completed, the system was gradually warmed to reflux (> 145 ℃) and the second step reaction was performed. The second step reaction was completed when less than 1% of starting material was analyzed by HPLC, and the second step reaction time was 4.0 hours. Then, the temperature was lowered to 130℃and filtration was carried out, diatomite (5.0 g) was added to the filtrate and stirred at 130℃for 10 minutes, filtration was carried out again, and then distillation under reduced pressure was carried out so as to completely remove the solvent, whereby bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite as a target was produced in a yield of 93% and purity was measured by liquid chromatography as described in the university of Tianjin science and technology, paper (antioxidant PEP-36 and dodecylphenol Synthesis Process study) according to Yang Teng, 99.3%.
The target bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite obtained in example 1 was identified using nuclear magnetism and infrared, the identification results being: the P31 (CDCl 3) spectrum of the product is shown in FIG. 1, the chemical shifts of the phosphite compounds are 122.58ppm and 122.51ppm, and the product shows double peaks. C13 (CDCl 3) spectrum is shown in FIG. 2, and the chemical shifts of the mixture of phosphite compounds as the main components were 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. The infrared spectrum is shown in FIG. 3, wherein 671cm -1 、688cm -1 、711cm -1 、736cm -1 、767cm -1 、783cm -1 、833cm -1 Is a bending vibration peak of benzene ring, 2918cm -1 、2956cm -1 Is C-H stretching vibration peak.
Examples 2 to 6 and comparative examples 1 to 3:
the procedure of examples 2-6 and comparative examples 1-3 was repeated except that "the mass ratio of tripropylamine/tributylamine was changed by adjustment, wherein the total mass of tripropylamine/tributylamine fed was maintained, and the second-step reaction duration data recorded when the raw materials were less than 1% in the second-step reactions of examples 2-6 and comparative examples 1-3 were analyzed by HPLC was summarized in Table 1. The reaction conditions and the final experimental results are shown in Table 1.
As shown in table 1, wherein the total reaction duration is the first step reaction duration plus the first step reaction duration. It can be seen that the ratio of tripropylamine/tributylamine has a significant effect on the yield and purity of the product.
TABLE 1 influence of the ratio of the tertiary amine acid-binding agent components on the yield and purity of the synthesized product
Comparative examples 4 to 6:
comparative examples 4-6 the procedure of example 1 was repeated except that "the temperature of the second-step reaction was adjusted as shown in Table 2", the reaction conditions were changed accordingly, and the experimental results finally obtained were as shown in Table 2. It can be seen that the change in reaction temperature has a significant effect on yield and purity.
TABLE 2 influence of the ratio of the tertiary amine acid-binding agent components on the yield and purity of the synthesized product
* HPLC analysis found starting material to be higher than always 1% and the reaction was completed for 20 hours.
In summary, the novel process of the invention greatly improves the yield of the synthesis reaction and the purity of the obtained product and shortens the reaction time as shown in experimental data.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.

Claims (12)

1. The synthesis method of phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is characterized by comprising the following reaction formula:
the method specifically comprises the following steps:
1) Adding pentaerythritol, a reaction solvent and a tripropylamine catalyst into a reactor, dropwise adding phosphorus trichloride under normal pressure, carrying out a heating reaction, introducing nitrogen in the reaction process to remove generated hydrogen chloride out of the system, and detecting the reaction progress through HPLC sampling analysis;
2) After the reaction of the step 1), directly adding a BHT raw material into the system, dropwise adding a tripropylamine-tributylamine mixture serving as an acid binding agent, performing a second step of reaction, sampling, analyzing and detecting the reaction to the end through HPLC, and performing post-treatment on the reacted feed liquid to obtain a target product;
the reaction solvent in the step 1) is dimethylbenzene, and the mass ratio of pentaerythritol to the reaction solvent is 1:8-30;
the mass ratio of the tripropylamine-tributylamine mixture of the acid-binding agent in the step 2) to the pentaerythritol in the step 1) is 2-3:1;
in the acid binding agent tripropylamine-tributylamine mixture in the step 2), the amount of tripropylamine is 10-100 parts by mass based on 100 parts by mass of the amount of tripropylamine;
and 2) dropwise adding an acid binding agent in the step 2), wherein the temperature of the mixed solution in the reactor is 75-85 ℃, and the reaction temperature is controlled to be more than 145 ℃ after the dropwise adding is finished, so that the reflux state is achieved.
2. The method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 1, wherein in the step 1), the mass ratio of pentaerythritol to tripropylamine catalyst is 30-80:1; the mass ratio of the pentaerythritol to the phosphorus trichloride is 1:1.2-3.
3. The method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein in the step 1), the mass ratio of pentaerythritol to tripropylamine catalyst is 40-50:1; the mass ratio of the pentaerythritol to the phosphorus trichloride is 1:1.5-2.
4. The method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 1, wherein in step 1), the temperature of the mixed solution in the reactor is 65-75 ℃ when phosphorus trichloride is dropwise added under normal pressure, and the reaction temperature is kept at 75-85 ℃ after the completion of the dropwise addition; the first reaction time of the step 1) is 1.5-2.5 hours.
5. The method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 1, wherein in the step 1), the mass ratio of pentaerythritol to a reaction solvent is 1:12-18.
6. The method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 1, wherein the mass ratio of the BHT raw material in the step 2) to pentaerythritol in the step 1) is 2-6:1.
7. The method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 6, wherein the mass ratio of the BHT raw material in step 2) to pentaerythritol in step 1) is 4-5: 1.
8. the method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 1, wherein the amount of tripropylamine is 20 to 80 parts by mass based on 100 parts by mass of tripropylamine in the mixture of tripropylamine and tributylamine in the step 2).
9. The method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 8, wherein the amount of tripropylamine is 30 to 70 parts by mass based on 100 parts by mass of the amount of tripropylamine in the mixture of tripropylamine and tributylamine in the step 2).
10. The method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 9, wherein the amount of tripropylamine is 40 to 60 parts by mass based on 100 parts by mass of tripropylamine in the mixture of tripropylamine and tributylamine in the step 2).
11. The method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 1, wherein the second reaction time of step 2) is 2.5-5 hours.
12. The method for synthesizing phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 1, wherein the post-treatment process of the reaction liquid in step 2) is as follows: cooling to 125-135 ℃ for filtering, adding diatomite into the filtrate, keeping the temperature and stirring for 5-20 minutes, filtering again, and then performing reduced pressure distillation to completely remove the solvent, thus finishing the treatment.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1040372A (en) * 1988-07-25 1990-03-14 博格-华纳特殊化学品有限公司 3,9-two phospha spiral shell undecanes and preparation method thereof
CN101418018A (en) * 2007-10-26 2009-04-29 中国石油化工股份有限公司 Method for preparing pentaerythritol bis-phosphite antioxidant
CN105949243A (en) * 2016-05-12 2016-09-21 营口市风光化工有限公司 Preparation method of phosphite antioxidant 9228
CN108707167A (en) * 2018-07-05 2018-10-26 营口风光新材料股份有限公司 A kind of synthetic method of high temperature resistant antioxidant S-9228
CN109232652A (en) * 2018-11-16 2019-01-18 锦州英诺威科技服务有限公司 A kind of preparation method of bis- (2,4- dicumylphenyl) pentaerythritol diphosphites
CN109503663A (en) * 2018-12-25 2019-03-22 萧县新秀新材料有限公司 A kind of industrialized preparing process of bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol phosphites
CN111747986A (en) * 2020-07-09 2020-10-09 上海石化西尼尔化工科技有限公司 Novel high-temperature-resistant phosphite antioxidant ST-636 as well as preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8278490B2 (en) * 2009-07-24 2012-10-02 Dover Chemical Corporation Phase transfer catalyst for synthesis of pentaerythritol diphosphites
CN115974924B (en) * 2022-12-09 2024-04-16 浙江万盛股份有限公司 Synthesis method of phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1040372A (en) * 1988-07-25 1990-03-14 博格-华纳特殊化学品有限公司 3,9-two phospha spiral shell undecanes and preparation method thereof
CN101418018A (en) * 2007-10-26 2009-04-29 中国石油化工股份有限公司 Method for preparing pentaerythritol bis-phosphite antioxidant
CN105949243A (en) * 2016-05-12 2016-09-21 营口市风光化工有限公司 Preparation method of phosphite antioxidant 9228
CN108707167A (en) * 2018-07-05 2018-10-26 营口风光新材料股份有限公司 A kind of synthetic method of high temperature resistant antioxidant S-9228
CN109232652A (en) * 2018-11-16 2019-01-18 锦州英诺威科技服务有限公司 A kind of preparation method of bis- (2,4- dicumylphenyl) pentaerythritol diphosphites
CN109503663A (en) * 2018-12-25 2019-03-22 萧县新秀新材料有限公司 A kind of industrialized preparing process of bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol phosphites
CN111747986A (en) * 2020-07-09 2020-10-09 上海石化西尼尔化工科技有限公司 Novel high-temperature-resistant phosphite antioxidant ST-636 as well as preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
抗氧剂PEP-36与十二烷基酚合成工艺研究;杨腾;《中国优秀硕士学位论文全文数据库工程科技I辑》;B016- 308，特别是第26页第2-5段，第2.4.3节，表2-8 *
离子交换树脂催化合成抗氧剂PEP-36;巩晓君等;《石油化工》;第34卷;第650-652页，特别是第1.2节，第652页左栏第3-4段 *

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