CN115974924A - 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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CN115974924A
CN115974924A CN202211580001.9A CN202211580001A CN115974924A CN 115974924 A CN115974924 A CN 115974924A CN 202211580001 A CN202211580001 A CN 202211580001A CN 115974924 A CN115974924 A CN 115974924A
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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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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 after the reaction, adds BHT as a raw material into a system, dropwise adds a tripropylamine-tributylamine mixture as an acid binding agent, performs a second-step reaction, and carries out post-treatment on the reacted feed liquid to obtain the efficient phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite with a spiro structure. The method can regulate and control the reaction of the second step to be carried out at high efficiency by changing the types of the acid-binding agent and the solvent, thereby greatly improving the yield, 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 and are chemical substances which, when present in only small amounts in polymer systems, retard or inhibit the progress of the oxidation process of the polymer and retard the deterioration of materials, articles and supplies during storage and use and are therefore also known as "anti-aging agents". Generally, the dosage is small, and most of the substances have reducing property. The general requirements of antioxidants are small amounts, high efficiency, low price and no adverse consequences.
Phosphite antioxidants decompose polymer peroxides and prevent the decomposition thereof from inducing polymer thermo-oxidative degradation, also known as peroxide decomposers, are usually used in combination with primary antioxidants and have a good synergistic effect. Therefore, the high-temperature processing stability of the polymer can be obviously improved, the color and melt index change during the processing of the polymer is inhibited, and the color and melt index stability of a plastic product are improved. At present, in the markets at home and abroad, a representative variety of general phosphite antioxidants with large use amount is antioxidant 168.
The antioxidant 626, the antioxidant 9228 and the antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (PEP-36) are representative high-performance phosphite antioxidants containing spiro rings, and compared with the general phosphite antioxidants, the antioxidant has higher antioxidant activity due to the unique spiro structure, and can be widely applied to middle and high-end formulas of general plastics and engineering plastics with harsh processing conditions. The structural formulas of the antioxidants 626, 9228 and PEP-36 are as follows:
Figure BDA0003990439720000021
three typical high-efficiency phosphite antioxidants with spiro unique structures
The pentaerythritol phosphite antioxidant is bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, the chemical name of which is 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 by Asahi Denka Kogyo Co, 20 th century, late 80 s to early 90 s, molecular formula: C35H54O6P2, the molecular weight of 632.75, the melting point of 235-240 ℃, the flash point of 380.5 ℃ and the trade name of PEP-36.
The synthesis of the antioxidant bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite in the literature or in the patent has three process routes: (1) a synthetic route of dichloropentaerythritol diphosphite; (2) a phosphite ester interchange method synthetic route; (3) a phosphorus trichloride synthesis route.
(1) Synthetic route of dichloro diphosphorous acid pentaerythritol ester the synthetic route of dichloro diphosphorous acid pentaerythritol ester is a synthetic route in the early stage. The catalyst is prepared by reacting pentaerythritol dichlorophosphite with 2, 6-di-tert-butyl-4-methylphenol under the action of a catalyst, and the reaction equation is as follows:
Figure BDA0003990439720000022
esterification synthesis route of dichloropentaerythritol diphosphite
Hobbs et al in EP0356688A disclose a synthesis method of a double-spiro phosphite ester compound, which uses pentaerythritol, phosphorus trichloride and hindered phenol as raw materials, and selects liquid tertiary amine as a catalyst. Pentaerythritol and phosphorus trichloride are firstly used for synthesizing a pentaerythritol dichlorophosphite intermediate, and the intermediate is separated and purified and then reacts with a hindered phenol compound 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 type of process and suggest that the substitution of the intermediate with BHT is facilitated by the addition of trialkylamine in an amount equimolar to the amount of HCl formed by the reaction.
The synthesis route of the dichloropentaerythritol diphosphite ester can directly join the dichloropentaerythritol diphosphite ester into bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite ester, and the synthesis process is simple. The reaction raw material of the dichloropentaerythritol diphosphite is an intermediate for synthesizing a plurality of phosphorus-containing double-spiro compounds, and the synthesis technology is mature. The biggest disadvantage of the route is that the purification and storage of pentaerythritol dichlorophosphite are very inconvenient. The dichloropentaerythritol diphosphite is generally synthesized from phosphorus trichloride and pentaerythritol, and because the reaction active sites are more, the product is comparatively miscellaneous, and the dichloropentaerythritol diphosphite is very easy to hydrolyze and deteriorate, and the purification difficulty is high.
(2) Phosphite ester exchange method the synthetic route of phosphite ester is that phosphite ester (triethyl phosphite, triphenyl phosphite, etc.), pentaerythritol and 2, 6-di-tert-butyl-4-methylphenol are used as raw materials to synthesize antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. In the case of triethyl phosphite, the reaction equation is shown below.
Figure BDA0003990439720000031
Synthetic route of phosphite ester exchange method
Zhanglifang prepared from pentaerythritol and P (OCH) 2 CH 3 ) 3 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. By investigating the influence of conditions such as material proportion, reaction temperature, reaction time and the like on the yield, the optimal process conditions are that n (pentaerythritol) n (triethyl phosphite) = n (BHT) = 1.12 2 CO 3 The reaction is carried out for 2h at 130-140 ℃, and then the reaction temperature is adjusted to 170-180 ℃ for 4h, and the yield is about 87%.
Larke et al reported in patent US 7342060 pentaerythritol, P (OPh) 3 And hindered phenol as a raw material to synthesize a series of phosphite ester compounds. Firstly, pentaerythritol and P (OPh) 3 The reaction generates intermediate diphenyl pentaerythritol diphosphite, phenol generated as a byproduct of the reaction is removed in a reduced pressure distillation mode, and the intermediate reacts with hindered phenol to generate phosphite antioxidant. If the hindered phenol is BHT, the product is antioxidantThe agent bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
The time for synthesizing the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite in the phosphite ester synthesis route is short, the condition is mild, the product does not contain acid, and the requirement on equipment is low. But the reactant triethyl phosphite serving as an industrial raw material is more than 5 times higher than that of phosphorus trichloride, the usage amount is larger, and the production cost is higher. Can be used for synthesis in a laboratory, but has larger difficulty in industrial production.
The synthetic route of phosphorus trichloride is as follows: the synthetic route of phosphorus trichloride is actually a synthetic route of a 'one-pot method'. The one-pot reaction is characterized in that the intermediate product is not separated. The one-pot method has simpler process in each step and not too many reaction steps, is generally suitable for synthesizing molecules with complex structures by using simple and cheap raw materials in a plurality of steps, and is particularly suitable for certain reactions with unstable intermediates or difficult separation. The yield is generally more desirable because the loss and consumption of the intermediate product separation process are eliminated by the reaction. The method is formally based on the consideration that phosphorus trichloride, pentaerythritol and 2, 6-tert-butyl-4-methylphenol are used as raw materials, and the raw materials are subjected to two-step reaction and one-step purification, wherein the reaction equation is as follows:
Figure BDA0003990439720000041
synthetic route of phosphorus trichloride
Hehailong et al in patent CN1948319A disclose a synthetic method of antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Pentaerythritol, phosphorus trichloride and BHT are taken as raw materials, antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is synthesized in a nonpolar aprotic solvent (toluene, xylene and the like), and ion exchange resin is adopted as a catalyst (wherein weak base resins of D301 and D370 types have the best effect). The reaction adopts two uninterrupted steps, wherein the first step of reaction is used for synthesizing dichloropentaerythritol diphosphite, and the reaction lasts for 2-10 h at 50-100 ℃. The second step is the synthesis of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, BHT is added in an amount of 2-4 times the mole number of pentaerythritol, the reaction is carried out for 8-24 h at 80-120 ℃, and the yield is 43.8% -67.5%.
Heximing et al, in patent CN102206234A, disclose a method for synthesizing an antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Pentaerythritol, phosphorus trichloride and BHT are taken as raw materials, liquid amine substances (triethylamine, piperidine and the like) are taken as catalysts, and the antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is synthesized. The method comprises the following steps of (1) reacting at 50-120 ℃ for 2-10 h, reacting at 80-130 ℃ for 8-24 h, washing with isopropanol (the mass ratio of isopropanol to product is 4-15).
Donald et al, in U.S. Pat. No. 5,8278490, disclose a one-pot synthesis route for phosphite antioxidants. Firstly, pentaerythritol, hindered phenol and catalyst quaternary ammonium salt compound are added into a system, and phosphorus trichloride is dripped for reaction. Firstly reacting for 2 hours at 79-81 ℃, and then heating to 140-142 ℃ for reacting for 12 hours. The byproduct HCl is absorbed by the caustic tower. If BHT is selected as hindered phenol, the product obtained by the reaction is antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
Although the synthetic route of phosphorus trichloride is a two-step reaction, the intermediate product is directly synthesized without separation and purification (the intermediate product pentaerythritol dichlorophosphite is unstable and has high purification difficulty), the solvent can be evaporated out after the synthesis, and the relatively pure product can be synthesized by means of washing with solvents such as methanol or isopropanol and the like. Although the method can generate a large amount of hydrochloric acid in the reaction, the requirement on equipment is high, the synthesis process is simple, the raw materials are all cheaper reagents commonly used in industry, the cost is low, and the method can be suitable for large-scale industrial production.
Yangteng discloses a process of first alcohol and then phenol (containing an acid-binding agent) in a Master academic paper of Tianjin science and technology university (antioxidant PEP-36 and dodecylphenol synthesis process research), which is characterized in that toluene is used as a solvent, excessive triethylamine is used as an acid-binding agent in the second step of esterification reaction, the reaction temperature is 125 ℃, the reaction time is 12 hours, the highest yield is 70.9 percent, and the purity is more than 98 percent.
Zhang Xixiu et al, in patent CN 109503663A, disclose an industrial production method of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite. 2, 6-di-tert-butyl-4-methylphenol, sodium methoxide and an organic solvent are prepared into 2, 6-di-tert-butyl-4-methylphenol sodium salt in a first-stage reaction kettle, pentaerythritol, phosphorus trichloride and the organic solvent are prepared into dichlorophosphote pentaerythritol ester solution in a second-stage reaction kettle, then the 2, 6-di-tert-butyl-4-methylphenol sodium salt prepared in the first-stage reaction kettle is added into the second-stage reaction kettle to prepare bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite ester reaction liquid, and then the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite ester product is obtained through centrifugal impurity removal, freeze crystallization separation, centrifugal desolventization and drying. The mol ratio of the 2, 6-di-tert-butyl-4-methylphenol to the sodium methoxide in the first step is 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 molar ratio of pentaerythritol to phosphorus trichloride in the second step is 1-1.5, the reaction temperature is 0-10 ℃, the pressure is-10 to-0.5 kPa, and the reaction time is kept at 0.5-3 h after the dripping is finished. The third step is that the reaction temperature is 60-80 ℃, the reaction pressure is 200-500 kPa, and the reaction time is 1.0-1.5 h. 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.
As described above, in the existing synthesis processes of bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, the yield is low with few steps and the reaction time is too long, while the number of steps is large, and hazardous organic metal compounds (corrosive and pyrophoric) such as sodium methoxide are used as raw materials, so that the process is complicated, and the industrial production is not facilitated.
Disclosure of Invention
In view of the above technical problems in the prior art, the present invention aims to provide a method for synthesizing a 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 the realization of the industrial production of 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, uses tripropylamine as a catalyst and xylene as a reaction solvent in the first step of reaction, uses a mixture formed by mixing tripropylamine and tributylamine according to a certain proportion as an acid binding agent and uses xylene as the reaction solvent in the second step of reaction, and synthesizes a mixture of high-efficiency novel phosphite compounds with a spiro structure by a 'one-pot method' with high efficiency and high yield. The reaction equation is as follows:
Figure BDA0003990439720000071
the invention relates to a high-efficiency high-yield one-pot synthesis method
The invention adopts the following specific technical scheme:
the method for synthesizing the high-efficiency phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite comprises the following steps:
1) Adding pentaerythritol, a reaction solvent and a tripropylamine catalyst into a reactor, dropwise adding phosphorus trichloride under normal pressure, heating for reaction, introducing nitrogen in the reaction process to remove generated hydrogen chloride out of the system, and sampling, analyzing and detecting the reaction process by HPLC;
2) And 1) after the reaction is finished, directly adding a BHT (butylated hydroxytoluene) raw material into the system, dropwise adding a tripropylamine-tributylamine mixture serving as an acid binding agent, carrying out the second-step reaction, carrying out HPLC (high performance liquid chromatography) sampling analysis and detection reaction until the reaction is finished, and carrying out post-treatment on a feed liquid after the reaction to obtain a target product.
Further, in the step 1), the mass ratio of the pentaerythritol to the tripropylamine catalyst is from 30 to 80, preferably from 40 to 50; the mass ratio of the pentaerythritol to the phosphorus trichloride is 1.2-3, preferably 1.5-2.
Further, in the step 1), the temperature of the mixed liquid in the reactor is 65-75 ℃ when the phosphorus trichloride is dripped under normal pressure, and the reaction temperature is kept at 75-85 ℃ after the dripping is finished; the first step reaction time of the step 1) is 1.5 to 2.5 hours.
Further, the reaction solvent in the step 1) is xylene, and can contain three isomers in any proportion, i, m and p. The mass ratio of the pentaerythritol to the reaction solvent is 1.
Further, the mass ratio of the BHT raw material in the step 2) to the pentaerythritol in the step 1) is 2-6, preferably 4-5: 1.
further, the mass ratio of the acid-binding agent tripropylamine-tributylamine mixture in the step 2) to the pentaerythritol in the step 1) is 1.5-5, preferably 2-3.
Further, in the acid-binding agent tripropylamine-tributylamine mixture in the step 2), 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 still more preferably 40 to 60 parts by mass, based on 100 parts by mass of tripropylamine. If the amount of tributylamine added 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, the temperature of the mixed liquid in the reactor is 75-85 ℃ when the acid binding agent is dripped in the step 2), and the reaction temperature is controlled to be above 145 ℃ after the dripping is finished to reach a reflux state; the second step reaction time of the step 2) is 2.5 to 5 hours.
Further, the post-treatment process of the reaction solution in the step 2) comprises the following steps: cooling to 125-135 ℃ for filtering, adding diatomite into the filtrate, keeping the temperature and stirring for 5-20 minutes, filtering again, and then carrying out reduced pressure distillation to completely remove the solvent, thus finishing the treatment.
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 finds out a novel alcohol-first phenol-then-phenol (acid-binding agent-containing) process for synthesizing bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and the high efficiency of the second step reaction (the reaction of pentaerythritol dichlorophosphite and 2, 6-di-tert-butyl-4-methylphenol) can be regulated and controlled by changing the types of the acid-binding agent and the solvent, so that the yield can be greatly improved, the reaction time can be shortened, the purity of the product can be improved, and the industrial production of bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite can be realized.
Drawings
FIG. 1 is a P31 (CDCl 3) spectrum of a target substance obtained in example 1;
FIG. 2 is a C13 (CDCl 3) spectrum of the target compound obtained in example 1;
FIG. 3 is an IR spectrum of a target substance obtained in example 1.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
a stirrer, a nitrogen inlet, a thermometer, a rectifying tube, and a cock (for sampling) were attached to a five-necked 1000ml flask, and a quantitative water receiver and a cooling tube were attached to the tip of the rectifying tube. Into the flask were charged pentaerythritol (13.6 g) as a raw material, xylene (200.0 g) as a solvent, and tripropylamine (0.3 g) as a catalyst, and phosphorus trichloride (27.4 g) as a raw material was added dropwise 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 ℃ to conduct the first-step reaction while removing the generated hydrogen chloride from the system. The first reaction was terminated when less than 1% of the starting material was analyzed by HPLC, and the duration of the first reaction was 2.0 hours. A PTFE hose was used to introduce nitrogen below the liquid level and a stirring operation was performed to remove residual hydrogen chloride gas. Thereafter, BHT (57.3 g) was added to the system, and a mixture of tripropylamine and tributylamine (the mass ratio tripropylamine/tributylamine =100/50, total 33.0 g) as an acid-binding agent was added dropwise at a temperature of 80 ℃. After the addition, the temperature of the system was gradually increased to reflux (> =145 ℃), and the second reaction step was carried out. The second reaction was terminated when less than 1% of the starting material was analyzed by HPLC, and the second reaction was carried out for 4.0 hours. Then, the temperature was lowered to 130 ℃ for filtration, diatomaceous earth (5.0 g) was added to the filtrate, and the mixture was stirred at 130 ℃ for 10 minutes, and then filtered again, and then subjected to reduced pressure distillation to completely remove the solvent, thereby producing bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite as a target with a yield of 93% and a purity detection of 99.3% by liquid chromatography as described in the master's paper of yangtang in tianjin scientific university [ antioxidant PEP-36 and dodecylphenol synthesis process research ].
The identification of the target bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite obtained in example 1 was carried out using nuclear magnetism and infrared, and the identification results were: the product has a P31 (CDCl 3) spectrum shown in FIG. 1, and phosphite compound chemical shifts of 122.58ppm and 122.51ppm, showing double peaks. C13 (CDCl 3) spectrum is shown in FIG. 2, and chemical shifts of a mixture of phosphite compounds as a main component 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, and 148.96ppm. The infrared spectrum of 671cm is shown in FIG. 3 -1 、688cm -1 、711cm -1 、736cm -1 、767cm -1 、783cm -1 、833cm -1 2918cm as the bending vibration peak of benzene ring -1 、2956cm -1 Is C-H stretching vibration peak.
Examples 2 to 6, comparative examples 1 to 3:
example 2-6 and comparative example 1-3 were repeated except that "the tripropylamine/tributylamine mass ratio was changed with the total tripropylamine/tributylamine charged mass maintained" was adjusted and the second-step reaction time length data recorded when the starting material was less than 1% by HPLC analysis in the second-step reactions of examples 2-6 and comparative examples 1-3 are summarized in table 1. The reaction conditions varied accordingly and the experimental results obtained finally are listed in table 1.
As shown in table 1, wherein the total reaction time period is the first step reaction time period plus the first step reaction time period. The tripropylamine/tributylamine ratio is seen to have a significant effect on product yield and purity.
TABLE 1 influence of Tertiary amine acid-binding agent ingredient ratio on yield and purity of synthesized product
Figure BDA0003990439720000111
Comparative examples 4 to 6:
comparative examples 4-6 procedure example 1 was repeated except that "the temperature of the second step reaction was adjusted as shown in table 2", and the reaction conditions changed accordingly and the experimental results finally obtained are shown in table 2. It can be seen that changes in reaction temperature have a significant effect on yield and purity.
TABLE 2 influence of Tertiary amine acid-binding agent ingredient ratio on yield and purity of the synthesized product
Figure BDA0003990439720000112
Figure BDA0003990439720000121
* HPLC analysis found the starting material to be more than 1% of the time, and the reaction was completed in 20 hours.
In conclusion, the new process greatly improves the yield of the synthesis reaction and the purity of the obtained product and shortens the reaction time.
The description is given for the sole purpose of illustrating the invention concept in its implementation form and the scope of the invention should not be considered as being limited to the particular form set forth in the examples.

Claims (10)

1. The synthesis method of phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is characterized by comprising the following steps: pentaerythritol, phosphorus trichloride and BHT are used as raw materials, tripropylamine is used as a catalyst to complete a first-step reaction in a reaction solvent, the reacted feed liquid directly enters the next step, BHT is added into the system as a raw material, a tripropylamine-tributylamine mixture used as an acid binding agent is dropwise added to perform a second-step reaction, and the reacted feed liquid is subjected to post-treatment to obtain the high-efficiency phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite with a spiro structure; the reaction formula is as follows:
Figure 511715DEST_PATH_IMAGE001
。
2. the method for synthesizing the phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite as claimed in claim 1, which comprises the following steps:
1) Adding pentaerythritol, a reaction solvent and a tripropylamine catalyst into a reactor, dropwise adding phosphorus trichloride under normal pressure, heating for reaction, introducing nitrogen in the reaction process to remove generated hydrogen chloride out of the system, and sampling, analyzing and detecting the reaction process by HPLC;
2) And 1) after the reaction is finished, directly adding a BHT (butylated hydroxytoluene) raw material into the system, dropwise adding a tripropylamine-tributylamine mixture serving as an acid binding agent, carrying out the second-step reaction, carrying out HPLC (high performance liquid chromatography) sampling analysis and detection reaction until the reaction is finished, and carrying out post-treatment on the feed liquid after the reaction to obtain a target product.
3. The method for synthesizing the 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 from 30 to 80, preferably from 40 to 50; the mass ratio of the pentaerythritol to the phosphorus trichloride is 1.2 to 3, preferably 1.5 to 2.
4. The method for synthesizing the phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite as claimed in claim 2, wherein in the step 1), when the phosphorus trichloride is added dropwise under normal pressure, the temperature of the mixed solution in the reactor is 65 to 75 ℃, and after the addition, the reaction temperature is kept at 75 to 85 ℃; the reaction time of the first step in the step 1) is 1.5 to 2.5 hours.
5. The method for synthesizing the phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein the reaction solvent in the step 1) is xylene, and the mass ratio of pentaerythritol to the reaction solvent is 1.
6. The method for synthesizing the phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein the mass ratio of the BHT raw material in the step 2) to the pentaerythritol in the step 1) is 2 to 6: 1.
7. the method for synthesizing the phosphite antioxidant bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein the mass ratio of the acid-binding agent tripropylamine-tributylamine mixture in the step 2) to the pentaerythritol in the step 1) is 1.5 to 5, preferably 2 to 3.
8. The method for synthesizing bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite as a phosphite antioxidant according to claim 2, wherein the amount of tributylamine in the tripropylamine-tributylamine mixture as the acid-binding agent 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, and still more preferably 40 to 60 parts by mass, based on 100 parts by mass of the tripropylamine.
9. The method for synthesizing bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite as a phosphite antioxidant according to claim 2, wherein the temperature of a mixed solution in a reactor is 75 to 85 ℃ when the acid-binding agent is dripped in the step 2), and the reaction temperature is controlled to be more than 145 ℃ after the dripping is finished, so that the reflux state is achieved; the reaction time of the second step in the step 2) is 2.5 to 5 hours.
10. The method for synthesizing bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite as a phosphite antioxidant according to claim 2, wherein the post-treatment process of the reaction solution in the step 2) comprises the following steps: and cooling to 125-135 ℃, filtering, adding diatomite into the filtrate, keeping the temperature and stirring for 5-20 minutes, filtering again, and then carrying out reduced pressure distillation to completely remove the solvent, thus finishing the treatment.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024119744A1 (en) * 2022-12-09 2024-06-13 浙江万盛股份有限公司 Synthesis method for phosphite antioxidant bis(2,6-di-ter-butyl-4-methylphenyl)pentaerythritol diphosphite

Citations (8)

* 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
US20110021839A1 (en) * 2009-07-24 2011-01-27 Dover Chemical Corporation Phase transfer catalyst for synthesis of pentaerythritol diphosphites
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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (8)

* 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
US20110021839A1 (en) * 2009-07-24 2011-01-27 Dover Chemical Corporation Phase transfer catalyst for synthesis of pentaerythritol diphosphites
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
巩晓君等: "离子交换树脂催化合成抗氧剂PEP-36", 《石油化工》, vol. 34, pages 650 - 652 *
杨腾: "抗氧剂PEP-36与十二烷基酚合成工艺研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》, pages 2 - 5 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024119744A1 (en) * 2022-12-09 2024-06-13 浙江万盛股份有限公司 Synthesis method for phosphite antioxidant bis(2,6-di-ter-butyl-4-methylphenyl)pentaerythritol diphosphite

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