LU103176B1 - Method for synthesizing phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite - Google Patents

Method for synthesizing phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Download PDF

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LU103176B1
LU103176B1 LU103176A LU103176A LU103176B1 LU 103176 B1 LU103176 B1 LU 103176B1 LU 103176 A LU103176 A LU 103176A LU 103176 A LU103176 A LU 103176A LU 103176 B1 LU103176 B1 LU 103176B1
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reaction
tert
butyl
pentaerythritol
methylphenyl
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LU103176A
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German (de)
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Yang Ni
Xufeng Li
Hailong Yu
Juntao Guan
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Zhejiang Wansheng Co Ltd
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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

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Abstract

Disclosed in the present invention is a method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. The method includes the steps: completing a first-step reaction in a reaction solvent by taking pentaerythritol, phosphorus trichloride, and butylated hydroxytoluene (BHT) as raw materials and tripropylamine as a catalyst, where after the reaction, a feed liquid directly enters a next step; adding BHT serving a raw material into a system, and dropwise adding a tripropylamine- tributylamine mixture serving as an acid-binding agent for a second-step reaction; and performing post-treatment on the feed liquid after the reaction to obtain the high-efficiency phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite with a spiro structure.

Description

H109WO8LU-PCT23019 30.06.2023
METHOD FOR SYNTHESIZING PHOSPHITE ANTIOXIDANT OF LU103176
BIS(2,6-DI-TERT-BUTYL-4-METHYLPHENYL) PENTAERYTHRITOL
DIPHOSPHITE
TECHNICAL FIELD
[01] The present invention relates to a method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
BACKGROUND ART
[02] A substance capable of delaying or preventing an oxidation or automatic oxidation process is referred to as an antioxidant, which is a kind of chemical substance. The progress of a polymer oxidation process can be delayed or inhibited when only a small amount of the antioxidant exists in a polymer system, and deterioration of materials, articles and supplies during storage and use can be delayed, such that the antioxidant is also referred to as an anti-aging agent. Generally, a usage amount of the antioxidant is small, and most of antioxidants are substances with a reduction property. Small usage amount, high efficiency, a low price and no adverse consequences are general requirements on the antioxidant.
[03] Phosphite antioxidants have an effect of decomposing polymer peroxy compounds to prevent induction of thermo-oxidative degradation of polymers due to cracking of the polymer peroxy compounds, and are also referred to as peroxide decomposing agents, which are usually used in conjunction with a main antioxidant, and have a good synergistic effect, and therefore, high-temperature processing stability of the polymers can be remarkably improved, the color and melt index change during polymer processing can be inhibited, and the color and the melt index stability of plastic products can be improved. At present, on the market at home and abroad, a representative variety of general phosphite antioxidants with relatively large usage amounts is an antioxidant 168.
[04] The antioxidant 626, the antioxidant 9228, and the antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol ~~ diphosphite (PEP-36) are representative high-performance phosphite antioxidants containing spiro. Compared with the general phosphite antioxidants, the antioxidant 626, the antioxidant 9228, and the antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite are higher 1
H109WO8LU-PCT23019 30.06.2023 in antioxidant activity, and can be widely used in medium and high-end formulas of general LU103176 plastics and engineering plastics with harsh processing conditions due to unique spiro structures. Structural formulas of the antioxidants 626, 9228 and PEP-36 are as follows: wd od M pen owed He A em = bond Ye d— 626 9228 s PEP® OM
[05]
[06] Three typical high-efficiency phosphite antioxidants with unique spiro structures
[07] The pentaerythritol phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite has a chemical name of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol ~~ diphosphite. ~~ Bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is a kind of high-efficiency phosphite antioxidant developed by Japan's Asahi
Denka Company from the late 1980s to the early 1990s, and has a molecular formula of
C35H5406P2, a molecular weight of 632.75, a melting point of 235-240°C, a flash point of 380.5C, and a commodity name of PEP-36.
[08] There are three process routes for synthesizing the antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite in literature or patents: (1) a pentaerythritol dichlorodiphosphite synthetic route; (2) a phosphite transesterification method synthetic route; and (3) a phosphorus trichloride synthetic route.
[09] (1) Pentaerythritol dichlorodiphosphite synthetic route: the pentaerythritol dichlorodiphosphite synthetic route is an early synthetic route, which is generated by enabling pentaerythritol dichlorodiphosphite to react with 2,6-di-tert-butyl-4-methylphenol under an action of a catalyst, and a reaction equation is shown as follows:
Bu = tBu
Ne Ny og sme A A 5
[10] a = P entaerythritol dichlorodiphosphite esterification reaction synthetic route
[11] A method for synthesizing double-spiro phosphite compounds is disclosed in the patent with No. EP0356688A by Hobbs, where pentaerythritol, phosphorus trichloride and 2
H109WO8LU-PCT23019 30.06.2023 hindered phenol are taken as raw materials, and liquid tertiary amine is used as a catalyst. A LU103176 pentaerythritol dichlorodiphosphite intermediate is first synthesized by using the pentaerythritol and the phosphorus trichloride, and the intermediate reacts with a hindered phenolic compound after being separated and purified to synthesize a series of double-spiro phosphite compounds. If the hindered phenol is 2,6-di-tert-butyl-4-methylphenol, a product is the antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
[12] Such a method is also reported in the US patents with No. 5137950 and No. 5308901, which propose a method in which when the intermediate reacts with a butylated hydroxytoluene (BHT) substitution, trialkylamine in an equal molar weight to HCI produced by the reaction is added for promotion.
[13] In the pentaerythritol dichlorodiphosphite synthetic route, the bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite can be directly synthesized from the pentaerythritol dichlorodiphosphite, and the synthetic process is simple. The reaction raw material of pentaerythritol dichlorodiphosphite is an intermediate in the synthesis of many phosphorus-containing double-spiro compounds, and the synthesis technology is relatively mature. The biggest defect of this route is that purification and storage of the pentaerythritol dichlorodiphosphite is very inconvenient. The pentaerythritol dichlorodiphosphite is generally synthesized from the phosphorus trichloride and the pentaerythritol. Because of many reaction active sites, the product is miscellaneous, and the pentaerythritol dichlorodiphosphite is likely to hydrolyze and deteriorate, such that purification is difficult.
[14] (2) Phosphite transesterification method synthetic route: in the phosphite transesterification method synthetic route, phosphite (triethyl phosphite, triphenyl phosphite, etc.), pentaerythritol, 2,6-di-tert-butyl-4-methylphenol serve as raw materials to synthesize the antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. By taking the triethyl phosphite as an example, a reaction equation is shown below. 3
H109WO8LU-PCT23019 30.06.2023 au LU103176
HO OH Se
NT + PL na C= tBu
Bu Bu
Catalyst. solvent YT) ef \ AA p=
[15] vos a
[16] Phosphite transesterification method synthetic route
[17] ZHANG Lifang, etc. takes pentaerythritol, P(OCH2CH3);3 and 2,6-di-tert-butyl-4-methylphenol as raw materials to synthesize the antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. By means of investigation of influence of a materials ratio, a reaction temperature, reaction time and other conditions on a yield, the optimum condition is n(pentaerythritol):n(triethyl phosphite): n(BHT)=1.0:2.12:2.04, anhydrous K2CO3 serves as a catalyst, a reaction is first performed at 130-140°C for 2 h, and then performed at 170-180°C for 4 h, and the yield is about 87%.
[18] Synthesis of a series of phosphite compounds by taking pentaerythritol, P(OPh)3 and hindered phenol as raw materials is reported by Larke, etc. in the patent with No. US 7342060, where firstly, the pentaerythritol reacts with the P(OPh)s to generate an intermediate of diphenyl pentaerythritol diphosphite, by-product phenol generated by the reaction is removed in a reduced pressure distillation manner, and the intermediate reacts with hindered phenol to generate a phosphite antioxidant. If the hindered phenol is BHT, the product is the antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
[19] In the phosphite synthetic route, time for synthesizing the bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is short, conditions are mild, no acids exists in the product, and requirements on an apparatus are low. However, the reactant of triethyl phosphite as an industrial raw material is higher over 5 times than that of phosphorus trichloride in price, and a usage amount is large, such that a production cost is high. The triethyl phosphite can be used for laboratory synthesis, but it is difficult to be used for industrial production. 4
H109WO8LU-PCT23019 30.06.2023
[20] Phosphorus trichloride synthetic route: The phosphorus trichloride synthetic route LU103176 is actually a one-pot synthetic route. The one-pot reaction is characterized by no separation of intermediate products. The one-pot method is relatively simple in each step, and the number of reaction steps cannot be too many. The method is generally suitable for synthesis of molecules with complex structures from simple and cheap raw materials, especially for reactions where some intermediates are unstable or difficult to separate.
Since the reaction omits loss and consumption of intermediate products in a separation process, a yield is generally satisfactory. Thus, in the route, phosphorus trichloride, pentaerythritol and 2,6-tert-butyl-4-methylphenol are used as raw materials, two steps of reaction and one time of purification are performed, and a reaction equation is as follows:
HO a Pu pe y pol me OH oa b ï TN NI t-Bu
I. Bu ; ‘ PP
[21] © Na — ’ Wo
[22] Phosphorus trichloride synthetic route
[23] A method for synthesizing an antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is disclosed by HE Hailong, etc. in the patent with No.
CN1948319A, where The antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is synthesized from raw materials of pentaerythritol, phosphorus trichloride and BHT in a nonpolar aprotic solvent (toluene, xylene, etc.), and a catalyst is ion exchange resin (models of D301 and D370 weak base resin are the best in effect). Uninterrupted two steps of reaction is employed, in the first-step reaction, pentaerythritol dichlorodiphosphite is synthesized, and the reaction is performed for 2 to 10 h at a temperature of 50-100 C . In the second-step reaction, synthesis of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is completed. An addition amount of the BHT is 2-4 times of the mole number of the pentaerythritol. The reaction is
H109WO8LU-PCT23019 30.06.2023 performed at a temperature of 80-120°C for 8-24 h, and a yield is 43.8%-67.5%. LU103176
[24] A method for synthesizing an antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is disclosed by HE Liming, etc. in the patent with No.
CN102206234A, where an antioxidant bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is synthesized by taking pentaerythritol, phosphorus trichloride and BHT as raw materials and liquid amine (triethylamine, piperidine, etc.) as a catalyst. In the method, a molar ratio of pentaerythritol: PCl:BHT=1:2-2.2:2-5, a first-step reaction is performed at a temperature of 50-120°C for 2-10 h, a second-step reaction is performed at a temperature of 80-130°C for 8-24 h. For treatment after the reaction, firstly, washing is performed with isopropanol (a mass ratio of the isopropanol to the product is 4-15:1), then washing is performed with n-hexane (a mass ratio of the n-hexane to the product is 2- 5:1), and finally drying is performed at a temperature of 80-130°C. A yield is 51.4%-70.5%.
[25] A one-pot method synthetic route for a phosphite antioxidant is disclosed in the patent with No. US8278490 by Donald, etc, and includes the steps of adding pentaerythritol, hindered phenol and a catalyst of a quaternary ammonium salt compound into a system, and dropwise adding phosphorus trichloride for reaction, where the reaction is performed at a temperature of 79-81°C for 2 h, and then heating is performed to 140-142°C for reaction for 12 h. A by-product of HCl is absorbed by a caustic tower. If the hindered phenol is BHT, the product obtained from the reaction is an antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
[26] Although the phosphorus trichloride synthetic route is a two-step reaction, the intermediate product is not separated and purified (the intermediate product of pentaerythritol dichlorodiphosphite is unstable and difficult to purify), and synthesis is directly performed. After the synthesis, the solvent can be distilled out, and the relatively pure product can be synthesized by means of solvent washing with methanol or isopropanol.
Although the method generates a large amount of hydrochloric acid in the reaction and has high requirements on an apparatus, the synthesis process is simple, the raw materials are cheap reagents commonly used in industry, the cost is low, and therefore, the method is suitable for large-scale industrial production.
[27] YANG Teng discloses a process of alcohol first followed by phenol (containing 6
H109WO8LU-PCT23019 30.06.2023 an acid-binding agent) in his master's degree thesis Study on synthesis process of LU103176 antioxidant PEP-36 and dodecylphenol of Tianjin University of Science and Technology, where toluene is used as a solvent, and excessive triethylamine is used as an acid-binding agent in a second-step esterification reaction, a reaction temperature is 125°C, reaction time is 12 h, the highest yield is 70.9%, and purity is over 98%.
[28] An industrial production method for bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite is disclosed by ZHANG Xiuxiu, etc. in the patent with No.
CN109503663 A, where 2,6-di-tert-butyl-4-methylphenol, sodium methoxide and an organic solvent react in a first-stage reaction kettle to — obtain 2,6-di-tert-butyl-4-methylphenol sodium salt, pentaerythritol, phosphorus trichloride and an organic solvent react in a second-stage reaction kettle to obtain a pentaerythritol dichlorodiphosphite solution, 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 obtain a bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite reaction solution, and finally, centrifugal impurity removal, freezing crystallization separation, centrifugal desolventizing and drying are performed to obtain the bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite product. In the first-step reaction, a molar ratio of the 2,6-di-tert-butyl-4-methylphenol to the sodium methoxide is 1:1.1-1.4, a reaction temperature is 60-80°C, pressure is 200-500 kPa, and reaction time is 1-2 h. In the second-step reaction, a molar ratio of the pentaerythritol to the phosphorus trichloride 1s 1:1-1.5, a reaction temperature is 0-10°C, pressure is -10 kPa to -0.5 kPa, and the reaction time for heat preservation is 0.5-3 h after dropwise addition is finished. In the third step, a reaction temperature is 60-80°C, reaction pressure is 200-500 kPa, and reaction time is 1.0-1.5 h. Purity of the bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite product is over 98.5%, and a yield is 90-92%.
[29] To sum up, for various existing synthetic processes of the bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, the yield is low and the reaction time is too long for those with few steps, while dangerous organometallic compounds (corrosive and pyrophoric) such as sodium methoxide are used as raw materials for those with multiple steps, which complicates the process and is not conducive to 7
H109WO8LU-PCT23019 30.06.2023 industrial production. LU103176
SUMMARY
[30] Aiming at the above technical problems existing in the prior art, an objective of the present invention is to provide a high-yield method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, which has few steps and uses safe raw materials, and facilitates industrial production of the bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
[31] The present invention provides a simple, convenient and high-efficiency synthetic method, where pentaerythritol, phosphorus trichloride and butylated hydroxytoluene (BHT) are taken as raw materials, in a first step of reaction, tripropylamine is taken as a catalyst, and xylene is taken as a reaction solvent. In a second step of reaction, a mixture obtained by mixing tripropylamine and tributylamine according to a certain ratio is taken as an acid-binding agent, and xylene is taken as a reaction solvent. A mixture of a new high-efficiency phosphite compound with a spiro structure is synthesized by using a high-efficiency and high-yield one-pot method. A reaction equation is shown as follows:
HO OH fo Oo + 4 Va --———— CP P—CI
HO— X—-0H Ci Tripropyviamine catalyst Nyt J
Xylene soivent
Bu / 2 / N —OH _ tBu Bu — © 0 a t-Bu J \ o p° a °
Tripropylamine and tributylamme \ FES \ / mixture acid-binding agent itt o— ° 2 \ /
Mylene solvent Bu tBu
[32]
[33] High-efficiency and high-yield one-pot synthetic method of present invention
[34] The specific technical solutions employed by the present invention are as follows:
[35] The method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite specifically includes the following steps:
[36] 1) adding pentaerythritol, a reaction solvent and a tripropylamine catalyst into a reactor, dropwise adding phosphorus trichloride under normal pressure for a heating 8
H109WO8LU-PCT23019 30.06.2023 reaction, introducing nitrogen during a reaction process to remove generated hydrogen LU103176 chloride out of the system, and detecting the reaction process by means of high performance liquid chromatography (HPLC) sampling analysis; and
[37] 2) after the reaction in 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 for the second-step reaction, detecting the reaction by means of the
HPLC sampling analysis until the reaction is finished, and performing post-treatment on the feed liquid after the reaction to obtain the target product.
[38] Furthermore, in step 1), a mass ratio of the pentaerythritol to the tripropylamine catalyst is 30-80:1 and preferably 40-50:1, and a mass ratio of the pentaerythritol to the phosphorus trichloride is 1:1.2-3 and preferably 1:1.5-2.
[39] Furthermore, in step 1), a temperature of the mixed liquid in the reactor is 65-75°C when the phosphorus trichloride is added dropwise under normal pressure, and a reaction temperature is kept at 75-85°C after dropwise addition is finished; and first-step reaction time in step 1) is 1.5-2.5 h.
[40] Furthermore, the reaction solvent in step 1) is xylene, which can includes three kinds of isomers, namely ortho-/meta-/para-isomers at any ratio. A mass ratio of the pentaerythritol to the reaction solvent is 1:8-30 and preferably 1:12-18.
[41] Furthermore, a mass ratio of the BHT raw material in step 2) to the pentaerythritol in step 1) is 2-6:1 and preferably 4-5:1.
[42] Furthermore, a mass ratio of the acid-binding agent of tripropylamine-tributylamine mixture in step 2) to the pentaerythritol in step 1) is 1.5-5:1 and preferably 2-3:1.
[43] Furthermore, in the acid-binding agent of tripropylamine-tributylamine mixture in step 2), a usage amount of tributylamine is 10-100 parts by mass, preferably 20-80 parts by mass, more preferably 30-70 parts by mass, and further preferably 40-60 parts by mass based on 100 parts of tripropylamine by mass. If a use level of the tributylamine is lower than 10 parts by mass or higher than 100 parts by mass, reaction efficiency is low, and a yield is poor.
[44] Furthermore, a temperature of the mixed liquid in the reactor is 75-85°C when 9
H109WO8LU-PCT23019 30.06.2023 the acid-binding agent is added dropwise, and a reaction temperature is controlled to be LU103176 over 145°C after the dropwise addition is finished to reach a reflux state; and second-step reaction time of step 2) is 2.5-5 h.
[45] Furthermore, the post-treatment in step 2) includes the steps: performing cooling to 125-135°C for filtration, adding diatomite into filtrate for stirring for 5-20 min under a heat preservation condition, performing filtration again, and then, performing reduced pressure distillation to remove the solvent completely, thereby completing the treatment.
[46] Compared with the prior art, the present invention achieves the beneficial effects as follows: deep research is made in the present invention on the synthesis of the bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and a new process of alcohol first followed by phenol (containing an acid-binding agent) for synthesizing the bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is found from results. By changing types of the acid-binding agent and the solvent, the second-step reaction (reaction between pentaerythritol dichlorodiphosphite solution and 2,6-di-tert-butyl-4-methylphenol) can be regulated and controlled to be performed efficiently, such that a yield can be greatly improved, reaction time can be shortened, purity of the product is improved, and implementation of industrial production of the bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite 1s facilitated.
BRIEF DESCRIPTION OF THE DRAWINGS
[47] FIG. 1 is a P31(CDCI3) spectrogram of a target product obtained from Example 1;
[48] FIG. 2 is a C13(CDCI3) spectrogram of a target product obtained from Example 1; and
[49] FIG. 3 is an infrared spectrogram of a target product obtained from Example 1.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[50] The present invention is further described below in conjunction with particular examples, but the protection scope of the present invention is not limited herein. [S1] Example 1:
H109WO8LU-PCT23019 30.06.2023
[52] A 1000 ml flask with five mouths was equipped with a stirrer, a nitrogen inlet LU103176 tube, a thermometer, a rectifying tube, and a cock (for sampling), then a moisture quantitative receiver and a cooling tube were further mounted at a tip of the rectifying tube, and the above devices were used as reaction devices. Pentaerythritol (13.6 g) serving as a raw material, xylene (200.0 g) serving as a solvent, and tripropylamine (0.3 g) serving as a catalyst were added to the flask, and phosphorus trichloride (27.4 g) serving as a raw material was added dropwise at a reaction temperature of 70°C under normal pressure.
After completion of the dropwise addition, a system was kept at a reaction temperature of 80°C, and the first-step reaction was performed while generated hydrogen chloride was removed out of the system. The first-step reaction was ended when the raw material was analyzed to be less than 1% by means of high performance liquid chromatography (HPLC), and first-step reaction time was 2.0 h. A polytetrafluoroethylene (PTFE) hose is used for introducing nitrogen below a liquid level, and stirring was performed to remove residual hydrogen chloride gas. Then, butylated hydroxytoluene (BHT) (57.3 g) was added to the system, and a mixture of tripropylamine and tributylamine (mass ratio tripropylamine/tributylamine=100/50, 33.0 g in total) as an acid-binding agent was added dropwise under normal pressure and at a temperature of 80°C. After the addition was completed, the system was gradually heated to reflux (>= 145°C) to perform a second-step reaction. The second-step was ended when a raw material was analyzed to be less than 1% by means of HPLC, and second-step reaction time was 4.0 h. Then, cooling was performed to 130°C for filtration, diatomite (5.0 g) was added into filtrate for stirring for 10 min at a temperature of 130°C, filtration was performed again, and then, reduced pressure distillation was performed to remove the solvent completely, thereby producing bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite serving as a target product.
A yield was 93%, and purity of 99.3% was determined by using a liquid chromatography method which was introduced in the master's degree thesis Study on synthesis process of antioxidant PEP-36 and dodecylphenol of Tianjin University of Science and Technology by YANG Teng.
[53] Identification of the target product of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite obtained in Example 1 was performed by means of nuclear 11
H109WO8LU-PCT23019 30.06.2023 magnetic resonance and infrared spectroscopy, and identification results were as follows: a LU103176
P31(CDCI3) spectrogram of the product is shown in FIG. 1, and chemical shifts of the phosphite compound are 122.58 ppm and 122.51 ppm, showing a doublet peak. A
C13(CDCI3) spectrogram is shown in FIG. 2, and chemical shifts of the mixture of the phosphite compound as the main component are 21.17 ppm, 31.83 ppm, 31.86 ppm, 35.31 ppm, 36.24 ppm, 36.28 ppm, 36.32 ppm, 63.75 ppm, 63.78 ppm, 63.94 ppm, 127.20 ppm, 132.26 ppm, 143.08 ppm, 143.11 ppm, 148.85 ppm, and 148.96 ppm. An infrared spectrogram is shown in FIG. 3, where 671 cm, 688 cml, 711 em”!, 736 cm‘, 767 em”, 783 em”! and 833 em”! are flexural vibration peaks of a benzene ring, and 2918 cm”! and 2956 cm”! are C-H stretching vibration peaks.
[54] Examples 2-6 and Comparative examples 1-3:
[55] Operating steps of Examples 2-6 and Comparative examples 1-3 are repetition of the operating steps of Example 1. Difference is only that a mass ratio of tripropylamine/tributylamine is adjusted and changed, where the total mass of added tripropylamine/tributylamine is maintained unchanged. In addition, data of the second-step reaction time recorded when the raw material is analyzed to be less than 1% by means of
HPLC in the second-step reaction of Examples 2-6 and Comparative examples 1-3 is summarized in Table 1. Reaction conditions changed accordingly and experimental results finally obtained are listed in Table 1.
[56] As shown in Table 1, the total reaction time is the sum of the first-step reaction time and the second-step reaction time. It can be seen that the ratio of tripropylamine/tributylamine has significant influence on the yield and purity of the product.
[57] Table 1. Influence of tertiary amine acid-binding agent component ratio on yield and purity of synthesized product ee
Tripropylamine/tributylamine yield purity | reaction mass ratio (%) (%) time (h) oe [En ee
Example ww Je we Jo 12
H109WO8LU-PCT23019 30.06.2023
Comparative example
[58] Comparative examples 4-6:
[59] Operating steps of Comparative examples 4-6 are repetition of the operating steps of Example 1. Difference is only that a temperature of a second-step reaction is adjusted.
As shown in Table 2, reaction conditions changed accordingly and experimental results finally obtained are listed in Table 2. It can be seen that changes of the reaction temperature has obvious influence on the yield and purity.
[60] Table 2. Influence of tertiary amine acid-binding agent component ratio on yield and purity of synthesized product
Reaction Second
Second step Product | Product temperature step
Control over yield purity (CC) Reaction reaction condition (%) (%) time (h)
Clee fr
Comparative example
Tes Jn we pw
[61] * represents that the raw material was found to be always higher than 1% by means of HPLC analysis, and the reaction was ended with 20 h.
[62] According to the experimental data, the new process of the invention greatly improves the yield of the synthetic reaction and the purity of the obtained product, and shortens the reaction time.
[63] The contents of this description are merely a list of the forms in which the invention concept is implemented, and the protection scope of the present invention should not be regarded as limited to the specific forms stated in the examples. 13

Claims (10)

H109WO8LU-PCT23019 30.06.2023 CLAIMS LU103176 WHAT IS CLAIMED IS:
1. A method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite, comprising the steps: completing a first- step reaction in a reaction solvent by taking pentaerythritol, phosphorus trichloride, and butylated hydroxytoluene (BHT) as raw materials and tripropylamine as a catalyst, where after the reaction, a feed liquid directly enters a next step; adding BHT serving a raw material into a system, and dropwise adding a tripropylamine-tributylamine mixture serving as an acid-binding agent for a second-step reaction; and performing post-treatment on the feed liquid after the reaction to obtain the high-efficiency phosphite antioxidant of bis(2,6-di-tert-butyl-4- methylphenyl) pentaerythritol diphosphite with a spiro structure, where a reaction formula is as follows: A aa — ee A Fd end Si A pot mt As te # % ; x 7 * + X à ; à F4 > à # el, Pros? ln) 2 AR SB
2. The method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 1, specifically comprising the following steps: 1) adding pentaerythritol, a reaction solvent and a tripropylamine catalyst into a reactor, dropwise adding phosphorus trichloride under normal pressure for a heating reaction, introducing nitrogen during a reaction process to remove generated hydrogen chloride out of the system, and detecting the reaction process by means of high performance liquid chromatography (HPLC) sampling analysis; and 2) after the reaction in 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 for the second-step reaction, detecting the reaction by means of the HPLC sampling 1
H109WO8LU-PCT23019 30.06.2023 analysis until the reaction is finished, and performing post-treatment on the feed liquid after the LU103176 reaction to obtain the target product.
3. The method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein in step 1), a mass ratio of the pentaerythritol to the tripropylamine catalyst is 30-80:1 and preferably 40- 50:1, and a mass ratio of the pentaerythritol to the phosphorus trichloride is 1:1.2-3 and preferably 1:1.5-2.
4. The method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein in step 1), a temperature of the mixed liquid in the reactor is 65-75°C when the phosphorus trichloride is added dropwise under normal pressure, and a reaction temperature is kept at 75-85°C after dropwise addition is finished; and first-step reaction time in step 1) is 1.5-2.5 h.
5. The method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein in step 1), the reaction solvent is xylene, and a mass ratio of the pentaerythritol to the reaction solvent is 1:8- and preferably 1:12-18.
6. The method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein a mass ratio of the BHT raw material in step 2) to the pentaerythritol in step 1) is 2-6:1 and preferably 4-
5:1.
7. The method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein a mass ratio of the acid-binding agent of tripropylamine-tributylamine mixture in step 2) to the pentaerythritol in step 1) is 1.5-5:1 and preferably 2-3:1.
8. The method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein in the acid- binding agent of tripropylamine-tributylamine mixture in step 2), a usage amount of tributylamine is 10-100 parts by mass, preferably 20-80 parts by mass, more preferably 30-70 parts by mass, and further preferably 40-60 parts by mass based on 100 parts of tripropylamine by mass.
9. The method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein in step 2), a temperature of the mixed liquid in the reactor is 75-85°C when the acid-binding agent is added dropwise, and a reaction temperature is controlled to be over 145°C after the dropwise addition 2
H109WO8LU-PCT23019 30.06.2023 is finished to reach a reflux state; and second-step reaction time of step 2) is 2.5-5 h. LU103176
10. The method for synthesizing a high-efficiency phosphite antioxidant of bis(2,6-di-tert- butyl-4-methylphenyl) pentaerythritol diphosphite according to claim 2, wherein the post- treatment in step 2) comprises the steps: performing cooling to 125-135°C for filtration, adding diatomite into filtrate for stirring for 5-20 min under a heat preservation condition, performing filtration again, and then, performing reduced pressure distillation to remove the solvent completely, thereby completing the treatment. 3
LU103176A 2022-12-09 2023-06-06 Method for synthesizing phosphite antioxidant of bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite LU103176B1 (en)

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