[go: up one dir, main page]

WO2019174360A1 - Procédé de synthèse d'antioxydant 1076 - Google Patents

Procédé de synthèse d'antioxydant 1076 Download PDF

Info

Publication number
WO2019174360A1
WO2019174360A1 PCT/CN2018/124803 CN2018124803W WO2019174360A1 WO 2019174360 A1 WO2019174360 A1 WO 2019174360A1 CN 2018124803 W CN2018124803 W CN 2018124803W WO 2019174360 A1 WO2019174360 A1 WO 2019174360A1
Authority
WO
WIPO (PCT)
Prior art keywords
tert
catalyst
reaction
butyl
hydroxyphenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/124803
Other languages
English (en)
Chinese (zh)
Inventor
郭骄阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Jiyi New Material Co Ltd
Original Assignee
Jiangsu Jiyi New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Jiyi New Material Co Ltd filed Critical Jiangsu Jiyi New Material Co Ltd
Publication of WO2019174360A1 publication Critical patent/WO2019174360A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group

Definitions

  • the invention relates to the field of organic chemical technology, in particular to an organic synthesis method of an antioxidant 1076, namely n-octadecanol 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
  • An antioxidant is an organic compound that inhibits or retards the thermal oxidation of high polymers and other organic compounds in the air. It is usually very effective by adding a small concentration of 1% antioxidant. For example, foods are susceptible to oxidative deterioration, and small amounts of antioxidants can be added to extend their storage time. Polymer materials such as plastics, synthetic fibers and rubber are prone to thermal oxygen degradation reaction. The addition of antioxidants can maintain the excellent properties of polymer materials and prolong the service life. The addition of antioxidants should be closer to the aging cycle, for example, in polymer drying. Before powdering
  • 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl ester which is an excellent unterminated hindered phenolic antioxidant with a white or yellowish solid powder. It is easily soluble in organic solvents such as benzene, chloroform, cyclohexane, acetone and esters. It is slightly soluble in ethylene glycol, ethanol and mineral oil. It is insoluble in water and can inhibit the oxidative degradation and thermal degradation of many organic compounds and polymers. It has been widely used in polyolefins, polyamides, polyesters, ABS resins, synthetic rubbers, greases, coatings, lubricants, etc., and is also suitable for certain food packaging materials. It has good compatibility, high anti-oxidation efficiency, no coloring, no pollution, washing resistance, extraction, heat resistance, low volatility, etc. It has synergistic effect with UV absorber.
  • the antioxidant 1076 has been industrially produced, the production process is old, the post-processing is complicated, the cost is high, and the pollutants are discharged.
  • sodium glycol sodium is used as a catalyst, and dimethyl sulfoxide is used as a solvent, and the reaction yield is low, which is generated by pollutants and pollutes the environment.
  • dioctyltin oxide as a catalyst, the reaction conditions are more moderate, the product yield is improved, the process is relatively simple, and environmentally friendly, but the use of the dioctyltin oxide catalyst in the preparation process is used.
  • the amount is 1.5% (mass fraction) of methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate, and the reaction temperature is also relatively high, which needs to reach 130-135 ° C, due to the comparison of catalyst prices. High, so the product yield is improved on the basis of reducing the amount of catalyst and lowering the reaction temperature. It has been reported that the laboratory yield of antioxidant 1076 can reach 97%, but it has been verified that the method is in the middle of the pilot process. For various practical reasons, the yield can only reach 70-80%, which means that there is still a certain gap between the effect achieved by the laboratory method and the effect achieved in actual production. Therefore, it is urgent to provide a method for improving the yield of the synthetic antioxidant 1076.
  • the present invention aims to provide an organic synthesis method in which the amount of the catalyst is small, the catalyst is cheap and easy to obtain, the reaction temperature is low, the purity of the obtained product is high, and the yield in the pilot test is still as high as 92% or more.
  • a method of synthesizing the n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate comprising the following synthetic route (A):
  • the method includes the following steps:
  • step (3) adding a certain amount of catalyst A to the reaction liquid of the step (2), and after reacting for one hour, adding an appropriate amount of the reactant stearyl alcohol, removing the ice bath, and placing the three-necked flask containing the reaction liquid in the oil bath. After reacting at 80-100 ° C for 3 hours, it was cooled to 60 ° C, crystallized, and suction filtered to give a product.
  • the solvent A is a mixed solution of ethylene glycol and toluene, and the ratio of the volume of the two is 1-5:10-200.
  • the solvent A used in the step (1) is a mixed solution of ethylene glycol and toluene in a volume ratio of 1:10.
  • the solvent A used in the step (1) is a mixed solution of ethylene glycol and toluene in a volume ratio of 2:100.
  • the solvent A used in the step (1) is a mixed solution of ethylene glycol and toluene in a volume ratio of 5:200.
  • the ratio of the amount of the reactant methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate in the above step (1) to the amount of the stearyl alcohol in the step (3) is 1-1.2:1.
  • the total mass of the reactant 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate in the above step (1) and the reactant stearyl alcohol in the step (3) and the total amount of the solvent The volume ratio is 6-12: 100-250 (g/mL).
  • the reaction time in the above step (2) in the ice bath condition is 10 to 30 min; preferably, 12 to 28 mim; further preferably 15 to 15 min.
  • the catalyst A added in the above step (3) may be selected from the group consisting of cesium carbonate, cesium carbonate, dibutyltin oxide, dibutyltin dilaurate, tributyltin acetate, tetramethyl titanate, tetrabutyl titanate, titanium.
  • the catalyst A added in the above step (3) may be selected from the group consisting of dibutyltin dilaurate, tributyltin acetate, tetramethyl titanate, tetrabutyl titanate, isobutyl titanate, zirconia and zirconium.
  • the catalyst A added in the above step (3) may be selected from one or more of tetramethyl titanate, tetrabutyl titanate, isobutyl titanate, zirconia and tetrabutyl zirconate. ;
  • the catalyst A added in the above step (3) may be selected from one or more of tetramethyl titanate, tetrabutyl titanate, isobutyl titanate and tetrabutyl zirconate.
  • the catalyst A in the step (3) is selected from the group consisting of tetrabutyl titanate and tetrabutyl zirconate in a mass ratio of 1:1.
  • the catalyst A in the step (3) is selected from the group consisting of tetramethyl titanate and tetrabutyl titanate in a mass ratio of 1:1.
  • the total amount of the catalyst used is 0.25-0.3% (mass fraction) of methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
  • the catalyst A when the mixed catalyst A is added, the catalyst A is added in stages, that is, in the step (3), first, half of the catalyst of the total amount of the catalyst A is added to the reaction liquid, and then the other half of the catalyst A is added after the addition of the stearyl alcohol. .
  • the present invention provides a method for synthesizing the above-mentioned starting material methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, the synthesis step is:
  • the reactant 2,6-di-tert-butylphenol and the catalyst B are added to a three-necked flask equipped with a N 2 gas pipe, a rotor and a dropping funnel, and melted under nitrogen gas protection and heating to obtain a reactant;
  • reaction temperature reaches 60-80 ° C
  • the reaction methyl ester is added dropwise to the reaction product of the step A.
  • the reaction is continued for 0.5 hour, and then the temperature is raised to 90-100 ° C to continue the reaction for 1 hour, followed by cooling.
  • the reaction solution is adjusted to neutral with hydrochloric acid, crystallized, and filtered to obtain a product;
  • the mass ratio of the reactant 2,6-di-tert-butylphenol in the above step A to the methyl acrylate of the reactant in the step B is 5:2.
  • the total amount of the catalyst B used in the above step B is 0.2 to 0.25% (mass fraction) of the total mass of the reactant 2,6-di-tert-butylphenol and methyl acrylate.
  • the catalyst B added in the above step B may be selected from one or more of zinc isooctanoate, zinc carbonate, zinc acetate, dibutyltin dilaurate, tributyltin acetate, stannous octoate and dibutyltin diacetate;
  • the catalyst B added in the above step B may be selected from one or more of zinc carbonate, zinc acetate, tributyltin acetate, stannous octoate and dibutyltin diacetate;
  • the catalyst B added in the above step B may be selected from one or more of zinc carbonate, zinc acetate, tributyltin acetate and stannous octoate;
  • the catalyst B in step B is selected from the group consisting of a mixture of zinc carbonate and tributyltin acetate in a mass ratio of 1:1.5.
  • the catalyst B in step B is selected from the group consisting of zinc acetate and stannous octoate in a mass ratio of 1:2.
  • the invention greatly improves the reaction efficiency and reduces the yield and purity of the reaction product by adjusting the kind of the reaction catalyst and the solvent required for the reaction, thereby reducing the amount of the catalyst, and does not generate polluting gas and pollutants, which is beneficial to the invention. protect environment. It provides a possibility for large-scale industrial production of n-octadecanol 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
  • V ethylene appears in the text to indicate the volume of ethylene glycol
  • V toluene represents the volume of toluene
  • Example 1 A method for synthesizing a raw material methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate
  • the final product yield was 99% and the purity without recrystallization was as high as 99.5%.
  • the catalysts used in Examples 2-5 were two catalysts with a mass ratio of 1:1.
  • Example 2 A method for synthesizing 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid n-octadecyl ester was synthesized as follows:
  • the final product yield is 98.5% and the purity is as high as 99.6%.
  • Example 3 A method for synthesizing 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid n-octadecyl ester was synthesized as follows:
  • the final product yield was 98.6% and the purity was as high as 99.7%.
  • Example 4 A method for synthesizing 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid n-octadecyl ester was synthesized as follows:
  • the final product yield was 99.2% and the purity was as high as 99.6%.
  • Example 5 A method for synthesizing 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl ester was synthesized as follows:
  • the final product yield was 99.6% and the purity was as high as 99.8%.
  • the catalyst used in Examples 6-9 is a catalyst
  • Example 6 A method for synthesizing 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid n-octadecyl ester was synthesized as follows:
  • the final product yield was 94.2% and the purity was as high as 97.4%.
  • Example 7 A method for synthesizing 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid n-octadecyl ester was synthesized as follows:
  • the final product yield was 95.2% and the purity was as high as 97.8%.
  • Example 8 A method for synthesizing 3-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. The synthesis steps are as follows:
  • a reaction product of methyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate (2.920 g) and ethylene glycol and toluene (V ethylene glycol : V toluene 1) were placed in a three-necked flask. 10) 200mL of the mixed solution, after adding the rotor, and the reflux condenser is fixed on the three-necked flask, vacuum treatment under nitrogen protection, cycle 3 times;
  • the final product yield was 93.9% and the purity was as high as 96.8%.
  • Example 9 A method for synthesizing 3-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. The synthetic steps are as follows:
  • a reaction product of methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate 7.018 g and ethylene glycol and toluene (V ethylene glycol : V toluene 1) were placed in a three-necked flask. 40) mixing the solution 250mL, after adding the rotor, and fixing the reflux condenser on the three-necked flask, vacuum treatment under nitrogen protection, cycle 3 times;
  • the final product yield was 94.5% and the purity was as high as 97.3%.
  • Comparative Example 1 A method for synthesizing 3-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate was synthesized as follows:
  • Example 5 The difference from Example 5 was that the solvent used in the step (1) was a single solvent ethylene glycol, and the other steps were the same as in the fifth embodiment.
  • the final product yield was 85.3% and the purity was as high as 92.4%.
  • Example 5 The difference from Example 5 was that the solvent used in the step (1) was a single solvent toluene, and the other steps were the same as in the example 5.
  • the final product yield was 85.7% and the purity was as high as 93.6%.
  • Example 5 The difference from Example 5 was that no vacuum treatment was carried out in the step (1), and the other steps were the same as in the fifth embodiment.
  • the final product yield was 83.6% and the purity was as high as 94.7%.
  • Example 5 The difference from Example 5 was that the catalyst was added in one step in the step (3), and the other steps were the same as in the example 5.
  • the final product yield was 85.6% and the purity was as high as 96.2%.
  • Example 5 The difference from Example 5 was that the mass ratio of the two catalysts in the step (3) was 1:4, and the other steps were the same as those in the example 5.
  • the final product yield was 80.4% and the purity was as high as 93.5%.
  • Example 5 The difference from Example 5 was that the mass ratio of the two catalysts in the step (3) was 5:1, and the other steps were the same as those in the example 5.
  • the final product yield was 81.4% and the purity was as high as 94.0%.
  • Methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate and stearyl alcohol, a catalyst and toluene were added to a three-necked flask equipped with a rotor and a thermometer, and a vacuum was applied through a nitrogen gas. The mixture was circulated three times, heated to 80 ° C for 5 hours, cooled to 60 ° C, crystallized, and suction filtered to obtain a product.
  • the final product yield was 83.2% and the purity was as high as 94.5%.
  • the preparation method for preparing the antioxidant 1076 provided by the present invention can be obtained, and the product yield can be as high as 93% or more, and the recrystallization purity can be as high as 96% or more.
  • the catalyst is mixed and used in the two catalysts provided by the present invention, and the mass ratio is controlled to be 1:1, which greatly improves the yield and purity of the antioxidant 1076.
  • the rate can be as high as 99.2%, the purity can be as high as 99.8%; and the two catalysts are also used in the comparative examples 5-6, but the mass ratio is different from the mass ratio provided by the invention, and the yield and purity are lower than only one kind Examples of the catalyst reaction (Examples 6-9) were 80.4%, 93.5% (Comparative Example 5), 81.4%, and 94.0% (Comparative Example 6), respectively; the catalysts provided by the present invention were used in Examples 6-9, respectively.
  • One of the preparation methods is the method provided by the present application, and the yield and purity of the antioxidant 1076 are still higher than the existing levels, the yield can be as high as 94%, and the purity is as high as 97.8%.
  • a pilot test of the antioxidant 1076 was carried out according to the method provided in Examples 2-9 of the present invention, and the yield of the finally obtained antioxidant 1076 was still above 90%, and the purity was as high as 99% or more, which was higher than the existing level, especially According to the pilot test conducted by the preparation method provided in Example 5, the yield of the antioxidant 1076 was over 92%, which provided a possibility for industrial mass production of antioxidants.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de synthèse d'antioxydant 1076 organique, qui est le 3(3,5-di-tert-butyl-4-hydroxyphényl) n-octadécanol propionate. Le procédé de préparation comprend les étapes suivantes consistant à : ajouter un catalyseur à une réaction avec un mélange d'éthylène glycol et de toluène servant de solvant, et avec du 3-(3,5-di-tert-butyl-4-hydroxyphényl))méthyl propionate et de l'octadécanol servant de réactifs, la réaction permet de produire du 3(3,5-di-tert-butyl-4-hydroxyphényl) n-octadécanol propionate. Dans la présente invention, le mélange sert de solvant et le catalyseur est ajouté en lots pendant le processus de réaction, la quantité du catalyseur utilisé est faible dans la réaction selon la présente invention pour la préparation de 3(3,5-di-tert-butyl-4-hydroxyphényl)) n-octadécanol propionate, la température de réaction est basse, la pureté du produit obtenu est élevée, et le rendement du procédé de synthèse organique est maintenu à 92 % ou plus pendant les tests pilotes.
PCT/CN2018/124803 2018-03-15 2018-12-28 Procédé de synthèse d'antioxydant 1076 Ceased WO2019174360A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810212587.0A CN108358781B (zh) 2018-03-15 2018-03-15 抗氧化剂1076合成工艺
CN201810212587.0 2018-03-15

Publications (1)

Publication Number Publication Date
WO2019174360A1 true WO2019174360A1 (fr) 2019-09-19

Family

ID=63000347

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/124803 Ceased WO2019174360A1 (fr) 2018-03-15 2018-12-28 Procédé de synthèse d'antioxydant 1076

Country Status (2)

Country Link
CN (1) CN108358781B (fr)
WO (1) WO2019174360A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292421A (zh) * 2021-06-09 2021-08-24 营口风光新材料股份有限公司 一种2，4，6-三羟基苯基甲酸丙二醇酯及其合成方法
CN113956163A (zh) * 2021-10-21 2022-01-21 盘锦新秀新材料有限公司 一种液体半对称受阻酚抗氧剂的合成生产方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109096102A (zh) * 2018-10-08 2018-12-28 天津工业大学 一种受阻酚类抗氧剂的合成技术
CN114790140A (zh) * 2022-04-01 2022-07-26 陕西艾科莱特新材料有限公司 一种抗氧剂1076的连续制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5081280A (en) * 1988-03-18 1992-01-14 Yoshitomi Pharmaceutical Industries, Ltd. Process for the production of ester compounds
CN105348103A (zh) * 2014-08-22 2016-02-24 天津市晨光化工有限公司 一种以新型含钛催化剂合成抗氧剂1076的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5081280A (en) * 1988-03-18 1992-01-14 Yoshitomi Pharmaceutical Industries, Ltd. Process for the production of ester compounds
CN105348103A (zh) * 2014-08-22 2016-02-24 天津市晨光化工有限公司 一种以新型含钛催化剂合成抗氧剂1076的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIU, TAO: "beta-(3, 5- (Study . on the Preparation of Octadecyl (3-(3, 5-di-tert-butyl-4-hydroxyphenyl) Propionate", CHINESE MASTER S THESES FULL-TEXT DATABASE , ENGINEERING SCIENCE & TECHNOLOGY 1., 15 April 2014 (2014-04-15), pages 22 - 24 ; 27-30 ; 47-50, ISSN: 1674-0246 *
LIU, TAO: "P- (3, 5- (Study on the Preparation of Octadecyl beta-(3, 5-di-tert-butyl-4-hydroxyphenyl) Propionate", CHINESE MASTER S THESES FULL-TEXT DATABASE, 15 April 2014 (2014-04-15), pages 22 - 24 ; 27-30 ; 47-50, ISSN: 1674-0246 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113292421A (zh) * 2021-06-09 2021-08-24 营口风光新材料股份有限公司 一种2，4，6-三羟基苯基甲酸丙二醇酯及其合成方法
CN113956163A (zh) * 2021-10-21 2022-01-21 盘锦新秀新材料有限公司 一种液体半对称受阻酚抗氧剂的合成生产方法

Also Published As

Publication number Publication date
CN108358781B (zh) 2019-02-19
CN108358781A (zh) 2018-08-03

Similar Documents

Publication Publication Date Title
WO2019174360A1 (fr) Procédé de synthèse d'antioxydant 1076
CN107849299A (zh) 增塑剂组合物和包含该增塑剂组合物的树脂组合物
CN101215235B (zh) 一种受阻酚类抗氧剂的合成方法
WO2019206199A1 (fr) Résine époxy hyper-ramifiée dégradable et procédé de préparation associé
CN108350154B (zh) 增塑剂组合物、树脂组合物及其制备方法
CN108699286A (zh) 增塑剂组合物和包含该增塑剂组合物的树脂组合物
TW201531458A (zh) 塑化劑和樹脂組成物及彼等之製備方法
WO2022156543A1 (fr) Antioxydant liquide composite et son procédé de préparation
CN1772829A (zh) 高稳定性无色松香季戊四醇酯及其制备方法
CN104370743A (zh) 增塑剂三乙二醇二异辛酸酯的制备方法
CN113004506A (zh) 一种耐热耐迁移的环保增塑剂的制备方法及其应用
CN109096102A (zh) 一种受阻酚类抗氧剂的合成技术
CN103288988A (zh) 苯乙烯化双酚a衍生物作为聚氯乙烯终止剂的制备方法
CN1192731A (zh) 酰胺基酯类化合物的制备
CN105542132A (zh) 一种低粘度水溶性聚酯树脂及其制备方法
CN114316474B (zh) 增塑剂组合物、树脂组合物及其制备方法
CN110511205A (zh) 一种高纯度乙交酯的制备方法
CN116532109B (zh) 一种负载型催化剂的制备方法及所得产品和应用
JPS62225558A (ja) 固状高分子安定剤化合物及びその製法
Zhang et al. Thermal antioxidation behavior of a new hindered phenol with branched structure for nitrile rubber
CN1927905A (zh) 杯芳烃[4]改性热固性酚醛树脂及其制备方法
CN116854593B (zh) 酯基化炔属硅氢加成抑制剂及制备方法和液体硅橡胶
CN1060200C (zh) 一种催化酯化松香的方法
CN101959839A (zh) 二羟基苯衍生物的制备方法
CN105153421B (zh) 一种制备四甲基哌啶氮氧自由基聚合物方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18909305

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18909305

Country of ref document: EP

Kind code of ref document: A1