WO2023210589A1 - Method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane - Google Patents

Method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane Download PDF

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WO2023210589A1
WO2023210589A1 PCT/JP2023/016136 JP2023016136W WO2023210589A1 WO 2023210589 A1 WO2023210589 A1 WO 2023210589A1 JP 2023016136 W JP2023016136 W JP 2023016136W WO 2023210589 A1 WO2023210589 A1 WO 2023210589A1
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tert
butyl
hydroxyphenyl
propionate
methane
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Japanese (ja)
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健一 渡邊
暢彦 山ノ内
直輝 山本
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株式会社Adeka
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids

Definitions

  • the present invention relates to a method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having good properties.
  • Tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane is a compound widely used as an antioxidant for synthetic resins.
  • Patent Document 1 discloses that tetrakis[methylene-3-(3',5 A method for producing '-tert-butyl-4'-hydroxyphenyl)propionate]methane is disclosed.
  • Patent Document 1 the product manufactured by the manufacturing method described in Patent Document 1 has room for further improvement in properties such as powder fluidity.
  • an object of the present invention is to provide a method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having good properties.
  • the present invention provides a method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane, which comprises '-tert-butyl-4'-hydroxyphenyl)propionate] methane and alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate were purified using a crystallization solvent.
  • the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product is A production method in which the amount of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane contained in the crude product is 1 to 7 parts by weight per 100 parts by weight of methane. .
  • the crystallization step includes a melting step of heating and melting the crude product to obtain a melt, and mixing the melt obtained in the melting step and the crystallization solvent. It is preferable to include a mixing step.
  • the production method of the present invention includes a reaction step of obtaining the crude product by a transesterification reaction between alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol. It is preferable to include.
  • the crystallization solvent contains alcohol.
  • tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having good properties can be produced.
  • the method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane of the present embodiment includes tetrakis[methylene-3-(3',5'-tert- A crude product containing methane and alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate was crystallized using a crystallization solvent. This includes a crystallization step.
  • the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product is determined by the amount of tetrakis[methylene- The amount is 1 to 7 parts by weight per 100 parts by weight of 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane.
  • tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having a ⁇ crystal structure can be produced.
  • tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane, which has a ⁇ -crystal structure has a crystal structure other than ⁇ -crystal, such as ⁇ -crystal or ⁇ -crystal.
  • the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product is It is preferably 1 to 6 parts by mass, and preferably 1 to 5 parts by mass, per 100 parts by mass of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane contained in It is more preferably 1 to 4 parts by weight, even more preferably 1 to 3 parts by weight.
  • the alkyl group possessed by the alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product that is, the group represented by R in the following general formula (1)
  • any alkyl group having 1 to 6 carbon atoms may be used.
  • examples of the alkyl group having 1 to 6 carbon atoms include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group, and isopropyl group.
  • Examples include branched alkyl groups such as a group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-amyl group, and a cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group.
  • branched alkyl groups such as a group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-amyl group, and a cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group.
  • methyl, ethyl, n-propyl and isopropyl groups are preferred, with methyl being particularly preferred.
  • crystallization solvent used in the crystallization step examples include alcohols such as methanol, ethanol, n-propanol, and isopropanol, acetone, acetonitrile, tetrahydrofuran, dimethylformamide, dimethylacetamide, and dimethylsulfoxide. These may be used alone or in combination of two or more. Further, the crystallization solvent may be a mixture of the above solvent and water.
  • the crystallization solvent preferably contains alcohol from the viewpoint of obtaining a product with better properties and improving the yield of the product.
  • the crystallization solvent preferably consists of only alcohol or a mixture of alcohol and water, and even more preferably a mixture of alcohol and water.
  • the alcohol is preferably at least one selected from the group consisting of methanol, ethanol, n-propanol and isopropanol, more preferably at least one selected from the group consisting of methanol and ethanol, and is methanol. It is even more preferable.
  • the crystallization solvent is preferably a mixture of methanol and water or a mixture of ethanol and water, and particularly preferably a mixture of methanol and water.
  • the content of water in the crystallization solvent may be, for example, 1 to 50% by mass of the entire crystallization solvent, and should be 3 to 30% by mass.
  • the amount is preferably 5 to 20% by mass, and more preferably 5 to 20% by mass.
  • the crystallization solvent is a mixture of methanol and water, and the content of water in the crystallization solvent may be 1 to 50% by mass, preferably 3 to 30% by mass of the entire crystallization solvent. It is preferably 5 to 20% by mass, and more preferably 5 to 20% by mass.
  • the amount of the crystallization solvent used may be, for example, 100 to 500 parts by mass per 100 parts by mass of the crude product.
  • the method for obtaining the crude product is not particularly limited, and any known method can be used. It is preferably produced by a transesterification reaction between alkyl -4'-hydroxyphenyl)propionate and pentaerythritol. That is, the production method of the present embodiment includes a reaction step of obtaining a crude product through a transesterification reaction between alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol. It is preferable to include.
  • the charging ratio of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol, which are raw materials, is, for example, a molar ratio of 3-(3',5'-tert-butyl-4'-hydroxyphenyl)
  • the ratio of alkyl '-tert-butyl-4'-hydroxyphenyl)propionate/pentaerythritol may be 2/1 to 15/1, preferably 4/1 to 10/1.
  • the solvent used in the above reaction step examples include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, hexadecane, and cyclohexane, benzene, toluene, and xylene. , aromatic hydrocarbon solvents such as tetralin, and polar solvents such as dimethyl sulfoxide and dimethyl formamide.
  • the reaction step may be a solvent-free reaction without using a solvent.
  • the amount of the solvent used is, for example, 5 to 50% of the theoretical yield of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane. It may be 100% by mass, and preferably 10 to 40% by mass.
  • examples of the catalyst used in the above reaction step include lithium methoxide, lithium amide, lithium hydride, sodium methoxide, sodium amide, and sodium hydride.
  • lithium methoxide is particularly preferred from the viewpoint of improving the color tone of the product, improving the yield of the product, and from the viewpoint of safety.
  • the amount of the catalyst to be used may be, for example, 0.01 to 0.5 mol per 1 mol of pentaerythritol as a raw material.
  • the reaction temperature in the above reaction step may be, for example, 100 to 200°C, and the pressure during the reaction may be, for example, 1 to 110 kPa.
  • the 3-( The content of alkyl 3',5'-tert-butyl-4'-hydroxyphenyl)propionate can be controlled, for example, by adjusting the amount of raw materials charged, reaction temperature, pressure during reaction, and the like.
  • the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate charged can be increased.
  • the crude product and the crystallization solvent may be mixed and then heated to completely dissolve the crude product in the crystallization solvent, but tetrakis[methylene- From the viewpoint of obtaining methane (3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate), the crystallization process consists of a melting process in which a crude product is heated and melted to obtain a molten product, and a melting process. It is preferable that the method includes a mixing step of mixing the melt obtained in step 1 with a crystallization solvent.
  • the solvent was distilled off by reducing the pressure to 2 mmHg at 210° C., and then the mixture was cooled to 100° C., nitrogen was introduced from a nitrogen introduction tube to bring the pressure to normal pressure, and acetic acid was added to neutralize. Subsequently, while maintaining the reaction mixture at 70° C. or higher, 150 g of water-containing methanol containing 10% by mass of water was added, and the mixture was gradually cooled to 20° C. to precipitate a white solid. The precipitated white solid was dried to obtain a crude product.
  • methyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol were charged so that the total amount was 100 g.
  • the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product was Tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]propionate] 3 is added in an amount (parts by mass) shown in Tables 1 and 2 based on 100 parts by mass of methane.
  • the charging ratio of alkyl -(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol was adjusted.
  • AO-M refers to 100 mass of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane contained in the crude product. represents the amount (parts by mass) of methyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product.
  • the flask was taken out from the water bath and stirred at room temperature of 20°C for 1 hour, and the precipitated crystals were filtered. After washing the crystals with 50 g of aqueous methanol containing 5% by mass of water, the mixture was stirred at 80°C. The product was dried under reduced pressure at 1 kPa for 2 hours to obtain a purified product of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane.
  • the crystal form of the purified product thus obtained was determined by differential scanning calorimetry (DSC). Specifically, 1 mg of the purified product was introduced into a differential scanning calorimetry analyzer (manufactured by Rigaku Corporation, device name "Thermo plus Evo"), and heated from 50 °C to 130 °C at a heating rate of 5 °C/min under a nitrogen atmosphere. The temperature was increased and a DSC curve was obtained. If only an endothermic peak at 119°C appears in the obtained DSC curve, it is assumed that the purified product consists only of ⁇ crystals, and it is entered as “ ⁇ crystal” in the crystal form column of Tables 1 and 2.
  • DSC differential scanning calorimetry
  • the purified products of Examples 1 to 7 were composed only of ⁇ crystals.
  • the purified products of Comparative Examples 1 to 3 were mixtures (mixed crystals) of ⁇ crystals and crystals having crystal forms other than ⁇ crystals.

Abstract

Provided is a method for producing a tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having good properties.　In a process for crystallizing, by means of a crystallization solvent, a crude product including tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane and 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate alkyl, the amount of the 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate alkyl contained in the crude product is 1-7 parts by mass with respect to 100 parts by mass of the tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane contained in the crude product.

Description

テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンの製造方法Method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane
　本発明は、良好な性状を有するテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンの製造方法に関する。 The present invention relates to a method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having good properties.
　テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンは、合成樹脂用の酸化防止剤等として広く用いられている化合物である。 Tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane is a compound widely used as an antioxidant for synthetic resins.
　下記特許文献１には、３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸メチルとペンタエリスリトールとのエステル交換反応により、テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンを製造する方法が開示されている。 Patent Document 1 below discloses that tetrakis[methylene-3-(3',5 A method for producing '-tert-butyl-4'-hydroxyphenyl)propionate]methane is disclosed.
特開平４－２３４３４５号公報Japanese Patent Application Publication No. 4-234345
　しかしながら、上記特許文献１に記載の製造方法により製造された製品は、粉体流動性などの性状について、さらなる改善の余地があった。 However, the product manufactured by the manufacturing method described in Patent Document 1 has room for further improvement in properties such as powder fluidity.
　そこで、本発明の目的は、良好な性状を有するテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンの製造方法を提供することにある。 Therefore, an object of the present invention is to provide a method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having good properties.
　本発明者らは、上記課題を解決すべく鋭意検討した結果、晶析工程において、粗生成物中におけるアルキルエステル化合物の含有割合を特定の数値範囲とすることによって上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors found that the above problems could be solved by setting the content ratio of the alkyl ester compound in the crude product within a specific numerical range in the crystallization step, The present invention has now been completed.
　すなわち、本発明は、テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンの製造方法であって、テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンと３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルとを含む粗生成物を、晶析溶剤を用いて晶析する晶析工程を含み、前記晶析工程において、前記粗生成物に含まれる３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルの量が、前記粗生成物に含まれるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン１００質量部に対して１～７質量部である製造方法である。 That is, the present invention provides a method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane, which comprises '-tert-butyl-4'-hydroxyphenyl)propionate] methane and alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate were purified using a crystallization solvent. In the crystallization step, the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product is A production method in which the amount of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane contained in the crude product is 1 to 7 parts by weight per 100 parts by weight of methane. .
　本発明の製造方法においては、前記晶析工程が、前記粗生成物を加熱溶融して溶融物を得る溶融工程と、前記溶融工程で得られた前記溶融物と前記晶析溶剤とを混合する混合工程と、を含むことが好ましい。 In the production method of the present invention, the crystallization step includes a melting step of heating and melting the crude product to obtain a melt, and mixing the melt obtained in the melting step and the crystallization solvent. It is preferable to include a mixing step.
　また、本発明の製造方法は、３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルとペンタエリスリトールとのエステル交換反応により、前記粗生成物を得る反応工程を含むことが好ましい。 Furthermore, the production method of the present invention includes a reaction step of obtaining the crude product by a transesterification reaction between alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol. It is preferable to include.
　さらに、本発明の製造方法においては、前記晶析溶剤がアルコールを含むことが好ましい。 Furthermore, in the production method of the present invention, it is preferable that the crystallization solvent contains alcohol.
　本発明によれば、良好な性状を有するテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンを製造することができる。 According to the present invention, tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having good properties can be produced.
　以下、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　本実施形態のテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンの製造方法は、テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンと３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルとを含む粗生成物を、晶析溶剤を用いて晶析する晶析工程を含む。ここで、晶析工程において、粗生成物に含まれる３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルの量は、粗生成物に含まれるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン１００質量部に対して、１～７質量部である。 The method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane of the present embodiment includes tetrakis[methylene-3-(3',5'-tert- A crude product containing methane and alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate was crystallized using a crystallization solvent. This includes a crystallization step. Here, in the crystallization step, the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product is determined by the amount of tetrakis[methylene- The amount is 1 to 7 parts by weight per 100 parts by weight of 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane.
　本実施形態の製造方法によれば、結晶構造がδ晶であるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンを製造することができる。ここで、結晶構造がδ晶であるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンは、結晶構造がα晶、β晶などδ晶以外であるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンと比べ、粉体流動性などの性状が良好なものとなる。したがって、本実施形態の製造方法によれば、良好な性状を有するテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンを製造することができる。 According to the production method of the present embodiment, tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having a δ crystal structure can be produced. Here, tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane, which has a δ-crystal structure, has a crystal structure other than δ-crystal, such as α-crystal or β-crystal. Compared to tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane, which is Therefore, according to the production method of the present embodiment, tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having good properties can be produced.
　製品の収率を向上させる観点から、晶析工程において、粗生成物に含まれる３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルの量は、粗生成物に含まれるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン１００質量部に対して、１～６質量部であることが好ましく、１～５質量部であることがより好ましく、１～４質量部であることがさらに好ましく、１～３質量部であることがさらに一層好ましい。 From the viewpoint of improving the yield of the product, in the crystallization step, the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product is It is preferably 1 to 6 parts by mass, and preferably 1 to 5 parts by mass, per 100 parts by mass of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane contained in It is more preferably 1 to 4 parts by weight, even more preferably 1 to 3 parts by weight.
　粗生成物に含まれる３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルが有するアルキル基、すなわち、下記一般式（１）においてＲで表される基は、例えば、炭素原子数１～６のアルキル基であればよい。ここで、炭素原子数１～６のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基などの直鎖アルキル基、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－アミル基などの分岐を有するアルキル基、シクロペンチル基、シクロヘキシル基などの環状アルキル基などが挙げられる。製品の収率を向上させる観点から、これらの中では、メチル基、エチル基、ｎ－プロピル基、イソプロピル基が好ましく、メチル基が特に好ましい。 The alkyl group possessed by the alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product, that is, the group represented by R in the following general formula (1), For example, any alkyl group having 1 to 6 carbon atoms may be used. Here, examples of the alkyl group having 1 to 6 carbon atoms include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group, and isopropyl group. Examples include branched alkyl groups such as a group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-amyl group, and a cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group. From the viewpoint of improving the yield of the product, methyl, ethyl, n-propyl and isopropyl groups are preferred, with methyl being particularly preferred.
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-I000001
　晶析工程において用いられる晶析溶剤としては、例えば、メタノール、エタノール、ｎ－プロパノール、イソプロパノール等のアルコール、アセトン、アセトニトリル、テトラヒドロフラン、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシドなどが挙げられる。これらは一種が単独で用いられても、二種以上が組み合わせて用いられてもよい。また、晶析溶剤は、上記溶剤と水との混合物であってもよい。 Examples of the crystallization solvent used in the crystallization step include alcohols such as methanol, ethanol, n-propanol, and isopropanol, acetone, acetonitrile, tetrahydrofuran, dimethylformamide, dimethylacetamide, and dimethylsulfoxide. These may be used alone or in combination of two or more. Further, the crystallization solvent may be a mixture of the above solvent and water.
　本実施形態の製造方法において、より良好な性状を有する製品を得る観点、および、製品の収率を向上させる観点から、晶析溶剤は、アルコールを含むことが好ましい。晶析溶剤は、アルコールのみからなるか、または、アルコールと水との混合物であることがより好ましく、アルコールと水との混合物であることがさらに好ましい。ここで、アルコールは、メタノール、エタノール、ｎ－プロパノールおよびイソプロパノールからなる群より選ばれる少なくとも一種であることが好ましく、メタノールおよびエタノールからなる群より選ばれる少なくとも一種であることがより好ましく、メタノールであることがさらに好ましい。さらに、晶析溶剤は、メタノールと水との混合物、または、エタノールと水との混合物であることが好ましく、メタノールと水との混合物であることが特に好ましい。 In the manufacturing method of this embodiment, the crystallization solvent preferably contains alcohol from the viewpoint of obtaining a product with better properties and improving the yield of the product. The crystallization solvent preferably consists of only alcohol or a mixture of alcohol and water, and even more preferably a mixture of alcohol and water. Here, the alcohol is preferably at least one selected from the group consisting of methanol, ethanol, n-propanol and isopropanol, more preferably at least one selected from the group consisting of methanol and ethanol, and is methanol. It is even more preferable. Further, the crystallization solvent is preferably a mixture of methanol and water or a mixture of ethanol and water, and particularly preferably a mixture of methanol and water.
　晶析溶剤がアルコールと水との混合物である場合、晶析溶剤中における水の含有割合は、例えば、晶析溶剤全体の１～５０質量％であればよく、３～３０質量％であることが好ましく、５～２０質量％であることがより好ましい。晶析溶剤は、メタノールと水との混合物であって、晶析溶剤中における水の含有割合が、晶析溶剤全体の１～５０質量％であればよく、３～３０質量％であることが好ましく、５～２０質量％であることがより好ましい。なお、晶析工程において、晶析溶剤の使用量は、例えば、粗生成物１００質量部に対して１００～５００質量部であればよい。 When the crystallization solvent is a mixture of alcohol and water, the content of water in the crystallization solvent may be, for example, 1 to 50% by mass of the entire crystallization solvent, and should be 3 to 30% by mass. The amount is preferably 5 to 20% by mass, and more preferably 5 to 20% by mass. The crystallization solvent is a mixture of methanol and water, and the content of water in the crystallization solvent may be 1 to 50% by mass, preferably 3 to 30% by mass of the entire crystallization solvent. It is preferably 5 to 20% by mass, and more preferably 5 to 20% by mass. In the crystallization step, the amount of the crystallization solvent used may be, for example, 100 to 500 parts by mass per 100 parts by mass of the crude product.
　本実施形態の製造方法において、粗生成物を得る方法は特に限定されるものではなく、公知の方法を用いることができるが、粗生成物は、３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルとペンタエリスリトールとのエステル交換反応で製造されることが好ましい。すなわち、本実施形態の製造方法は、３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルとペンタエリスリトールとのエステル交換反応により、粗生成物を得る反応工程を含むことが好ましい。 In the production method of this embodiment, the method for obtaining the crude product is not particularly limited, and any known method can be used. It is preferably produced by a transesterification reaction between alkyl -4'-hydroxyphenyl)propionate and pentaerythritol. That is, the production method of the present embodiment includes a reaction step of obtaining a crude product through a transesterification reaction between alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol. It is preferable to include.
　上記反応工程において、原料である３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルおよびペンタエリスリトールの仕込み比は、例えば、モル比で３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキル／ペンタエリスリトールが２／１～１５／１であればよく、４／１～１０／１であることが好ましい。 In the above reaction step, the charging ratio of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol, which are raw materials, is, for example, a molar ratio of 3-(3',5'-tert-butyl-4'-hydroxyphenyl) The ratio of alkyl '-tert-butyl-4'-hydroxyphenyl)propionate/pentaerythritol may be 2/1 to 15/1, preferably 4/1 to 10/1.
　また、上記反応工程で使用される溶剤としては、例えば、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、トリデカン、テトラデカン、ヘキサデカン、シクロヘキサンなどの脂肪族炭化水素系溶剤、ベンゼン、トルエン、キシレン、テトラリンなどの芳香族炭化水素系溶剤、ジメチルスルホキシド、ジメチルホルムアミドなどの極性溶剤などが挙げられる。さらに、上記反応工程は、溶剤を使用しない、無溶剤での反応であってもよい。ここで、上記反応工程においては、溶剤として脂肪族炭化水素系溶剤を使用することが好ましい。この場合、得られる製品の色調が良好なものとなる。 Examples of the solvent used in the above reaction step include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, hexadecane, and cyclohexane, benzene, toluene, and xylene. , aromatic hydrocarbon solvents such as tetralin, and polar solvents such as dimethyl sulfoxide and dimethyl formamide. Furthermore, the reaction step may be a solvent-free reaction without using a solvent. Here, in the above reaction step, it is preferable to use an aliphatic hydrocarbon solvent as the solvent. In this case, the resulting product will have a good color tone.
　上記反応工程において溶剤を使用する場合、溶剤の使用量は、例えば、テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンの理論収量の５～１００質量％であればよく、１０～４０質量％であることが好ましい。 When a solvent is used in the above reaction step, the amount of the solvent used is, for example, 5 to 50% of the theoretical yield of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane. It may be 100% by mass, and preferably 10 to 40% by mass.
　また、上記反応工程で使用される触媒としては、例えば、リチウムメトキシド、リチウムアミド、水素化リチウム、ナトリウムメトキシド、ナトリウムアミド、水素化ナトリウムなどが挙げられる。製品の色調を良好なものとし、製品の収率を向上させる観点および安全性の観点から、これらの中では、リチウムメトキシドが特に好ましい。触媒の使用量は、例えば、原料のペンタエリスリトール１モルに対して０．０１～０．５モルであればよい。さらに、上記反応工程における反応温度は、例えば、１００～２００℃であればよく、反応時の圧力は、例えば、１～１１０ｋＰａであればよい。 Further, examples of the catalyst used in the above reaction step include lithium methoxide, lithium amide, lithium hydride, sodium methoxide, sodium amide, and sodium hydride. Among these, lithium methoxide is particularly preferred from the viewpoint of improving the color tone of the product, improving the yield of the product, and from the viewpoint of safety. The amount of the catalyst to be used may be, for example, 0.01 to 0.5 mol per 1 mol of pentaerythritol as a raw material. Further, the reaction temperature in the above reaction step may be, for example, 100 to 200°C, and the pressure during the reaction may be, for example, 1 to 110 kPa.
　粗生成物が、３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルとペンタエリスリトールとのエステル交換反応で製造される場合、粗生成物に含まれる３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルの含有量は、例えば、原料の仕込み量や反応温度、反応時の圧力などを調整することなどによって制御できる。例えば、ペンタエリスリトールの仕込み量に対する３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルの仕込み量を適宜増大させることにより、粗生成物に含まれる３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルの含有量を増大させることができる。 When the crude product is produced by the transesterification reaction of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate with pentaerythritol, the 3-( The content of alkyl 3',5'-tert-butyl-4'-hydroxyphenyl)propionate can be controlled, for example, by adjusting the amount of raw materials charged, reaction temperature, pressure during reaction, and the like. For example, by appropriately increasing the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate charged relative to the amount of pentaerythritol charged, the amount of 3-(3 The content of alkyl ',5'-tert-butyl-4'-hydroxyphenyl)propionate can be increased.
　晶析工程においては、粗生成物と晶析溶剤とを混合した後、加熱して、粗生成物を晶析溶剤に完全に溶解させてもよいが、より良好な性状を有するテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンを得る観点から、晶析工程は、粗生成物を加熱溶融して溶融物を得る溶融工程と、溶融工程で得られた溶融物と晶析溶剤とを混合する混合工程と、を含むものであることが好ましい。 In the crystallization step, the crude product and the crystallization solvent may be mixed and then heated to completely dissolve the crude product in the crystallization solvent, but tetrakis[methylene- From the viewpoint of obtaining methane (3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate), the crystallization process consists of a melting process in which a crude product is heated and melted to obtain a molten product, and a melting process. It is preferable that the method includes a mixing step of mixing the melt obtained in step 1 with a crystallization solvent.
　以下、実施例を挙げて、本発明をさらに具体的に説明するが、本発明は以下の実施例によって何ら制限を受けるものではない。 Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited in any way by the following Examples.
（実施例１～７および比較例１～３）
　攪拌機、還流冷却器、温度計および窒素導入管を備えた容量２リットルの４口フラスコに、３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸メチルおよびペンタエリスリトールを仕込み、さらに、リチウムメトキシドをペンタエリスリトールの仕込み量に対して８モル％になるように仕込み、脂肪族炭化水素系溶媒（ＩＰ－１６２０　出光石油化学社製）２６ｇを加えて、１００～１９０℃で１０ｍｍＨｇまで徐々に減圧しながら８時間攪拌した。さらに、２１０℃で２ｍｍＨｇまで減圧して溶媒を留去した後、１００℃まで冷却し、窒素導入管から窒素を導入して常圧にした後、酢酸を加えて中和した。続いて、反応混合物を７０℃以上に保ちながら水を１０質量％含有する含水メタノールを１５０ｇ加え、２０℃まで徐々に冷却し、白色固体を析出させた。析出した白色固体を乾燥させ、これを粗生成物とした。 (Examples 1 to 7 and Comparative Examples 1 to 3)
Methyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol were added to a 2 liter 4-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. Further, lithium methoxide was added to the amount of pentaerythritol to make it 8 mol%, 26 g of aliphatic hydrocarbon solvent (IP-1620 manufactured by Idemitsu Petrochemical Co., Ltd.) was added, and the mixture was heated at 100 to 190°C. The mixture was stirred for 8 hours while gradually reducing the pressure to 10 mmHg. Further, the solvent was distilled off by reducing the pressure to 2 mmHg at 210° C., and then the mixture was cooled to 100° C., nitrogen was introduced from a nitrogen introduction tube to bring the pressure to normal pressure, and acetic acid was added to neutralize. Subsequently, while maintaining the reaction mixture at 70° C. or higher, 150 g of water-containing methanol containing 10% by mass of water was added, and the mixture was gradually cooled to 20° C. to precipitate a white solid. The precipitated white solid was dried to obtain a crude product.
　ここで、３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸メチルおよびペンタエリスリトールは、合計が１００ｇとなるように仕込んだ。実施例１～７および比較例１～３において、粗生成物に含まれる３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルの量が、粗生成物に含まれるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン１００質量部に対して表１～２に示す量（質量部）となるように、３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルおよびペンタエリスリトールの仕込み比を調整した。 Here, methyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol were charged so that the total amount was 100 g. In Examples 1 to 7 and Comparative Examples 1 to 3, the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product was Tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]propionate] 3 is added in an amount (parts by mass) shown in Tables 1 and 2 based on 100 parts by mass of methane. The charging ratio of alkyl -(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol was adjusted.
　ここで、表１～２において、「ＡＯ－Ｍ」は、粗生成物に含まれるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン１００質量部に対する、粗生成物に含まれる３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸メチルの量（質量部）を表す。なお、実施例１～７および比較例１～３において、粗生成物に含まれるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンおよび３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸メチルの量は、液体クロマトグラフィー法によって定量した。 Here, in Tables 1 and 2, "AO-M" refers to 100 mass of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane contained in the crude product. represents the amount (parts by mass) of methyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product. In Examples 1 to 7 and Comparative Examples 1 to 3, tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane and 3- The amount of methyl (3',5'-tert-butyl-4'-hydroxyphenyl)propionate was determined by liquid chromatography.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例１～７および比較例１～３の粗生成物５０ｇをフラスコに仕込み、オイルバスで加熱して粗生成物を完全に溶融させて溶融物を得た。得られた溶融物を１３５℃に昇温した後、５０℃の湯浴でフラスコを冷却し、フラスコの内容物をマグネチックスターラーで撹拌しながら、水を５質量％含有する含水メタノール７０ｇを３０～６０分かけて滴下した。滴下終了後、５０℃の湯浴中で冷却撹拌を続け、フラスコの内容物の温度が６０℃になった時点で種結晶を添加した。種結晶を添加した後、さらに６０℃で１時間撹拌した。続いて、フラスコを湯浴から取り出して、２０℃の室温下で１時間撹拌した後、析出した結晶をろ過し、水を５質量％含有する含水メタノール５０ｇで結晶を洗浄した後、８０℃、１ｋＰａで２時間減圧乾燥して、テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンの精製製品を得た。 50 g of the crude products of Examples 1 to 7 and Comparative Examples 1 to 3 were charged into a flask and heated in an oil bath to completely melt the crude products to obtain a melt. After heating the resulting melt to 135°C, the flask was cooled in a 50°C water bath, and while stirring the contents of the flask with a magnetic stirrer, 30 g of water-containing methanol containing 5% by mass of water was added. It was added dropwise over ~60 minutes. After the dropwise addition was completed, cooling and stirring were continued in a 50°C water bath, and when the temperature of the contents of the flask reached 60°C, seed crystals were added. After adding the seed crystals, the mixture was further stirred at 60°C for 1 hour. Subsequently, the flask was taken out from the water bath and stirred at room temperature of 20°C for 1 hour, and the precipitated crystals were filtered. After washing the crystals with 50 g of aqueous methanol containing 5% by mass of water, the mixture was stirred at 80°C. The product was dried under reduced pressure at 1 kPa for 2 hours to obtain a purified product of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane.
　こうして得られた精製製品の結晶形を、示差走査熱分析（ＤＳＣ）によって決定した。具体的には、精製製品１ｍｇを示差走査熱分析装置（リガク社製、装置名「Ｔｈｅｒｍｏ　ｐｌｕｓ　Ｅｖｏ」）に導入し、窒素雰囲気下、５０℃から５℃／分の昇温速度で１３０℃まで昇温して、ＤＳＣ曲線を得た。得られたＤＳＣ曲線において、１１９℃の吸熱ピークのみが出現する場合、精製製品はδ晶のみからなるものであるとして、表１～２の結晶形の欄に「δ晶」と記載し、１１９℃の吸熱ピークに加えて、これ以外の吸熱ピークが出現する場合、精製製品はδ晶と、δ晶以外の結晶形を有する結晶との混合物（混晶）であるとして、表１～２の結晶形の欄に「混晶」と記載した。なお、精製製品の結晶形は、粉末Ｘ線回折（ＸＲＤ）および赤外分光分析（ＩＲ）によっても確認した。 The crystal form of the purified product thus obtained was determined by differential scanning calorimetry (DSC). Specifically, 1 mg of the purified product was introduced into a differential scanning calorimetry analyzer (manufactured by Rigaku Corporation, device name "Thermo plus Evo"), and heated from 50 °C to 130 °C at a heating rate of 5 °C/min under a nitrogen atmosphere. The temperature was increased and a DSC curve was obtained. If only an endothermic peak at 119°C appears in the obtained DSC curve, it is assumed that the purified product consists only of δ crystals, and it is entered as “δ crystal” in the crystal form column of Tables 1 and 2. If other endothermic peaks appear in addition to the endothermic peak at "Mixed crystal" was written in the crystal form column. The crystal form of the purified product was also confirmed by powder X-ray diffraction (XRD) and infrared spectroscopy (IR).
　表１～２に示す結果より、実施例１～７の精製製品は、δ晶のみからなるものであった。一方、比較例１～３の精製製品は、δ晶と、δ晶以外の結晶形を有する結晶との混合物（混晶）であった。 From the results shown in Tables 1 and 2, the purified products of Examples 1 to 7 were composed only of δ crystals. On the other hand, the purified products of Comparative Examples 1 to 3 were mixtures (mixed crystals) of δ crystals and crystals having crystal forms other than δ crystals.
　以上より、本発明の製造方法によれば、δ晶のみからなり結晶構造がδ晶であるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンを製造することができることが確認された。すなわち、本発明の製造方法によれば、良好な性状を有するテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンを製造することができることがわかった。 From the above, according to the production method of the present invention, tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane, which consists only of δ crystals and has a crystal structure of δ crystals, It was confirmed that it can be manufactured. That is, it has been found that according to the production method of the present invention, tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having good properties can be produced. Ta.

Claims (5)

  1. 　テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンの製造方法であって、
    　テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタンと３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルとを含む粗生成物を、晶析溶剤を用いて晶析する晶析工程を含み、
    　前記晶析工程において、前記粗生成物に含まれる３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルの量が、前記粗生成物に含まれるテトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン１００質量部に対して１～７質量部である製造方法。     A method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane, comprising:
    Tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane and alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate A crystallization step of crystallizing a crude product containing using a crystallization solvent,
    In the crystallization step, the amount of alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate contained in the crude product is greater than the amount of tetrakis[methylene- A method for producing 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate] in an amount of 1 to 7 parts by weight per 100 parts by weight of methane.
  2. 　前記晶析工程が、前記粗生成物を加熱溶融して溶融物を得る溶融工程と、前記溶融工程で得られた前記溶融物と前記晶析溶剤とを混合する混合工程と、を含む請求項１記載の製造方法。 A claim in which the crystallization step includes a melting step of heating and melting the crude product to obtain a melt, and a mixing step of mixing the melt obtained in the melting step and the crystallization solvent. 1. The manufacturing method described in 1.
  3. 　３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルとペンタエリスリトールとのエステル交換反応により、前記粗生成物を得る反応工程を含む請求項１記載の製造方法。 2. The production method according to claim 1, comprising a reaction step of obtaining the crude product by a transesterification reaction between alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol.
  4. 　３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオン酸アルキルとペンタエリスリトールとのエステル交換反応により、前記粗生成物を得る反応工程を含む請求項２記載の製造方法。 3. The production method according to claim 2, comprising a reaction step of obtaining the crude product by a transesterification reaction between alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate and pentaerythritol.
  5. 　前記晶析溶剤がアルコールを含む請求項１～４のうちいずれか一項記載の製造方法。 The manufacturing method according to any one of claims 1 to 4, wherein the crystallization solvent contains alcohol.
PCT/JP2023/016136 2022-04-27 2023-04-24 Method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane WO2023210589A1 (en)

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JPS62201846A (en) * 1986-02-28 1987-09-05 Mitsui Petrochem Ind Ltd Production of fine particle of tetrakis (3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl)metha-ne
JPS62258343A (en) * 1986-04-30 1987-11-10 Musashino Geigy Kk Independent particulate beta-crystal tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl)-methane and production thereof
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JPH03284652A (en) * 1990-03-30 1991-12-16 Kokusai Kagaku Gijutsu Consultant Kk Granular tetrakis(3-(3,5-dibutyl-4-hydroxyphenyl) propionyloxymethyl)methane improved in coloring and production thereof
JPH0648988A (en) * 1992-07-29 1994-02-22 Dainippon Ink & Chem Inc Production of tetrakis(3-@(3754/24)3,5-dialkyl-4--hydroxyphenyl) propionyloxyalkyl) methane
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JPH0840984A (en) * 1994-08-03 1996-02-13 Asahi Denka Kogyo Kk Method for granulating tetrakis(9146/28)3-(3',5'-di-tertiary butyl-4'-hydroxyphenyl) propionyloxymethyl(9147/28)methane

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JPS5699444A (en) * 1980-01-14 1981-08-10 Mitsui Petrochem Ind Ltd Preparation of tetrakis 3- 3,5-di-t-butyl-4-hydroxyphenyl propionyloxymethyl methane
JPS62201846A (en) * 1986-02-28 1987-09-05 Mitsui Petrochem Ind Ltd Production of fine particle of tetrakis (3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl)metha-ne
JPS62258343A (en) * 1986-04-30 1987-11-10 Musashino Geigy Kk Independent particulate beta-crystal tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl)-methane and production thereof
WO1988005773A1 (en) * 1987-02-03 1988-08-11 Yoshitomi Pharmaceutical Industries, Ltd. Process for preparing tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl)methane
WO1989009202A1 (en) * 1988-03-31 1989-10-05 Yoshitomi Pharmaceutical Industries, Ltd. METHOD OF CRYSTALLIZATION AND PURIFICATION FOR OBTAINING STABE beta CRYSTAL OF TETRAKIS[3-(3,5-DI-TERTIARY-BUTYL-4-HYDROXYPHENYL)PROPIONYLOXYMETHYL]METHANE ON AN INDUSTRIAL SCALE
JPH0311038A (en) * 1989-06-08 1991-01-18 Yoshitomi Pharmaceut Ind Ltd Alpha crystal tetrakis(3-(3,5-di-tert.-butyl-4-hydroxyphenyl) propionyloxymethyl)methane having excellent powder characteristic and production thereof
JPH03284652A (en) * 1990-03-30 1991-12-16 Kokusai Kagaku Gijutsu Consultant Kk Granular tetrakis(3-(3,5-dibutyl-4-hydroxyphenyl) propionyloxymethyl)methane improved in coloring and production thereof
JPH0648988A (en) * 1992-07-29 1994-02-22 Dainippon Ink & Chem Inc Production of tetrakis(3-@(3754/24)3,5-dialkyl-4--hydroxyphenyl) propionyloxyalkyl) methane
JPH06128195A (en) * 1992-10-15 1994-05-10 Asahi Denka Kogyo Kk Production of tetrakis(3-@(3754/24)3,5-di-tertiary-butyl-4-hydroxyphenyl)propionyloxymethyl)methane
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