JP7109697B1 - 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 PDFInfo
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- JP7109697B1 JP7109697B1 JP2022073706A JP2022073706A JP7109697B1 JP 7109697 B1 JP7109697 B1 JP 7109697B1 JP 2022073706 A JP2022073706 A JP 2022073706A JP 2022073706 A JP2022073706 A JP 2022073706A JP 7109697 B1 JP7109697 B1 JP 7109697B1
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- butyl
- tert
- hydroxyphenyl
- propionate
- methylene
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 55
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 35
- 230000008025 crystallization Effects 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000012043 crude product Substances 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- -1 alkyl propionate Chemical compound 0.000 abstract description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 abstract 2
- 235000019260 propionic acid Nutrition 0.000 abstract 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 8
- 239000012264 purified product Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
【課題】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。【解決手段】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を、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質量部とする。【選択図】なしA method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane having good properties is provided. SOLUTION: Tetrakis[methylene-3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane and 3-(3′,5′-tert-butyl-4′-hydroxyphenyl) 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionic acid contained in the crude product in the step of crystallizing the crude product containing alkyl propionate using a crystallization solvent The amount of alkyl is 1 to 7 parts by mass per 100 parts by mass of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane contained in the crude product. . [Selection figure] None
Description
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。 In Patent Document 1 below, tetrakis[methylene-3-(3′,5 A method for making '-tert-butyl-4'-hydroxyphenyl)propionate]methane is disclosed.
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。 Accordingly, 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 favorable 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 aimed at solving the above problems, the present inventors found that the above problems can be solved by setting the content ratio of the alkyl ester compound in the crude product to a specific numerical range in the crystallization step. The present invention has 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, comprising tetrakis[methylene-3-(3′,5 The crude product containing '-tert-butyl-4'-hydroxyphenyl)propionate]methane and alkyl 3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate was treated with 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 Tetrakis[methylene-3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane contained in the crude product is 1 to 7 parts by mass per 100 parts by mass. .
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 comprises a melting step of heating and melting the crude product to obtain a melt, and mixing the melt obtained in the melting step with the crystallization solvent. and 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。 Further, the production method of the present invention includes a reaction step of obtaining the crude product by transesterification reaction between alkyl 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate and pentaerythritol. preferably included.
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, the crystallization solvent preferably 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。 BEST MODE FOR CARRYING OUT THE INVENTION 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 comprises tetrakis[methylene-3-(3′,5′-tert- The crude product containing butyl-4′-hydroxyphenyl)propionate]methane and alkyl 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate was crystallized using a crystallization solvent. including 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 tetrakis[methylene- 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane is 1 to 7 parts by mass per 100 parts by mass.
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 crystal structure of δ crystal can be produced. Here, tetrakis [methylene-3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane, which has a crystal structure of δ crystal, has a crystal structure other than δ crystal such as α crystal, β crystal, etc. As compared with tetrakis[methylene-3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane, the properties such as powder fluidity are better. 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, the amount of alkyl 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate contained in the crude product in the crystallization step is Per 100 parts by mass of tetrakis [methylene-3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane contained in 1 to 6 parts by mass, preferably 1 to 5 It is more preferably 1 to 4 parts by mass, even more preferably 1 to 3 parts by mass.
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, an alkyl group having 1 to 6 carbon atoms may be used. Here, the alkyl group having 1 to 6 carbon atoms includes, for example, a linear alkyl group such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl branched alkyl groups such as isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and tert-amyl group; and cyclic alkyl groups such as cyclopentyl group and cyclohexyl group. From the viewpoint of improving the yield of the product, among these, a methyl group, an ethyl group, an n-propyl group and an isopropyl group are preferred, and a methyl group is particularly preferred.
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. One of these may be used alone, or two or more may be used in combination. The crystallization solvent may also 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 production method of the present embodiment, the crystallization solvent preferably contains alcohol from the viewpoint of obtaining a product having better properties and improving the yield of the product. More preferably, the crystallization solvent consists of alcohol alone or a mixture of alcohol and water, and 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. is more preferred. Furthermore, the crystallization solvent is preferably a mixture of methanol and water or a mixture of ethanol and water, 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 total crystallization solvent, and should be 3 to 30% by mass. is preferred, and 5 to 20% by mass is more preferred. 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 total crystallization solvent. Preferably, it is 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 with respect to 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 the present embodiment, the method for obtaining the crude product is not particularly limited, and a 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 by transesterification reaction between alkyl 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate and pentaerythritol. preferably included.
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 feed ratio of the raw materials, alkyl 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate and pentaerythritol, is, for example, 3-(3′,5 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 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 dimethylsulfoxide and dimethylformamide. Furthermore, the reaction step may be a solventless reaction that does not use a solvent. Here, in the reaction step, it is preferable to use an aliphatic hydrocarbon solvent as the solvent. In this case, the color tone of the obtained product is good.
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 solvent used is, for example, 5 to 5 of the theoretical yield of tetrakis[methylene-3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane. It may be 100% by mass, 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。 Examples of the catalyst used in the reaction step include lithium methoxide, lithium amide, lithium hydride, sodium methoxide, sodium amide, sodium hydride and the like. Among these, lithium methoxide is particularly preferred from the viewpoints of improving the color tone of the product, improving the yield of the product, and safety. The amount of catalyst used may be, for example, 0.01 to 0.5 mol per 1 mol of pentaerythritol as a starting material. Furthermore, the reaction temperature in the 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。 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, the reaction temperature, the pressure during the reaction, and the like. For example, by appropriately increasing the charged amount of alkyl 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate relative to the charged amount of pentaerythritol, 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. From the viewpoint of obtaining 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane, the crystallization step includes a melting step of heating and melting the crude product to obtain a melt, and a melting step of and a mixing step of mixing the melt and the crystallization solvent obtained in .
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。 The present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples below.
（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 1-7 and Comparative Examples 1-3)
Methyl 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate and pentaerythritol were placed in a 2-liter four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. Further, lithium methoxide was charged so as to be 8 mol% with respect to the charged amount of pentaerythritol, 26 g of an aliphatic hydrocarbon solvent (IP-1620, manufactured by Idemitsu Petrochemical Co., Ltd.) was added, and the temperature was 100 to 190 ° C. The mixture was stirred for 8 hours while the pressure was gradually reduced to 10 mmHg. Further, the pressure was reduced to 2 mmHg at 210.degree. Subsequently, while maintaining the reaction mixture at 70° C. or higher, 150 g of hydrous 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 and used as 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 added so that the total amount was 100 g. In Examples 1-7 and Comparative Examples 1-3, 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] 3 The charge 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" is 100 mass of tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane contained in the crude product. It represents the amount (parts by mass) of methyl 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate contained in the crude product per part. 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 quantified by a liquid chromatography method.
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 placed in a flask and heated in an oil bath to completely melt the crude products to obtain melts. After heating the resulting melt to 135° C., the flask was cooled in a hot water bath at 50° C., and while stirring the contents of the flask with a magnetic stirrer, 70 g of hydrous methanol containing 5% by mass of water was added to 30 ml of water. It was added dropwise over ~60 minutes. After the dropwise addition was completed, cooling and stirring were continued in a 50°C hot water bath, and seed crystals were added when the temperature of the contents of the flask reached 60°C. After adding seed crystals, the mixture was further stirred at 60° C. for 1 hour. Subsequently, the flask was removed from the hot water bath, and after stirring at room temperature of 20°C for 1 hour, the precipitated crystals were filtered, washed with 50 g of water-containing methanol containing 5% by mass of water, and heated to 80°C. After drying under reduced pressure at 1 kPa for 2 hours, a purified product of tetrakis[methylene-3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane was obtained.
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 crystalline 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 calorimeter (manufactured by Rigaku Co., Ltd., device name "Thermo plus Evo"), and heated from 50 ° C. to 130 ° C. at a rate of 5 ° C./min under a nitrogen atmosphere. A DSC curve was obtained at elevated temperatures. In the obtained DSC curve, when only the endothermic peak at 119 ° C. appears, it is assumed that the purified product consists only of δ crystal, and it is described as "δ crystal" in the column of crystal form in Tables 1 and 2, and 119 In addition to the endothermic peak at ° C., when other endothermic peaks appear, the purified product is assumed to be a mixture (mixed crystal) of δ crystal and crystals having a crystal form other than δ crystal, and the values shown in Tables 1 and 2 "Mixed crystal" is described 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 consisted 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 a crystal form 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。 As described above, according to the production method of the present invention, tetrakis[methylene-3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane which is composed only of δ crystals and has a crystal structure of δ crystals was confirmed to be able to produce That is, it was found that tetrakis[methylene-3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane having good properties can be produced according to the production method of the present invention. rice field.
Claims (5)
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
In the crystallization step, the amount of alkyl 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate contained in the crude product is equal to the amount of tetrakis[methylene- 3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane 1 to 7 parts by mass per 100 parts by mass.
The production method according to any one of claims 1 to 4, wherein the crystallization solvent contains alcohol.
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| JP2022114180A JP2023163103A (en) | 2022-04-27 | 2022-07-15 | Method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane |
| PCT/JP2023/016136 WO2023210589A1 (en) | 2022-04-27 | 2023-04-24 | Method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane |
| TW112115493A TW202400550A (en) | 2022-04-27 | 2023-04-26 | Method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane |
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| JP3284652B2 (en) | 1993-03-11 | 2002-05-20 | 松下電器産業株式会社 | air purifier |
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| JPS6013017B2 (en) * | 1980-01-14 | 1985-04-04 | 三井化学株式会社 | Method for producing 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 |
| JPH0657676B2 (en) * | 1986-04-30 | 1994-08-03 | ムサシノガイギ−株式会社 | Independent particle β-crystal tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane and method for producing the same |
| DE3868164D1 (en) * | 1987-02-03 | 1992-03-12 | Yoshitomi Pharmaceutical | METHOD FOR PRODUCING TETRAKIS (3- (3,5-DI-TERT-BUTYL-4-HYDROXYPHENYL) PROPIONYLOXYMETHYL) METHANE. |
| EP0366808B1 (en) * | 1988-03-31 | 1994-06-15 | Yoshitomi Pharmaceutical Industries, Ltd. | Method of crystallization and purification for obtaining stable crystalls of tetrakis 3-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionyloxymethyl- methane on an industrial scale |
| JP2736265B2 (en) * | 1989-06-08 | 1998-04-02 | 吉富製薬株式会社 | Method for producing α-crystal tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane having excellent powder properties |
| 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 |
| JP3215728B2 (en) * | 1992-10-15 | 2001-10-09 | 旭電化工業株式会社 | Method for producing tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane |
| 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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