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CN-122010877-A - Preparation method of ascorbyl tetraisopalmitate

CN122010877ACN 122010877 ACN122010877 ACN 122010877ACN-122010877-A

Abstract

The invention discloses a preparation method of ascorbyl tetraisopalmitate, which is characterized in that L-ascorbic acid and 2-hexyl decanal are used as raw materials, SO 4 2‑ /Fe 3 O 4 @TiO 2 -ZrO 2 is used as a main catalyst, GO-Cu-PMA is used as a cocatalyst, and the oxidation and esterification reaction is carried out in the presence of an oxidant to prepare the ascorbyl tetraisopalmitate, wherein the mass ratio of the main catalyst to the cocatalyst is (4.5-5.5): 1, and the oxidant is persulfate. The preparation method of the ascorbyl tetraisopalmitate provided by the invention has the advantages of mild reaction conditions, high reaction efficiency, simple preparation process, easiness in recovery of the catalyst, high product yield and purity, easiness in realization of large-scale production and extremely high industrial application value.

Inventors

  • WU JIANYU
  • SUN YUANYUAN
  • SUN JINZHONG
  • LU WEIMIN

Assignees

  • 安徽天寅生物技术有限公司

Dates

Publication Date
20260512
Application Date
20251226

Claims (10)

  1. 1. The preparation method of the ascorbyl tetraisopalmitate is characterized in that L-ascorbic acid and 2-hexyl decanal are used as raw materials, SO 4 2- /Fe 3 O 4 @TiO 2 -ZrO 2 is used as a main catalyst, GO-Cu-PMA is used as a cocatalyst, and the oxidation and esterification reaction is carried out in the presence of an oxidant to obtain the ascorbyl tetraisopalmitate, wherein the mass ratio of the main catalyst to the cocatalyst is (4.5-5.5): 1, and the oxidant is persulfate.
  2. 2. The preparation method of the tetraisopalmitate of ascorbic acid of claim 1, wherein the main catalyst SO 4 2- /Fe 3 O 4 @TiO 2 -ZrO 2 is prepared by taking Fe 3 O 4 as a core, coating a TiO 2 and ZrO 2 composite shell on the surface of Fe 3 O 4 to obtain Fe 3 O 4 @TiO 2 -ZrO 2 , and then carrying out sulfation treatment on the Fe 3 O 4 @TiO 2 -ZrO 2 , wherein the cocatalyst GO-Cu-PMA is prepared by firstly compositing graphene oxide GO with Cu 2+ to obtain a GO-Cu 2+ composite, then adopting a reducing agent to reduce Cu 2+ in the GO-Cu 2+ composite to form Cu + , and then carrying phosphomolybdic acid on the GO-Cu composite.
  3. 3. The method for preparing tetraisopalmitate ascorbate according to claim 2, characterized in that the preparation of the main catalyst SO 4 2- /Fe 3 O 4 @TiO 2 -ZrO 2 comprises the following steps: 1) Under the protection of nitrogen, dissolving ferric trichloride hexahydrate and ferrous chloride tetrahydrate in water, heating to 55-65 ℃, adding ammonia water, carrying out heat preservation and stirring reaction for 1-2 hours, ending the reaction, carrying out magnetic separation, washing and drying to obtain Fe 3 O 4 powder; 2) Uniformly dispersing Fe 3 O 4 powder in absolute ethyl alcohol, adding tetrabutyl titanate and zirconium oxychloride, stirring for 25-45 minutes, slowly dripping dilute nitric acid, stirring and gelling at 55-65 ℃ for 5-7 hours after dripping, ending the reaction, centrifugally separating, separating the obtained solid, washing, drying and roasting to obtain Fe 3 O 4 @TiO 2 -ZrO 2 ; 3) Soaking Fe 3 O 4 @TiO 2 -ZrO 2 in sulfuric acid water solution for 5-7 hr, filtering, drying, roasting, magnetic separation to obtain SO 4 2- /Fe 3 O 4 @TiO 2 -ZrO 2 .
  4. 4. The method for producing tetraisopalmitate of ascorbic acid according to claim 3, wherein in the step 1), the molar ratio of ferric trichloride hexahydrate to ferrous chloride tetrahydrate is 2:1, and in the step 2), the molar ratio of Fe 3 O 4 to tetrabutyl titanate to zirconium oxychloride is 1 (2-2.5): 2-2.5.
  5. 5. The method for preparing tetraisopalmitate ascorbate according to claim 2, characterized in that the preparation of the co-catalyst GO-Cu-PMA comprises the following steps: a) Dispersing graphene oxide in water to obtain GO dispersion liquid, adding copper nitrate trihydrate, and stirring at room temperature for 10-14 hours to obtain GO-Cu 2+ mixed liquid; b) Heating to 50-60 ℃, adding acetic acid, regulating the pH to 4.5+/-0.2, slowly dripping an aqueous solution of a reducing agent, and carrying out heat preservation reaction for 1-2 hours after the dripping is finished, wherein the color of the solution is gradually changed from blue-green to dark brown or dark green, so as to obtain a GO-Cu mixed solution; c) Adding phosphomolybdic acid, continuously preserving heat at 50-60 ℃ for 5-7 hours, ending the reaction, cooling to room temperature, collecting solid products, washing and drying to obtain GO-Cu-PMA.
  6. 6. The method for preparing tetraisopalmitate of ascorbic acid according to claim 5, wherein in the step a), the concentration of the GO dispersion liquid is 1.5-2.5mg/mL, the mass ratio of GO to copper nitrate trihydrate is 1 (0.5-0.7), in the step b), the reducing agent is L-ascorbic acid, the amount of the reducing agent is 55-65% of the molar amount of copper nitrate trihydrate, and in the step c), the amount of phosphomolybdic acid is 35-45% of the molar amount of copper nitrate trihydrate.
  7. 7. The method for producing tetraisopalmitate ascorbate according to claim 1, wherein the oxidizing agent is any one of ammonium persulfate, potassium persulfate and sodium persulfate.
  8. 8. The method for preparing tetraisopalmitate of ascorbic acid according to claim 1, wherein the molar ratio of L-ascorbic acid to 2-hexyl decanal is 1 (4-4.5), the molar ratio of oxidant to L-ascorbic acid is (2.5-3) 1, and the total amount of the catalyst is 5.5-6.5% of the mass of L-ascorbic acid.
  9. 9. The method for preparing ascorbyl tetraisopalmitate according to claim 1, characterized in that the preparation of ascorbyl tetraisopalmitate comprises the following steps: Dispersing L-ascorbic acid, 2-hexyl decanal, a main catalyst and a cocatalyst into ethyl acetate to form a suspension; Heating the suspension to 35-45 ℃, slowly dropwise adding an oxidant solution, after the dropwise adding, carrying out heat preservation and stirring reaction for 2-4 hours, ending the reaction, adding sodium bicarbonate aqueous solution to adjust the pH of the reaction system to 6.0+/-0.2, and carrying out heat preservation and stirring reaction for 14-16 hours to obtain the ascorbyl tetraisopalmitate.
  10. 10. The method for preparing tetraisopalmitate of ascorbic acid according to claim 9, wherein after the reaction is finished, the reaction liquid is magnetically separated, a main catalyst is separated, ethyl acetate is washed, a washing liquid is combined into the reaction liquid, the reaction liquid is filtered, a cocatalyst is recovered, the filtrate is transferred to a separating funnel, the filtrate is placed for layering, an organic phase is collected, washed, dried, filtered and distilled under reduced pressure, a crude product is obtained, and the crude product is recrystallized by n-hexane, so that the pure tetraisopalmitate of ascorbic acid is obtained.

Description

Preparation method of ascorbyl tetraisopalmitate Technical Field The invention relates to a preparation method of ascorbyl tetraisopalmitate, and belongs to the technical field of chemical synthesis. Background Ascorbyl tetraisopalmitate is an oil-soluble vitamin C derivative and has wide application in various fields, mainly in cosmetics and personal care products, and also in the fields of foods and medicines. In the cosmetic field, ascorbyl tetraisopalmitate is often used in products such as essence, emulsion, cream, spray, facial mask and the like, and plays roles of resisting oxidation, aging, whitening, moisturizing and the like, for example, the ascorbyl tetraisopalmitate can promote collagen synthesis, improve skin elasticity and compactness, reduce fine lines and wrinkles, inhibit melanin generation and help to even skin color. In the food industry, ascorbyl tetraisopalmitate can be used as an antioxidant to prolong the shelf life of foods, and is commonly used in oily foods, edible oils, baked goods and other scenes. In the field of medicine, the ascorbyl tetraisopalmitate can be used as a nutrition enhancer or an antioxidant additive and used in preparations such as ointments, capsules and the like. At present, the ascorbyl tetraisopalmitate is mainly prepared by a chemical catalysis method, wherein the selection of a catalyst has an important influence on the preparation method. At present, the preparation of the ascorbyl tetraisopalmitate usually takes concentrated sulfuric acid as a catalyst, and has the defects of low production efficiency, strong corrosiveness, high equipment requirement, dangerous operation, severe reaction heat release, difficult temperature control and the like. Disclosure of Invention The invention aims to solve the problems in the prior art and provide a preparation method of ascorbyl tetraisopalmitate. In order to achieve the above purpose, the present invention adopts the following technical scheme: The preparation method of the ascorbyl tetraisopalmitate is characterized in that L-ascorbic acid and 2-hexyl decanal are used as raw materials, SO 42-/Fe3O4@TiO2-ZrO2 is used as a main catalyst, GO-Cu-PMA (PMA is abbreviated as phosphomolybdic acid) is used as a cocatalyst, and the oxidation esterification reaction is carried out in the presence of an oxidant to prepare the ascorbyl tetraisopalmitate, wherein the mass ratio of the main catalyst to the cocatalyst is (4.5-5.5): 1, and the oxidant is persulfate. In one embodiment, the main catalyst SO 42-/Fe3O4@TiO2-ZrO2 is prepared by taking Fe 3O4 as a core, coating a composite shell of TiO 2 and ZrO 2 on the surface of Fe 3O4 to obtain Fe 3O4@TiO2-ZrO2, and then carrying out sulfation treatment on Fe 3O4@TiO2-ZrO2, wherein the cocatalyst GO-Cu-PMA is prepared by compounding graphene oxide GO with Cu 2+ to obtain a GO-Cu 2+ composite, then adopting a reducing agent to partially reduce Cu 2+ in the GO-Cu 2+ composite to Cu + to obtain a GO-Cu composite, and then loading phosphomolybdic acid on the GO-Cu composite. In a preferred embodiment, the preparation of the main catalyst SO 42-/Fe3O4@TiO2-ZrO2 comprises the following steps: 1) Under the protection of nitrogen, dissolving ferric trichloride hexahydrate and ferrous chloride tetrahydrate in water, heating to 55-65 ℃, adding ammonia water, carrying out heat preservation and stirring reaction for 1-2 hours, ending the reaction, carrying out magnetic separation, washing and drying to obtain Fe 3O4 powder; 2) Uniformly dispersing Fe 3O4 powder in absolute ethyl alcohol, adding tetrabutyl titanate and zirconium oxychloride, stirring for 25-45 minutes, slowly dripping dilute nitric acid, stirring and gelling at 55-65 ℃ for 5-7 hours after dripping, ending the reaction, centrifugally separating, separating the obtained solid, washing, drying and roasting to obtain Fe 3O4@TiO2-ZrO2; 3) Soaking Fe 3O4@TiO2-ZrO2 in sulfuric acid water solution for 5-7 hr, filtering, drying, roasting, magnetic separation to obtain SO 42-/Fe3O4@TiO2-ZrO2. In a preferred scheme, in the step 1), the mole ratio of ferric trichloride hexahydrate to ferrous chloride tetrahydrate is 2:1, and in the step 2), the mole ratio of Fe 3O4 to tetrabutyl titanate to zirconium oxychloride is 1 (2-2.5) to 2-2.5. In a preferred scheme, in the step 2), the roasting temperature is 540-560 ℃ and the roasting time is 3-5 hours, and in the step 3), the roasting temperature is 490-510 ℃ and the roasting time is 2-4 hours. In a preferred scheme, the preparation of the cocatalyst GO-Cu-PMA comprises the following steps: a) Dispersing graphene oxide in water to obtain GO dispersion liquid, adding copper nitrate trihydrate, and stirring at room temperature for 10-14 hours to obtain GO-Cu 2+ mixed liquid; b) Heating to 50-60 ℃, adding acetic acid, regulating the pH to 4.5+/-0.2, slowly dripping an aqueous solution of a reducing agent, and carrying out heat preservation reaction for 1-2 hours after the dripping is finished, wher