阅读说明：本技术 一种用于生产化妆品用甲基柏木酮的方法 (Method for producing methyl cedryl ketone for cosmetics ) 是由 李金国 于 2020-08-04 设计创作，主要内容包括：本发明公开了一种用于生产化妆品用甲基柏木酮的方法,将醋酐和柏木烯混合均匀加入到微波反应器中,通入氮气后加催化剂反应,反应结束后,将催化剂分离并将所得的产物经精馏操作后得到甲基柏木酮成品；通过PO<Sub>4</Sub><Sup>3-</Sup>/MCM-41固体磷酸的制备、离子液体前驱体TEAPS的制备、Zr基固态离子液体的原位负载得到以具有强稳定性能的固体磷酸PO<Sub>4</Sub><Sup>3-</Sup>/MCM-41与Zr基固态离子液体相结合的复合催化剂。本发明所制备的复合催化剂既能解决催化剂与产物分离困难的问题,又能解决催化剂酸性容易流失造成催化剂失活的不足,同时所制备的催化剂能保持固体状态,其对反应装置无腐蚀性、催化效率高且主产物选择性好。(The invention discloses a method for producing methyl cedryl ketone for cosmetics, which comprises the steps of uniformly mixing acetic anhydride and cedryl alkene, adding the mixture into a microwave reactor, introducing nitrogen, adding a catalyst for reaction, separating the catalyst after the reaction is finished, and rectifying the obtained product to obtain a finished product of the methyl cedryl ketone; by PO 4 3‑ Preparation of MCM-41 solid phosphoric acid, preparation of ionic liquid precursor TEAPS, in-situ loading of Zr-based solid ionic liquid to obtain solid phosphoric acid PO with strong stability 4 3‑ The composite catalyst combines MCM-41 and Zr-based solid ionic liquid. The composite catalyst prepared by the invention can solve the problem of difficult separation of the catalyst and the productAnd the defect that the catalyst is easy to lose acidity and inactivate is overcome, and the prepared catalyst can keep a solid state, has no corrosion to a reaction device, is high in catalytic efficiency and good in selectivity of a main product.)

1. A method for producing methyl cedryl ketone for cosmetics is characterized in that: uniformly mixing acetic anhydride and cedrene, adding into a microwave reactor, introducing nitrogen for 30min, adding a catalyst, reacting the reaction mixture at 90 ℃ for 5h, and cooling to room temperature; after centrifugally separating the catalyst, rectifying the obtained product to obtain a finished product of the methyl cedryl ketone; the catalyst is prepared from PO₄ ^3-The catalyst comprises MCM-41 solid phosphoric acid and Zr-based solid ionic liquid, wherein the mass fraction of the Zr-based solid ionic liquid in the catalyst is 45-55 wt%, and the Zr-based solid ionic liquid is Zr_0.25[TEAPS]₃SiW₁₂O₄₀、Zr_0.50[TEAPS]₂SiW₁₂O₄₀、Zr_0.75[TEAPS]SiW₁₂O₄₀、Zr_0.25[TEAPS]₂HSiW₁₂O₄₀One kind of (1).

2. The process for producing methyl cedryl ketone for cosmetics according to claim 1, characterized in that: the catalyst is realized by the following specific steps:

（1）PO₄ ^3-preparation of MCM-41 solid phosphoric acid

Firstly, MCM-41 molecular sieve is ultrasonically dispersed into deionized water, then pyrophosphoric acid is added into the deionized water, the mixture is continuously stirred for 2 hours at room temperature, then the mixture is evaporated to dryness under the condition of 70 ℃ water bath, the material obtained by evaporation to dryness is roasted for 5 hours at 500 ℃ to obtain PO₄ ^3-PO in an amount of 10 to 25wt%₄ ^3-MCM-41 solid phosphoric acid;

(2) preparation of ionic liquid precursor TEAPS

Adding triethylamine and p-xylene into a microwave reactor, stirring and dissolving, then introducing nitrogen for 1h, opening the microwave reactor, keeping the power at 200-300W, then dropwise adding 1, 3-propane sultone into the mixture, reacting for 1-2 h to obtain a mixture, centrifuging and washing the obtained mixture, and drying at 90 ℃ for 12h to obtain an ionic liquid precursor, which is marked as TEAPS;

(3) in-situ loading of Zr-based solid ionic liquid

To PO₄ ^3-adding/MCM-41 solid phosphoric acid, silicotungstic acid, zirconium oxychloride and TEAPS into deionized water to obtain a mixture, stirring at room temperature for 30min, transferring the mixture into a microwave reactor, reacting for 4-8 h at 200-300W, and then sequentially centrifuging, washing and drying to obtain a composite catalyst of the solid phosphoric acid and the Zr-based solid ionic liquid; wherein Zr-based solid ionic liquid prepared from silicotungstic acid, zirconium oxychloride and TEAPS in the reaction process is Zr_0.25[TEAPS]₃SiW₁₂O₄₀、Zr_0.50[TEAPS]₂SiW₁₂O₄₀、Zr_0.75[TEAPS]SiW₁₂O₄₀、Zr_0.25[TEAPS]₂HSiW₁₂O₄₀One kind of (1).

3. The process for producing methyl cedryl ketone for cosmetics according to claim 1, characterized in that: the mass ratio of the acetic anhydride to the cedrene is (0.6-1.0) to 1; the mass ratio of the catalyst to the cedrene is 1 (25-40).

4. The process for producing methyl cedryl ketone for cosmetics according to claim 2, characterized in that: in the step (2), the mass ratio of triethylamine to 1, 3-propane sultone is 1:1, and the mass concentration of triethylamine in p-xylene is 0.1 mol/L.

5. The process for producing methyl cedryl ketone for cosmetics according to claim 2, characterized in that: in the step (3), the mass ratio of TEAPS to silicotungstic acid is (1-3): 1, the mass ratio of zirconium oxychloride to silicotungstic acid is (0.25-0.75): 1, and the mass fraction of Zr-based solid ionic liquid in the composite catalyst is 45-55 wt%.

Technical Field

The invention belongs to the technical field of cosmetics, relates to a preparation method of a perfume for cosmetics, and particularly relates to a method for producing methyl cedryl ketone for cosmetics.

Background

The methyl cedryl ketone is a classic spice with costustoot fragrance and musk bottom accumulation, and is widely applied to daily-use chemical industry, health care industry and the like of cosmetics, perfume, detergents and the like. The methyl cedryl ketone has wide application in the preparation of essence, is used in a plurality of cosmetics and high-grade perfume, is used together with cedar oil, cedrene, cedryl alcohol, cedryl acetate and the like, and has very long fragrance-lasting time. Because of the advantages of low price, unique fragrance, good stability, long fragrance-lasting time and the like, the methyl cedryl ketone becomes one of important fragrance raw materials of various essences such as cosmetics, perfumes, perfumed soaps, shampoos, creams, hair care water, indoor fragrances and the like.

The methyl cedryl ketone is prepared by reacting cedryl alkene with acetic anhydride in the presence of a catalyst. The type of catalyst is the determining factor for the synthesis of methyl cedryl ketone. At present, the production process of the methyl cedryl ketone mostly adopts polyphosphoric acid as a catalyst to react with acetic anhydride at a certain temperature. In actual industrial production, the process is modified in various ways, such as adding a second catalyst to form a combined catalyst or using other hydrated inorganic acids to change the raw material ratio, the temperature and the like. The existing processes all have a common defect that inorganic liquid acid is adopted as a catalyst, so that the method has the disadvantages of more side reactions, low selectivity, low yield, equipment corrosion and environmental pollution. In the present day that environmental protection and sustainable development have more and more attracted people's attention, it has important practical significance to find a suitable green catalyst to replace the traditional inorganic liquid acid catalyst.

Chinese patent CN200810061328.9 takes acetic anhydride and cedrene as raw materials and takes solid super acid (S)₂O₈ ^2-/ZrO₂-SiO₂、SO₄ ^2-/TiO₂-SiO₂) The method for preparing the methyl cedryl ketone by using the catalyst for reaction has the advantages of convenient operation, low cost, less waste acid discharge and the like, but the traditional SO₄ ^2-The solid super acid is easy to lose acidity in the reaction process to cause inactivation and has short service life. Chinese patent CN201410265363.8 uses cedrene as raw material, niobic acid loaded aluminum chloride as catalyst, and excessive acetic acid as reaction solvent and reagent to prepare cedryl methyl ketone. The synthesis method is environment-friendly, simple and convenient to operate and suitable for industrial production. However, aluminum chloride is easily decomposed in water to cause the loss of the activity of the catalyst and further the inactivation.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a method for producing methyl cedryl ketone for cosmetics, which is used for preparing solid phosphoric acid PO with strong stability₄ ^3-The composite catalyst combines MCM-41 and Zr-based solid ionic liquid.

The invention is realized by the following technical scheme:

the invention discloses a method for producing methyl cedryl ketone for cosmetics, which comprises the steps of uniformly mixing acetic anhydride and cedryl alkene, adding the mixture into a microwave reactor, introducing nitrogen for 30min, adding a catalyst into the microwave reactor, reacting the reaction mixture at 90 ℃ for 5 hours, and cooling to room temperature. After centrifugally separating the catalyst, rectifying the obtained product to obtain a finished product of the methyl cedryl ketone, and carrying out chromatographic analysis to obtain the product yield and ketone content; the catalyst is prepared from PO₄ ^3-The catalyst comprises MCM-41 solid phosphoric acid and Zr-based solid ionic liquid, wherein the mass fraction of the Zr-based solid ionic liquid in the catalyst is 45-55 wt%, and the Zr-based solid ionic liquid is Zr_0.25[TEAPS]₃SiW₁₂O₄₀、Zr_0.50[TEAPS]₂SiW₁₂O₄₀、Zr_0.75[TEAPS]SiW₁₂O₄₀、Zr_0.25[TEAPS]₂HSiW₁₂O₄₀One kind of (1).

In a preferred embodiment, the mass ratio of the acetic anhydride to the cedrene is (0.6-1.0): 1; the mass ratio of the catalyst to the cedrene is 1 (25-40).

Wherein, the catalyst is realized by the following specific steps:

（1）PO₄ ^3-preparation of MCM-41 solid phosphoric acid

Firstly, MCM-41 molecular sieve is ultrasonically dispersed into deionized water, then pyrophosphoric acid is added into the deionized water, the mixture is continuously stirred for 2 hours at room temperature, then the mixture is evaporated to dryness under the condition of 70 ℃ water bath, the material obtained by evaporation to dryness is roasted for 5 hours at 500 ℃ to obtain PO₄ ^3-PO in an amount of 10 to 25wt%₄ ^3-MCM-41 solid phosphoric acid;

(2) preparation of ionic liquid precursor TEAPS

Adding triethylamine and p-xylene into a microwave reactor, stirring and dissolving, then introducing nitrogen for 1h, opening the microwave reactor, keeping the power at 200-300W, then dropwise adding 1, 3-propane sultone into the mixture, reacting for 1-2 h to obtain a mixture, centrifuging and washing the obtained mixture, and drying at 90 ℃ for 12h to obtain an ionic liquid precursor, which is marked as TEAPS;

(3) in-situ loading of Zr-based solid ionic liquid

To PO₄ ^3-adding/MCM-41 solid phosphoric acid, silicotungstic acid, zirconium oxychloride and TEAPS into deionized water to obtain a mixture, stirring at room temperature for 30min, transferring the mixture into a microwave reactor, reacting for 4-8 h at 200-300W, and then sequentially centrifuging, washing and drying to obtain a composite catalyst of the solid phosphoric acid and the Zr-based solid ionic liquid; wherein Zr-based solid ionic liquid prepared from silicotungstic acid, zirconium oxychloride and TEAPS in the reaction process is Zr_0.25[TEAPS]₃SiW₁₂O₄₀、Zr_0.50[TEAPS]₂SiW₁₂O₄₀、Zr_0.75[TEAPS]SiW₁₂O₄₀、Zr_0.25[TEAPS]₂HSiW₁₂O₄₀One kind of (1).

As a preferred embodiment, in the step (2), the ratio of the amount of the triethylamine to the amount of the 1, 3-propane sultone is 1:1, and the concentration of the amount of the triethylamine in p-xylene is 0.1 mol/L.

In a preferred embodiment, in the step (3), the mass ratio of TEAPS to silicotungstic acid is (1-3): 1, the mass ratio of zirconium oxychloride to silicotungstic acid is (0.25-0.75): 1, and the mass fraction of Zr-based solid ionic liquid in the composite catalyst is 45-55 wt%.

Compared with the prior art, the invention has the following beneficial technical effects.

1) The zirconium-based solid ionic liquid exists in a solid state, heteropoly acid radicals with multi-charge characteristics are used as anions, organic cations, metal cations and protons are simultaneously used as counter ions, a heteropoly acid functional ionic liquid organic-inorganic hybrid material with a cation part having B-L dual acidity is constructed, and the Lewis acidity is introduced, so that the water solubility and water instability of the material are effectively avoided, and the guarantee is provided for the good catalytic performance in a reaction system with water and a polar solvent. Meanwhile, a strong acid functional group, an organic cation and a metal cation are introduced into the organic cation to replace a counter-charged proton to form an acid salt, so that the acid strength of the organic cation reaches the level of super acid, and higher catalytic activity and reaction stability are reflected in the reaction process.

2) Zr-based solid ionic liquid and PO in the composite catalyst₄ ^3-the/MCM-41 solid phosphoric acid has various types of acid sites, so that the reaction performance of the catalyst can be prevented from being reduced after the inactivation of the catalytic active sites of the same type.

3）PO₄ ^3-The MCM-41 solid phosphoric acid not only serves as an active component, but also can form a geometric confinement for a reaction component due to the self mesoporous structure, so that the side reaction is effectively prevented, and the selectivity of a main fragrance component is improved. In addition, PO₄ ^3-Compared with the conventional polyphosphoric acid, the active component of the MCM-41 solid phosphoric acid is not easy to lose, and the reaction stability is higher.

4) The composite catalyst prepared by the invention can solve the problem of difficult separation of the catalyst and the product, can also solve the defect of catalyst inactivation caused by easy loss of the acidity of the catalyst, can keep a solid state, and has no corrosion to a reaction device, high catalytic efficiency and good selectivity of a main product.

Detailed Description

The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.