阅读说明：本技术 一种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,通入氮气再加入催化剂反应,分离催化剂后将所得的产物经精馏操作后得到甲基柏木酮成品；通过介孔ZrO<Sub>2</Sub>-SnO<Sub>2</Sub>复合氧化物制备、MoO<Sub>3</Sub>/ZrO<Sub>2</Sub>-SnO<Sub>2</Sub>固体超强酸制备、离子液体前驱体MIMPS制备、Cu基固态离子液体原位负载,得到以具有超强稳定性能的固体超强酸MoO<Sub>3</Sub>/ZrO<Sub>2</Sub>-SnO<Sub>2</Sub>与Cu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,其对反应器无腐蚀性、催化效率高且选择性好。(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, and rectifying the obtained product to obtain a finished product of the methyl cedryl ketone; through the mesoporous ZrO 2 ‑SnO 2 Preparation of composite oxide, MoO 3 /ZrO 2 ‑SnO 2 Preparation of solid super strong acid, preparation of ionic liquid precursor MIMPS (metal insulator polymer), and Cu-based solid ionLiquid is loaded in situ to obtain solid super acidic MoO with super strong stability 3 /ZrO 2 ‑SnO 2 A composite catalyst combined with a Cu-based solid ionic liquid. 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 reactor, high catalytic efficiency and good selectivity.)

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 made of MoO₃/ZrO₂-SnO₂The catalyst comprises solid superacid and Cu-based solid ionic liquid, wherein the mass fraction of the Cu-based solid ionic liquid in the catalyst is 35-55 wt%, and the Cu-based solid ionic liquid is Cu [ MIMPS ]]PMo₁₂O₄₀、Cu_0.5[MIMPS]₂PMo₁₂O₄₀、Cu_0.5[MIMPS]HPMo₁₂O₄₀One kind of (1).

2. The method for producing methyl cedryl ketone for cosmetics according to claim 1, which is realized by the following specific steps:

(1) mesoporous ZrO₂-SnO₂Preparation of composite oxides

Dissolving zirconium sulfate and tin tetrachloride in deionized water, adding CTAB (cetyltrimethyl ammonium bromide) into the deionized water, continuously stirring for 30min, then dropwise adding ammonia water into the deionized water to enable the pH value of the mixed solution to reach 9-11, continuously standing and aging for 12-24 h, centrifuging and washing the obtained product, drying the product at 110 ℃ for 12 h, and finally roasting the obtained solid at 500-600 ℃ for 4-6 h to obtain ZrO with a mesoporous structure₂-SnO₂A composite oxide;

（2）MoO₃/ZrO₂-SnO₂preparation of solid superacid

Firstly, ZrO with mesoporous structure₂-SnO₂Ultrasonically dispersing the composite oxide into deionized water, adding ammonium molybdate, evaporating to dryness in a water bath at 80-100 ℃, roasting the evaporated material at 550 ℃ for 5 hours to obtain MoO₃MoO with the content of 20-30 wt%₃/ZrO₂-SnO₂Solid super acid;

(3) preparation of ionic liquid precursor MIMPS

Adding N-methylimidazole and p-xylene into a microwave reactor, stirring and dissolving, introducing nitrogen for 1h, opening the microwave reactor, keeping the power at 150-300W, 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 6 h to obtain an ionic liquid precursor, which is marked as MIMPS;

(4) in-situ loading of Cu-based solid ionic liquids

Adding MoO₃/ZrO₂-SnO₂Adding solid superacid, phosphomolybdic acid, copper sulfate and MIMPS into deionized water to obtain a mixture, stirring at room temperature for 30min, transferring the mixture into a microwave reactor to react for 4-6 h at 200-300W, and then sequentially centrifuging, washing and drying to obtain a composite catalyst of the solid superacid and the Cu-based solid ionic liquid; wherein the Cu-based solid ionic liquid prepared by phosphomolybdic acid, copper sulfate and MIMPS in the reaction process is Cu [ MIMPS]PMo₁₂O₄₀、Cu_0.5[MIMPS]₂PMo₁₂O₄₀、Cu_0.5[MIMPS]HPMo₁₂O₄₀One kind of (1).

3. The method for producing methyl cedryl ketone for cosmetics according to claim 1, wherein: 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 method for producing methyl cedryl ketone for cosmetics according to claim 2, wherein: in the step (1), the CTAB is added in an amount of 2-4 wt% of the total weight of the zirconium sulfate and the stannic chloride; the mass concentration of the zirconium sulfate solution is 0.1 to 0.3 mol/L, and the mass concentration of the tin tetrachloride solution is 0.1 to 0.3 mol/L.

5. The method for producing methyl cedryl ketone for cosmetics according to claim 2, wherein: in the step (3), the mass ratio of the N-methylimidazole to the 1, 3-propane sultone is 1:1, and the mass concentration of the N-methylimidazole in the p-xylene is 0.1 mol/L.

6. The method for producing methyl cedryl ketone for cosmetics according to claim 2, wherein: in the step (4), the mass ratio of MIMPS to phosphomolybdic acid is (1-2): 1, the mass ratio of copper sulfate to phosphomolybdic acid is (0.50-1.0): 1, and the mass fraction of the Cu-based solid ionic liquid in the composite catalyst is 45-65 wt%.

Technical Field

The invention belongs to the technical field of cosmetics, relates to a production technology 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 uses solid super acidic MoO with super high stability₃/ZrO₂-SnO₂A composite catalyst combined with a Cu-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. And (3) after centrifugally separating the catalyst, rectifying the obtained product to obtain a finished product of the methyl cedryl ketone, and performing chromatographic analysis to obtain the product yield and ketone content. The catalyst consists of MoO₃/ZrO₂-SnO₂The catalyst comprises solid superacid and Cu-based solid ionic liquid, wherein the mass fraction of the Cu-based solid ionic liquid in the catalyst is 35-55 wt%, and the Cu-based solid ionic liquid is Cu [ MIMPS ]]PMo₁₂O₄₀、Cu_0.5[MIMPS]₂PMo₁₂O₄₀、Cu_0.5[MIMPS]HPMo₁₂O₄₀One 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) mesoporous ZrO₂-SnO₂Preparation of composite oxides

Dissolving zirconium sulfate and tin tetrachloride in deionized water, adding CTAB (cetyltrimethyl ammonium bromide) into the deionized water, continuously stirring for 30min, dropwise adding ammonia water into the deionized water to enable the pH value of the mixed solution to reach 9-11, continuously standing and aging for 12-24 h, centrifuging and washing the obtained product, drying the product at 110 ℃ for 12 h, and finally roasting the obtained solid at 500-600 ℃ for 4-6 h to obtain ZrO with a mesoporous structure₂-SnO₂A composite oxide; the CTAB is added in an amount of 2-4 wt% of the total weight of zirconium sulfate and stannic chloride; the mass concentration of the zirconium sulfate solution was 01-0.3 mol/L, the mass concentration of the stannic chloride solution is 0.1-0.3 mol/L;

（2）MoO₃/ZrO₂-SnO₂preparation of solid superacid

Firstly, ZrO with mesoporous structure₂-SnO₂Ultrasonically dispersing the composite oxide into deionized water, adding ammonium molybdate, evaporating to dryness in a water bath at 80-100 ℃, roasting the evaporated material at 550 ℃ for 5 hours to obtain MoO₃MoO with the content of 20-30 wt%₃/ZrO₂-SnO₂Solid super acid;

(3) preparation of ionic liquid precursor MIMPS

Adding N-methylimidazole and p-xylene into a microwave reactor, stirring and dissolving, introducing nitrogen for 1h, opening the microwave reactor, keeping the power at 150-300W, 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 6 h to obtain an ionic liquid precursor, which is marked as MIMPS; wherein the mass ratio of N-methylimidazole to 1, 3-propane sultone is 1:1, and the mass concentration of N-methylimidazole in p-xylene is 0.1 mol/L;

(4) in-situ loading of Cu-based solid ionic liquids

Adding MoO₃/ZrO₂-SnO₂Adding solid superacid, phosphomolybdic acid, copper sulfate and MIMPS into deionized water to obtain a mixture, stirring at room temperature for 30min, transferring the mixture into a microwave reactor to react for 4-6 h at 200-300W, and then sequentially centrifuging, washing and drying to obtain a composite catalyst of the solid superacid and the Cu-based solid ionic liquid; wherein the Cu-based solid ionic liquid prepared by phosphomolybdic acid, copper sulfate and MIMPS in the reaction process is Cu [ MIMPS]PMo₁₂O₄₀、Cu_0.5[MIMPS]₂PMo₁₂O₄₀、Cu_0.5[MIMPS]HPMo₁₂O₄₀One kind of (1).

In a preferred embodiment, in the step (4), the mass ratio of the MIMPS to the phosphomolybdic acid is (1-2): 1, the mass ratio of the copper sulfate to the phosphomolybdic acid is (0.50-1.0): 1, and the mass fraction of the Cu-based solid ionic liquid in the composite catalyst is 45-65 wt%.

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

1) The Cu-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, the 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) Cu-based solid ionic liquid and MoO in composite catalyst₃/ZrO₂-SnO₂The solid super acid has various types of acid sites, so that the reaction performance of the catalyst can be prevented from being reduced after the deactivation of the catalytic active sites of the same type.

3）MoO₃/ZrO₂-SnO₂The solid superacid not only serves as an active component, but also can form a geometric confinement for a reaction component due to the self mesoporous structure of the solid superacid, so that the occurrence of side reactions is effectively prevented, and the selectivity of the main fragrance component is improved. Further, MoO₃/ZrO₂-SnO₂Solid superacid with conventional SO₄ ^2-/TiO₂The solid super strong acid phase active component is not easy to lose, and has higher reaction stability.

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 reactor, high catalytic efficiency and good selectivity.

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.