CN112774728A - A method for producing cosmetic perfume - Google Patents

A method for producing cosmetic perfume Download PDF

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CN112774728A
CN112774728A CN202110188698.4A CN202110188698A CN112774728A CN 112774728 A CN112774728 A CN 112774728A CN 202110188698 A CN202110188698 A CN 202110188698A CN 112774728 A CN112774728 A CN 112774728A
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王强
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings

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Abstract

The invention discloses a method for producing a cosmetic perfume, which comprises the steps of uniformly mixing cyclohexanone, 1, 3-propylene glycol and a catalyst, adding the mixture into a reaction kettle, centrifugally separating the catalyst after the reaction is finished, washing the obtained organic phase with water and saturated salt water in sequence to be neutral, drying anhydrous magnesium sulfate, and then carrying out fine reduced pressure distillation operation to obtain a finished product of cyclohexanone-1, 3-propylene glycol ketal; the catalyst is prepared from solid super acidic SO4 2‑/SnO2‑ZrO2The catalyst is combined with acidic ionic liquid, the mass fraction of solid super acid in the catalyst is 50-80 wt%, and the solid super acid passes through mesoporous SnO2‑ZrO2Preparation of solid super acidic SO4 2‑/SnO2‑ZrO2Preparation of solid super acidic SO4 2‑/SnO2‑ZrO2And acidic ionic liquid. The catalyst prepared by the invention not only can solve the defect that the catalytic activity is greatly reduced due to easy loss of acidity, but also can inhibit the corrosion of the catalyst to reaction equipment and the occurrence of side reactions to a great extent.

Description

A method for producing cosmetic perfume
Technical Field
The invention belongs to the technical field of daily chemicals, relates to a production technology of a perfume for daily cosmetics, and particularly relates to a production method of a cosmetic perfume cyclohexanone-1, 3-propylene glycol ketal.
Background
The perfume consists of two parts of natural perfume and synthetic perfume, and the synthetic perfume has the advantages of stable quality, small price fluctuation, stable supply guarantee and the like due to the fact that the production is not limited by climate, natural environment and geographical conditions, and is widely applied to the fields of daily cosmetics, skin care products, foods and the like. The natural perfume plants are often limited by natural conditions and are subjected to certain influences on variety quantity and product quality due to factors such as processing and the like. Because the synthetic spice is not limited by natural conditions, the quality is stable, the production scale can be arranged by people, and the price of the product is much cheaper than that of natural sources. Therefore, the development and development of new synthetic perfumes are becoming more and more important. Especially, with the continuous improvement of the recent scientific research and analysis technology level, the main fragrant components and the structure of the natural perfume can be separated and analyzed, so that the defects of the natural perfume can be overcome and the economic cost can be reduced by the research and the chemical synthesis method.
The synthetic perfume belongs to the fine chemical technology category in the chemical industry, and relates to a high-temperature and high-pressure process means in the production process, and also relates to the discharge of a plurality of three wastes, which directly endangers the ecological environment. However, to solve the problem of environmental pollution caused by three wastes, the treatment needs to be carried out from the source of generating the three wastes. This requires that advanced routes must be used for the selection and evaluation of the process route during the production of the product, thereby reducing the number of process steps and optimizing the reaction conditions to avoid high temperature and high pressure and the use of toxic and harmful raw materials. The cyclohexanone ketal perfume, namely cyclohexanone and diol ketal product, generally has flower fragrance and costustoot fragrance, can be used in daily chemical essence, and representative substances thereof are cyclohexanone-1, 3-propanediol ketal, cyclohexanone-1, 3-butanediol ketal and the like. The ketal perfume is a novel perfume developed in recent years, has mild, mellow and lasting fragrance, effectively overcomes the defect of unstable property of a parent ketone compound, is mainly applied to daily chemical essence, plays the role of a main perfume agent or a coordinating agent, and also increases the natural taste of the perfume. The conventional production process of ketal formation reaction is to directly react ketone and alcohol to generate ketal under the catalysis of inorganic strong acid (sulfuric acid, hydrochloric acid, phosphoric acid and the like), but the conventional liquid strong acid has serious corrosion to equipment, long reaction time, complex post-treatment and serious environmental pollution. With the increasing awareness of environmental protection, higher requirements are put on the production of ketals, and a production process with low cost, high quality and less environmental pollution is expected. Therefore, the search for the traditional inorganic liquid acid catalyst to be used for producing the ketal spices has important practical significance.
Disclosure of Invention
The invention provides a method for producing cyclohexanone-1, 3-propylene glycol ketal as cosmetic perfume aiming at the defects of serious corrosion of inorganic strong acid, serious environmental pollution and more side reactions in the traditional production process of cyclohexanone-1, 3-propylene glycol ketal, wherein the used catalyst is solid super strong acid SO4 2-/SnO2-ZrO2And an acidic ionic liquid. The prepared catalyst can not only solve the defect that the catalytic activity is greatly reduced due to easy loss of acidity, but also inhibit the corrosion of the catalyst to reaction equipment and the occurrence of side reactions to a great extent.
The invention is realized by the following technical scheme:
on one hand, the invention discloses a method for producing a cosmetic perfume cyclohexanone-1, 3-propylene glycol ketal, comprising the steps of uniformly mixing the cyclohexanone and the 1, 3-propylene glycol, adding the mixture into a reaction kettle provided with a magnetic stirring and water separator, adding a catalyst into the reaction kettle, stirring the mixture at room temperature for 1 hour, heating and refluxing the mixture to be in a water separation state, and reacting until no water is separated out from the water separator; cooling the reaction kettle to room temperature, centrifugally separating out the catalyst, washing the obtained organic phase with water and saturated salt water in sequence to be neutral, drying the organic phase with anhydrous magnesium sulfate, and then carrying out fine pressure reduction distillation operation to obtain a cyclohexanone-1, 3-propanediol ketal finished product; the mass ratio of cyclohexanone and 1, 3-propanediol is 2: 3, the mass molar ratio of the catalyst to the cyclohexanone is 20 g/mol;
the catalyst is prepared from solid super acidic SO4 2-/SnO2-ZrO2The catalyst is combined with acidic ionic liquid, the mass fraction of the solid super acid in the catalyst is 50-80 wt%, and the acidic ionic liquid is shown as the following formula:
Figure DEST_PATH_IMAGE001
。
on the other hand, the invention also discloses a preparation method of the catalyst for producing the cosmetic perfume cyclohexanone-1, 3-propylene glycol ketal, which is realized by the following steps:
(1) mesoporous SnO2-ZrO2Preparation of
Respectively dissolving zirconyl chloride, stannic chloride and CTAC into deionized water, stirring at room temperature for 10-20 min, adding urea, continuously stirring for 15min, stirring the obtained mixture in a water bath at 90 ℃ for 18-24 h, filtering and washing the obtained product until no Cl exists-Drying at 100-110 ℃ for 15-18 h, and finally roasting the obtained product at 550 ℃ for 5h to obtain SnO2-ZrO2；
(2) Solid super acidic SO4 2-/SnO2-ZrO2Preparation of
Firstly, SnO prepared in step (1) is2-ZrO2Dispersing into deionized water, adding ammonium persulfate, slowly evaporating to dryness in 70 deg.C water bath under stirring, and roasting the obtained material at 550 deg.C for 5 hr to obtain SO4 2-/SnO2-ZrO2Solid super acid;
(3) solid super acidic SO4 2-/SnO2-ZrO2Complexing with acidic ionic liquids
Adding acidic ionic liquid into deionized water to form a mixed solution of 1g/mL, and then adding the acidic ionic liquid into the deionized water
Adding solid super strong acid SO4 2-/SnO2-ZrO2Stirring for 6h at room temperature, and slowly evaporating the obtained mixture in a water bath at 80 ℃ to dryness to obtain the composite catalyst; the structural formula of the acidic ionic liquid is as follows:
Figure 714215DEST_PATH_IMAGE002
the detailed preparation procedure of the acidic ionic liquid was obtained according to Journal of Molecular Liquids 225 (2017) 585-591 of the reference.
In a preferable embodiment, in the step (1), the CTAC is added in an amount of 4-6 wt% of the weight of the zirconyl chloride; the mass concentration of the zirconium oxychloride solution is 0.2-0.4 mol/L; the mass concentration of the stannic chloride is 0.2-0.4 mol/L; the amount of urea added was 15 times the amount of the total of zirconyl chloride and tin tetrachloride.
As a preferred embodiment, in the step (2), SO4 2-/SnO2-ZrO2SO in solid super acid4 2-The content of (A) is 15wt% -20 wt%.
In a preferred embodiment, in the step (3), the mass fraction of the solid super acid in the composite catalyst is 50wt% to 80 wt%.
Compared with the prior art, the invention has the following beneficial effects:
1) the method combines the solid super acid and the acidic ionic liquid, embodies good catalytic activity in the process of catalytically synthesizing the cyclohexanone-1, 3-propylene glycol ketal, has the advantages of less catalyst consumption, simple post-treatment, recyclable catalyst and the like which are not possessed by the traditional inorganic acid catalyst, and thus provides a new idea for synthesizing the cyclohexanone ketal compounds.
2) The composite catalyst is prepared by reacting SO4 2-/SnO2-ZrO2The solid super acid is combined with the acidic ionic liquid, has both Lewis acidic sites and Bronsted acidic sites, and can provide multiple active sites for catalytic reaction, so that the reduction of activity caused by the loss of a single acidic species is prevented.
3) Solid super acidic SO4 2-/SnO2-ZrO2On one hand, the acidic ionic liquid can be used as an active component to participate in the reaction, and on the other hand, the acidic ionic liquid can be used as a carrier to effectively improve the dispersity of the acidic ionic liquid; meanwhile, the sulfonic acid group on the ionic liquid can be reacted with SnO2-TiO2The interaction forms a new super strong acid site, thereby greatly improving the activity and stability of the catalytic reaction.
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.
Example 1
A preparation method of a catalyst for producing cyclohexanone-1, 3-propanediol ketal as a cosmetic perfume is realized by the following specific steps:
(1) mesoporous SnO2-ZrO2Preparation of
Respectively dissolving zirconyl chloride, stannic chloride and CTAC in deionized water, stirring at room temperature for 15min, adding urea into the mixed solution, stirring for 15min, stirring the obtained mixture in water bath at 90 deg.C for 18h, filtering the obtained product, and washing until no Cl exists-Drying at 105 deg.C for 16h, and calcining at 550 deg.C for 5h to obtain SnO2-ZrO2(ii) a The CTAC is added in an amount of 4wt% of the weight of the zirconyl chloride; the mass concentration of the zirconyl chloride solution is 0.2 mol/L; the mass concentration of tin tetrachloride was 0.4 mol/L; the amount of urea added was 15 times the amount of the total of zirconyl chloride and tin tetrachloride.
(2) Solid super acidic SO4 2-/SnO2-ZrO2Preparation of
Firstly, preparing SnO2-ZrO2Dispersing into deionized water, adding ammonium persulfate, slowly evaporating to dryness in 70 deg.C water bath under stirring, and roasting the obtained material at 550 deg.C for 5 hr to obtain SO4 2-/SnO2-ZrO2Solid superacids of which SO4 2-The content of (B) is 15 wt%;
(3) preparation of acidic ionic liquids
The structure of the acidic ionic liquid is shown in a formula 1, and the detailed preparation steps are obtained according to the Journal of Molecular Liquids 225 (2017) 585-591 in the reference.
(4) Solid super acidic SO4 2-/SnO2-ZrO2Complexing with acidic ionic liquids
The ionic liquid prepared as described above was added to deionized water to form a mixed solution of 1g/mL, followed by adding thereto
Adding solid super strong acid SO4 2-/SnO2-ZrO2Stirring at room temperature for 6h, and slowly evaporating the obtained mixture in 80 deg.C water bath to dryness to obtainTo a composite catalyst. The mass fraction of the solid super acid in the obtained composite catalyst is 50wt%, and the obtained catalyst is marked as # 1.
0.1 mol of cyclohexanone and 0.15 mol of 1, 3-propylene glycol are uniformly mixed and then added into a reaction kettle with a magnetic stirring and water separator, then 2.0g of 1# catalyst is added into the mixture, the mixture is stirred for 1 hour at room temperature, then heated and refluxed to be in a water separation state, and the mixture reacts until no water is separated out from the water separator. Cooling the reaction kettle to room temperature, centrifugally separating out the catalyst, washing the obtained organic phase with water, washing with saturated salt water to neutrality, drying with anhydrous magnesium sulfate, and performing fine pressure reduction distillation to obtain the final product of cyclohexanone-1, 3-propylene glycol ketal with the calculated yield of 96.4%.
Example 2
A preparation method of a catalyst for producing cyclohexanone-1, 3-propanediol ketal as a cosmetic perfume is realized by the following specific steps:
(1) mesoporous SnO2-ZrO2Preparation of
Respectively dissolving zirconyl chloride, stannic chloride and CTAC in deionized water, stirring at room temperature for 10min, adding urea into the mixed solution, stirring for 15min, stirring the obtained mixture in water bath at 90 deg.C for 18h, filtering the obtained product, and washing until no Cl exists-Drying at 100 deg.C for 18h, and calcining at 550 deg.C for 5h to obtain SnO2-ZrO2(ii) a The CTAC is added in an amount of 5wt% of the weight of the zirconyl chloride; the mass concentration of the zirconyl chloride solution is 0.3 mol/L; the mass concentration of tin tetrachloride was 0.3 mol/L; the amount of urea added was 15 times the amount of the total of zirconyl chloride and tin tetrachloride.
(2) Solid super acidic SO4 2-/SnO2-ZrO2Preparation of
Firstly, preparing SnO2-ZrO2Dispersing into deionized water, adding ammonium persulfate, slowly evaporating to dryness in 70 deg.C water bath under stirring, and roasting the obtained material at 550 deg.C for 5 hr to obtain SO4 2-/SnO2-ZrO2Solid state ultrasmallStrong acid, wherein SO4 2-Is 18 wt%;
(3) preparation of acidic ionic liquids
The structure of the acidic ionic liquid is shown in a formula 1, and the detailed preparation steps are obtained according to the Journal of Molecular Liquids 225 (2017) 585-591 in the reference.
(4) Solid super acidic SO4 2-/SnO2-ZrO2Complexing with acidic ionic liquids
The ionic liquid prepared as described above was added to deionized water to form a mixed solution of 1g/mL, followed by adding thereto
Adding solid super strong acid SO4 2-/SnO2-ZrO2Stirring for 6h at room temperature, and slowly evaporating the obtained mixture in a water bath at 80 ℃ to dryness to obtain the composite catalyst. The mass fraction of the solid super acid in the obtained composite catalyst is 65 wt%, and the obtained catalyst is marked as # 2.
0.1 mol of cyclohexanone and 0.15 mol of 1, 3-propylene glycol are uniformly mixed and then added into a reaction kettle with a magnetic stirring and water separator, then 2.0g of No. 2 catalyst is added into the mixture, the mixture is stirred for 1 hour at room temperature, then heated and refluxed to be in a water separation state, and the mixture is reacted until no water is separated out from the water separator. Cooling the reaction kettle to room temperature, centrifugally separating out the catalyst, washing the obtained organic phase with water, washing with saturated salt water to neutrality, drying with anhydrous magnesium sulfate, and performing fine pressure reduction distillation to obtain the final product of cyclohexanone-1, 3-propylene glycol ketal with the calculated yield of 97.2%.
Example 3
A preparation method of a catalyst for producing cyclohexanone-1, 3-propanediol ketal as a cosmetic perfume is realized by the following specific steps:
(1) mesoporous SnO2-ZrO2Preparation of
Respectively dissolving zirconyl chloride, stannic chloride and CTAC in deionized water, stirring at room temperature for 20min, adding urea into the mixed solution, stirring for 15min, stirring the obtained mixture in water bath at 90 deg.C for 24h, filtering the obtained product, and washing until no Cl exists-Drying at 110 deg.C for 15h, and calcining at 550 deg.C for 5h to obtain SnO2-ZrO2(ii) a The CTAC is added in an amount of 6wt% of the weight of the zirconyl chloride; the mass concentration of the zirconyl chloride solution is 0.4 mol/L; the mass concentration of tin tetrachloride was 0.2 mol/L; the amount of urea added was 15 times the amount of the total of zirconyl chloride and tin tetrachloride.
(2) Solid super acidic SO4 2-/SnO2-ZrO2Preparation of
Firstly, preparing SnO2-ZrO2Dispersing into deionized water, adding ammonium persulfate, slowly evaporating to dryness in 70 deg.C water bath under stirring, and roasting the obtained material at 550 deg.C for 5 hr to obtain SO4 2-/SnO2-ZrO2Solid superacids of which SO4 2-The content of (B) is 20 wt%;
(3) preparation of acidic ionic liquids
The structure of the acidic ionic liquid is shown in a formula 1, and the detailed preparation steps are obtained according to the Journal of Molecular Liquids 225 (2017) 585-591 in the reference.
(4) Solid super acidic SO4 2-/SnO2-ZrO2Complexing with acidic ionic liquids
The ionic liquid prepared as described above was added to deionized water to form a mixed solution of 1g/mL, followed by adding thereto
Adding solid super strong acid SO4 2-/SnO2-ZrO2Stirring for 6h at room temperature, and slowly evaporating the obtained mixture in a water bath at 80 ℃ to dryness to obtain the composite catalyst. The mass fraction of the solid super acid in the composite catalyst is 80 wt%. The resulting catalyst was labeled # 3.
0.1 mol of cyclohexanone and 0.15 mol of 1, 3-propylene glycol are uniformly mixed and then added into a reaction kettle with a magnetic stirring and water separator, then 2.0g of 3# catalyst is added into the mixture, the mixture is stirred for 1 hour at room temperature, then heated and refluxed to be in a water separation state, and the mixture reacts until no water is separated out from the water separator. Cooling the reaction kettle to room temperature, centrifugally separating out the catalyst, washing the obtained organic phase with water, washing with saturated salt water to neutrality, drying with anhydrous magnesium sulfate, and performing fine pressure reduction distillation to obtain the final product of cyclohexanone-1, 3-propylene glycol ketal with the calculated yield of 98.9%.
Comparative example 1
(1) Mesoporous SnO2-ZrO2Preparation of
Respectively dissolving zirconyl chloride, stannic chloride and CTAC in deionized water, stirring at room temperature for 15min, adding urea into the mixed solution, stirring for 15min, stirring the obtained mixture in water bath at 90 deg.C for 18h, filtering the obtained product, and washing until no Cl exists-Drying at 105 deg.C for 16h, and calcining at 550 deg.C for 5h to obtain SnO2-ZrO2(ii) a The CTAC is added in an amount of 4wt% of the weight of the zirconyl chloride; the mass concentration of the zirconyl chloride solution is 0.2 mol/L; the mass concentration of tin tetrachloride was 0.4 mol/L; the amount of urea added was 15 times the amount of the total of zirconyl chloride and tin tetrachloride.
(2) Solid super acidic SO4 2-/SnO2-ZrO2Preparation of
Firstly, preparing SnO2-ZrO2Dispersing into deionized water, adding ammonium persulfate, slowly evaporating to dryness in 70 deg.C water bath under stirring, and roasting the obtained material at 550 deg.C for 5 hr to obtain SO4 2-/SnO2-ZrO2Solid superacids of which SO4 2-The content of (B) is 15 wt%;
0.1 mol of cyclohexanone and 0.15 mol of 1, 3-propylene glycol are evenly mixed and added into a reaction kettle with magnetic stirring and a water separator, and then 2.0g of solid super acidic SO prepared in the step is added into the reaction kettle4 2-/SnO2-ZrO2The mixture is stirred for 1h at room temperature, then heated and refluxed to be in a water diversion state, and reacted until no water is separated out from a water segregator. Cooling the reaction kettle to room temperature, centrifugally separating out the catalyst, washing the obtained organic phase with water and saturated salt water in sequence to neutrality, drying the anhydrous magnesium sulfate, and then carrying out fine pressure reduction distillation operation to obtain cyclohexanone-The calculated yield of the finished 1, 3-propanediol ketal is 78.4%.
Comparative example 2
The structure of the acidic ionic liquid is shown in a formula 1, and the detailed preparation steps are obtained according to the Journal of Molecular Liquids 225 (2017) 585-591 in the reference.
Uniformly mixing 0.1 mol of cyclohexanone and 0.15 mol of 1, 3-propylene glycol, adding the mixture into a reaction kettle with a magnetic stirring and water separator, adding 2.0g of the acidic ionic liquid prepared in the step into the reaction kettle, stirring the mixture at room temperature for 1 hour, heating and refluxing the mixture to be in a water separation state, and reacting until no water is separated from the water separator. Cooling the reaction kettle to room temperature, centrifugally separating out the catalyst, washing the obtained organic phase with water, washing with saturated salt water to neutrality, drying with anhydrous magnesium sulfate, and performing fine pressure reduction distillation to obtain the final product of cyclohexanone-1, 3-propylene glycol ketal with the calculated yield of 85.2%.
Example 4
The 1# catalyst was centrifuged and subjected to the following cycle test:
TABLE 11 catalyst cycle test results
Number of cycles Cyclohexanone-1, 3-propanediol ketal yield
Cycle 1 96.1%
2 nd cycle 95.6%
Cycle 3 94.9%
Cycle 4 94.5%
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (5)

1. A method for producing a cosmetic fragrance, characterized by: the cosmetic perfume is cyclohexanone-1, 3-propylene glycol ketal, and the preparation method comprises the steps of uniformly mixing cyclohexanone and 1, 3-propylene glycol, adding the mixture into a reaction kettle with a magnetic stirring device and a water separator, adding a catalyst into the reaction kettle, stirring the mixture at room temperature for 1 hour, heating and refluxing the mixture to be in a water separation state, and reacting until no water is separated out from the water separator; cooling the reaction kettle to room temperature, centrifugally separating out the catalyst, washing the obtained organic phase with water and saturated salt water in sequence to be neutral, drying the organic phase with anhydrous magnesium sulfate, and then carrying out fine pressure reduction distillation operation to obtain a cyclohexanone-1, 3-propanediol ketal finished product; the mass ratio of cyclohexanone and 1, 3-propanediol is 2: 3, the mass molar ratio of the catalyst to the cyclohexanone is 20 g/mol;
the catalyst is prepared from solid super acidic SO4 2-/SnO2-ZrO2The catalyst is combined with acidic ionic liquid, the mass fraction of the solid super acid in the catalyst is 50-80 wt%, and the acidic ionic liquid is shown as the following formula:
Figure DEST_PATH_IMAGE002
。
2. the method for producing a cosmetic fragrance according to claim 1, wherein the catalyst is obtained by:
(1) mesoporous SnO2-ZrO2Preparation of
Respectively dissolving zirconyl chloride, stannic chloride and CTAC into deionized water, stirring at room temperature for 10-20 min, adding urea, continuously stirring for 15min, stirring the obtained mixture in a water bath at 90 ℃ for 18-24 h, filtering and washing the obtained product until no Cl exists-Drying at 100-110 ℃ for 15-18 h, and finally roasting the obtained product at 550 ℃ for 5h to obtain SnO2-ZrO2；
(2) Solid super acidic SO4 2-/SnO2-ZrO2Preparation of
Firstly, SnO prepared in step (1) is2-ZrO2Dispersing into deionized water, adding ammonium persulfate, slowly evaporating to dryness in 70 deg.C water bath under stirring, and roasting the obtained material at 550 deg.C for 5 hr to obtain SO4 2-/SnO2-ZrO2Solid super acid;
(3) solid super acidic SO4 2-/SnO2-ZrO2Complexing with acidic ionic liquids
Adding acidic ionic liquid into deionized water to form a mixed solution of 1g/mL, and then adding solid super acidic SO4 2-/SnO2-ZrO2Stirring for 6h at room temperature, and slowly evaporating the obtained mixture in a water bath at 80 ℃ to dryness to obtain the composite catalyst; the structural formula of the acidic ionic liquid is as follows:
Figure DEST_PATH_IMAGE003
。
3. the method for preparing a catalyst for the production of cosmetic perfumes according to claim 2, wherein: in the step (1), the CTAC is added in an amount of 4-6 wt% of the weight of the zirconyl chloride; the mass concentration of the zirconium oxychloride solution is 0.2-0.4 mol/L; the mass concentration of the stannic chloride is 0.2-0.4 mol/L; the amount of urea added was 15 times the amount of the total of zirconyl chloride and tin tetrachloride.
4. The method for preparing a catalyst for the production of cosmetic perfumes according to claim 2, wherein: in step (2), SO4 2-/SnO2-ZrO2SO in solid super acid4 2-In an amount of 15wt%~20wt%。
5. The method for preparing a catalyst for the production of cosmetic perfumes according to claim 2, wherein: in the step (3), the mass fraction of the solid superacid in the composite catalyst is 50-80 wt%.
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