CN114956994B - Preparation method of salicylate - Google Patents
Preparation method of salicylate Download PDFInfo
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- CN114956994B CN114956994B CN202110221168.5A CN202110221168A CN114956994B CN 114956994 B CN114956994 B CN 114956994B CN 202110221168 A CN202110221168 A CN 202110221168A CN 114956994 B CN114956994 B CN 114956994B
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- salicylate
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- alcohol
- dolomite
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- 229960001860 salicylate Drugs 0.000 title claims abstract description 39
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000003054 catalyst Substances 0.000 claims abstract description 99
- 239000010459 dolomite Substances 0.000 claims abstract description 82
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 82
- 229910003251 Na K Inorganic materials 0.000 claims abstract description 60
- 229960001047 methyl salicylate Drugs 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 68
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 22
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 claims description 18
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 10
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 10
- IPNFHEWNDOORKH-UHFFFAOYSA-N 6-methylheptyl 2-hydroxybenzoate Chemical compound CC(C)CCCCCOC(=O)C1=CC=CC=C1O IPNFHEWNDOORKH-UHFFFAOYSA-N 0.000 claims description 9
- DUKPKQFHJQGTGU-UHFFFAOYSA-N Hexyl salicylic acid Chemical compound CCCCCCOC(=O)C1=CC=CC=C1O DUKPKQFHJQGTGU-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 26
- 238000005809 transesterification reaction Methods 0.000 description 25
- 239000011777 magnesium Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000011780 sodium chloride Substances 0.000 description 13
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 7
- 229960004889 salicylic acid Drugs 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 150000003902 salicylic acid esters Chemical class 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000834 fixative Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000010921 Betula lenta Nutrition 0.000 description 1
- 240000001746 Betula lenta Species 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The application relates to a preparation method of salicylate, which belongs to the technical field of chemical industry, and comprises the following steps: s1: mixing and stirring methyl salicylate, alcohol and a catalyst uniformly, and reacting for 5-10 h at the temperature of 130-190 ℃; wherein, the mol ratio of the methyl salicylate to the alcohol is 1: (1.7-2.0); the catalyst adopts an Sn-Rh-La-Mg-Na-K/dolomite catalyst, and the dosage of the Sn-Rh-La-Mg-Na-K/dolomite catalyst is 0.1-0.5% of the total mass of methyl salicylate and alcohol; s2: and (3) filtering the obtained product in the step (S1) to remove the catalyst, washing with water, then carrying out reduced pressure distillation under the pressure of 0.93-1.8 kPa, and collecting fractions to obtain the product. The preparation method has the advantages of simple process, higher product yield, higher purity and good product fragrance.
Description
Technical Field
The application relates to the field of chemical industry, in particular to a preparation method of salicylate.
Background
Salicylic acid is a fat-soluble organic acid, is present in willow bark, white pearl tree leaves and sweet birch in nature, and is an important fine chemical raw material. The salicylate synthesized by using salicylic acid as a raw material is widely applied to the perfume industry and the daily chemical industry, and is an important fine chemical product.
In general, salicylate is synthesized mainly by esterification, and salicylic acid and alcohol are heated and esterified under the catalysis of sulfuric acid. However, salicylic acid is extremely easy to generate side reactions in the reaction, so that oxidative discoloration or peculiar smell is generated, and the salicylic acid is not easy to recycle once the salicylic acid is deteriorated. Therefore, it is common in industry to use transesterification to synthesize salicylates, i.e. methyl salicylate and other alcohols than methanol are used to produce new salicylates under catalytic heating of the catalyst. The inventors found that the conversion rate of the process of synthesizing salicylate by transesterification is still to be improved.
Disclosure of Invention
In order to simplify the process and improve the yield of the product, so that the fragrance of the product is better, the application provides a preparation method of salicylate.
The preparation method of the salicylate provided by the application adopts the following technical scheme:
a process for the preparation of a salicylate comprising the steps of:
s1: mixing and stirring methyl salicylate, alcohol and a catalyst uniformly, and reacting for 5-10 h at the temperature of 130-190 ℃;
wherein, the mol ratio of the methyl salicylate to the alcohol is 1: (1.7-2.0); the catalyst adopts an Sn-Rh-La-Mg-Na-K/dolomite catalyst, and the dosage of the Sn-Rh-La-Mg-Na-K/dolomite catalyst is 0.1-0.5% of the total mass of methyl salicylate and alcohol;
s2: and (3) filtering the obtained product in the step (S1) to remove the catalyst, washing with water, then carrying out reduced pressure distillation under the pressure of 0.93-1.8 kPa, and collecting fractions to obtain the product.
Through adopting above-mentioned technical scheme, the methyl salicylate and the alcohol in specific molar ratio range carry out transesterification under the catalytic action of specific catalyst to control the temperature and the time of transesterification process in specific range, make methyl salicylate and the transesterification of alcohol more thorough, promote the reaction to going on forward, improved the conversion rate of methyl salicylate.
The molar ratio range of the methyl salicylate and the alcohol is controlled, and the transesterification is a reversible reaction, so that the addition amount of the alcohol is higher than a certain range of the methyl salicylate according to the Lexagline principle, the transesterification can be promoted to be carried out towards the forward direction, and the conversion rate of the methyl salicylate is improved. However, if the amount of the added alcohol is higher than the range of the present application, the time for recovering the alcohol by distillation under reduced pressure may be increased, which may cause side reactions, and since part of the methyl salicylate is azeotropically carried away during distillation of the alcohol under reduced pressure, the amount of the added alcohol is increased, which may correspondingly increase the amount of the methyl salicylate azeotropically with the alcohol, resulting in a decrease in the conversion rate of the methyl salicylate, thereby decreasing the yield.
Meanwhile, the reaction temperature in the transesterification reaction process is controlled within a specific range, and the boiling point of the methyl alcohol is higher than that of the methyl alcohol, so that the methyl alcohol is distilled out, products produced by the reaction are reduced, the reaction is carried out forward, and the conversion rate of methyl salicylate is improved. However, if the reaction temperature is too high, the conversion rate of methyl salicylate is not increased, and the oxidation reaction of phenolic hydroxyl groups is caused to influence the quality of products.
The method controls the reaction time of the transesterification reaction process within a specific range, so that the methyl salicylate and the alcohol are fully reacted, the reaction is more thorough, the residual quantity of the methyl salicylate is reduced, and the purity of the product is improved. The continuous improvement of the reaction time does not increase the conversion rate of methyl salicylate, but rather increases the production cost.
According to the method, sn-Rh-La-Mg-Na-K/dolomite is used as a catalyst for transesterification, the addition amount of the catalyst is controlled within a specific range, and the catalyst fully catalyzes the transesterification, so that the transesterification is more thorough, and the conversion rate of methyl salicylate is improved. If the addition amount of the catalyst is lower than the range, the catalyst is too little in contact with the materials, so that the reaction speed is influenced; however, if the amount of the catalyst is in this range, agglomeration is likely to occur, but the surface area contacting with the material is reduced, the effect of improving the conversion rate cannot be achieved, and the production cost is increased.
Meanwhile, the Sn-Rh-La-Mg-Na-K/dolomite is a solid alkaline catalyst, the catalytic activity is higher, and a large number of lamellar substances are piled on the surface of the Sn-Rh-La-Mg-Na-K/dolomite solid alkaline catalyst to form ravines, so that the Sn-Rh-La-Mg-Na-K/dolomite solid alkaline catalyst can be fully contacted with reactants, and the conversion rate of transesterification reaction is improved. Meanwhile, the Sn-Rh-La-Mg-Na-K/dolomite solid base catalyst has excellent reusability, is easy to separate from a product, can still keep higher catalytic activity after being used for multiple times, reduces the production cost and meets the requirement of green production. Meanwhile, the Sn-Rh-La-Mg-Na-K/dolomite solid base catalyst has little influence on the aroma of salicylate.
In conclusion, the salicylate prepared by the preparation method has higher yield and higher purity, and the prepared salicylate has good fragrance.
Preferably, the alcohol in the step S1 is benzyl alcohol; the reaction temperature of the methyl salicylate and the benzyl alcohol is 160-190 ℃ and the reaction time is 6-8 h; and in the step S2, collecting the fraction at 170-175 ℃ under the pressure of 0.93-0.95 kPa to obtain benzyl salicylate.
By adopting the technical scheme, benzyl alcohol and methyl salicylate are adopted to carry out transesterification reaction within a specific reaction temperature and a specific reaction time, and benzyl salicylate is collected by decompression fractionation under a specific pressure condition and a specific temperature condition, and the benzyl salicylate has sweet fragrance and is commonly used as a fragrance fixative for cosmetics and soap essence. The proper reaction conditions promote the forward reaction, so that the transesterification reaction is more fully carried out, the conversion rate of methyl salicylate is improved, and the yield and purity of benzyl salicylate are improved.
Preferably, the alcohol in the step S1 is isooctyl alcohol; the reaction temperature of methyl salicylate and isooctyl alcohol is 130-150 ℃ and the reaction time is 5-9 h; and in the step S2, collecting the fraction at 174-178 ℃ under the pressure of 1.0-1.2 kPa to obtain isooctyl salicylate.
Through adopting above-mentioned technical scheme, the application adopts isooctyl alcohol and methyl salicylate to carry out transesterification in specific reaction temperature and reaction time to collect isooctyl salicylate through decompression fractionation under specific pressure condition and temperature condition, isooctyl salicylate has good fragrance, is the fine chemical raw materials of common use. The proper reaction conditions promote the forward reaction, so that the transesterification reaction is more fully carried out, and the conversion rate of methyl salicylate is improved, thereby improving the yield and purity of isooctyl salicylate.
Preferably, the alcohol in the step S1 is n-hexanol; the reaction temperature of methyl salicylate and n-hexanol is 140-190 ℃, and the reaction time is 6-10 h; and in the step S2, collecting the fraction at 167-168 ℃ under the pressure of 1.6-1.8 kPa to obtain the hexyl salicylate.
Through adopting above-mentioned technical scheme, the application adopts normal hexanol and methyl salicylate to carry out transesterification in specific reaction temperature and reaction time to collect the hexyl salicylate by decompression fractionation in specific pressure condition and temperature condition, the hexyl salicylate has the fragrant fruit fragrance characteristic of flowers, and the while accompanies soft sweet herbal fragrance, is the fragrance fixative of cosmetics spices commonly used. The proper reaction conditions promote the forward reaction, so that the transesterification reaction is more fully carried out, the conversion rate of methyl salicylate is improved, and the yield and purity of hexyl salicylate are improved.
Preferably, the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
mixing dolomite powder with Sn 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + Immersing for 2-5 h, drying, and calcining for 1-2 h at the temperature of 500-600 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
By adopting the technical scheme, the Sn is prepared by adopting the dipping method 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The ions are loaded onto dolomite powder. Dolomite powder mainly comprises calcium carbonate and magnesium carbonate, and Sn is calcined at high temperature 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + After the ions are loaded on the dolomite powder, the grain size of calcium oxide in the dolomite powder can be reduced, and the smaller calcium oxide particles are beneficial to the full contact between the active ingredients of the catalyst and reactants, so that the conversion rate of methyl salicylate is improved.
And Sn is 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + After the ions are loaded on dolomite powder, the specific surface area and the average pore diameter of the Sn-Rh-La-Mg-Na-K/dolomite catalyst are reduced, the mesoporous performance is improved, the mass transfer of the transesterification reaction is enhanced, and the catalytic performance of the catalyst is improved, so that the conversion rate of methyl salicylate is improved.
Meanwhile, the method controls the dolomite powder to be in Sn 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The soaking time, the calcining temperature and the calcining time in the mixed solution are in a specific range, so that each ion is fully loaded on the surface of dolomite powder, the alkali strength and the catalytic activity of the Sn-Rh-La-Mg-Na-K/dolomite catalyst are improved, and the conversion rate of methyl salicylate is improved.
Preferably, sn in the mixed solution 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The ion molar concentration of the catalyst is 0.65-0.70 mol/L, 0.02-0.04 mol/L, 0.05-0.06 mol/L, 0.45-0.55 mol/L, 0.22-0.26 mol/L and 0.32-0.36 mol/L respectively.
By adopting the technical proposal, the utility model has the advantages that,the application strictly controls Sn in the mixed solution 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The molar concentration of the catalyst is in a specific range, so that each metal ion can be well attached to dolomite powder, the Sn-Rh-La-Mg-Na-K/dolomite catalyst has high alkali strength and high catalytic activity, and the catalyst has excellent reusability, is easy to separate from a product, can still keep high catalytic activity after being used for many times, reduces the production cost and meets the requirements of green production.
Preferably, the drying condition is that the drying is carried out for 1-2 hours at the temperature of 80-90 ℃.
Through adopting above-mentioned technical scheme, this application is dried to mixed solution under specific temperature range, gets rid of moisture, has reduced the possibility that moisture produced the interference to follow-up calcination, has improved the alkali strength and the catalytic activity of Sn-Rh-La-Mg-Na-K/dolomite catalyst to the conversion of methyl salicylate has been improved.
Preferably, in the step S1, N is introduced during the reaction 2 And (5) protecting.
By adopting the technical scheme, N is introduced in the process of transesterification 2 The reaction is protected, so that oxygen in a reaction system can be removed, and the possibility of thermal oxidative degradation caused by the existence of oxygen at high temperature is reduced. At the same time N 2 The existence of the catalyst can improve the pressure in the system, promote the reaction to proceed forward, and improve the conversion rate of methyl salicylate.
Preferably, in the step S1, a fraction at 64-70 ℃ is continuously fractionated during the reaction.
Through adopting above-mentioned technical scheme, the present application is continuously fractioned and is got 64~70 ℃ fraction in transesterification reaction in-process for the methyl alcohol that produces in the transesterification reaction is continuously fractioned out reaction system, and the continuous volume of reducing the methyl alcohol that the reaction produced promotes the reaction to going forward, has increased the conversion rate of methyl salicylate.
Preferably, in the step S2, the number of times of washing is 2 to 3.
Through adopting above-mentioned technical scheme, the obtained thing after will filtering in this application wash certain number of times for the unreacted material in obtained thing surface is fully got rid of, reduces impurity, has improved the purity of salicylic acid other esters that transesterification generated.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the preparation method of the application ensures that the conversion rate of the methyl salicylate is high, so that the prepared salicylate has higher yield and the product has higher purity;
2. the catalyst in the preparation method has high catalytic activity, is easy to separate from raw materials, can be recycled, can still keep higher catalytic activity after being used for many times, and does not influence the aroma of the prepared salicylate;
3. the preparation method of the salicylate has the advantages of simple steps, mild reaction conditions and low production cost, and is suitable for large-scale industrial production.
Detailed Description
The present application is described in further detail below with reference to examples.
In the following examples and comparative examples:
methyl salicylate was purchased from Beijing Beida Zhengyuan technology Co., ltd;
benzyl alcohol was purchased from Shandong Wei Anhua chemical engineering Co., ltd;
isooctanol was purchased from jinan grong chemical industry limited;
n-hexanol was purchased from atanan yuno chemical industry limited;
SnCl 2 purchased from Henan Hongzhu chemical products Co., ltd;
Rh(NO 3 ) 3 purchased from Shanghai Jiujiu Iridium New Material technologies Co., ltd;
La(NO 3 ) 3 purchased from Hubei Xingzheng technologies limited;
Mg(NO 3 ) 2 purchased from shan-western Chemie Co., ltd;
NaCl and KCl are purchased from Jinan Kunfeng chemical industry Co.
Example 1
A process for the preparation of a salicylate comprising the steps of:
s1: 152kg of methyl salicylate (1000 mol), 183.6kg of benzyl alcohol (1700 mol) and 0.3356kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst are mixed and stirred uniformly, and N is introduced 2 Protecting, reacting for 6 hours at 160 ℃, and continuously fractionating a fraction at 64-70 ℃ in the reaction process;
s2: filtering the obtained product in the step S1 to remove the catalyst, washing the product for 2 times, and collecting the fraction at 170-175 ℃ under the pressure of 0.93kPa to obtain benzyl salicylate;
the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The molar concentration of NaCl and KCl is respectively 0.65mol/L, 0.02mol/L, 0.05mol/L, 0.45mol/L, 0.22mol/L and 0.32mol/L, and then the mixture is immersed in the mixed solution for 2 hours, dried for 1 hour at 80 ℃, and calcined for 1 hour at 500 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 2
A process for the preparation of a salicylate comprising the steps of:
s1: 152kg of methyl salicylate (1000 mol), 199.8kg of benzyl alcohol (1850 mol) and 1.0554kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst are mixed and stirred uniformly, and N is introduced 2 Protecting, reacting for 7 hours at the temperature of 175 ℃, and continuously fractionating a fraction at the temperature of 64-70 ℃ in the reaction process;
s2: filtering the obtained product in the step S1 to remove the catalyst, washing the product for 2 times, and collecting the fraction at 170-175 ℃ under the pressure of 0.94kPa to obtain benzyl salicylate;
the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The molar concentrations of NaCl and KCl are respectively 0.675mol/L, 0.03mol/L, 0.055mol/L, 0.5mol/L and 0Immersing the mixture of 24mol/L and 0.34mol/L for 3.5h, drying the mixture at the temperature of 85 ℃ for 1.5h, and calcining the mixture at the temperature of 550 ℃ for 1.5h to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 3
A process for the preparation of a salicylate comprising the steps of:
s1: 152kg of methyl salicylate (1000 mol), 216kg of benzyl alcohol (2000 mol) and 1.84kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst are mixed and stirred uniformly, and N is introduced 2 Protecting, reacting for 8 hours at the temperature of 190 ℃, and continuously fractionating a fraction at the temperature of 64-70 ℃ in the reaction process;
s2: filtering the obtained product in the step S1 to remove the catalyst, washing for 3 times, and then collecting the fraction at 170-175 ℃ under the pressure of 0.95kPa to obtain benzyl salicylate;
the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The molar concentration of NaCl and KCl is respectively 0.7mol/L, 0.04mol/L, 0.06mol/L, 0.55mol/L, 0.26mol/L and 0.36mol/L, and then the mixture is immersed in the mixed solution for 5 hours, dried for 2 hours at 90 ℃, and calcined for 2 hours at 600 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 4
A process for the preparation of a salicylate comprising the steps of:
s1: 152kg of methyl salicylate (1000 mol), 221kg of isooctanol (1700 mol) and 0.373kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst are mixed and stirred uniformly, and N is introduced 2 Protecting, reacting for 5 hours at the temperature of 130 ℃, and continuously fractionating a fraction at 64-70 ℃ in the reaction process;
s2: filtering the obtained product in the step S1 to remove the catalyst, washing the catalyst with water for 2 times, and then collecting the fraction at 174-178 ℃ under the pressure of 1.0kPa to obtain isooctyl salicylate;
the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The molar concentration of NaCl and KCl is respectively 0.65mol/L, 0.02mol/L, 0.05mol/L, 0.45mol/L, 0.22mol/L and 0.32mol/L, and then the mixture is immersed in the mixed solution for 2 hours, dried for 1 hour at 80 ℃, and calcined for 1 hour at 500 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 5
A process for the preparation of a salicylate comprising the steps of:
s1: 152kg of methyl salicylate (1000 mol), 240.5kg of isooctanol (1850 mol) and 1.1775kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst are mixed and stirred uniformly, and N is introduced 2 Protecting, reacting for 7 hours at 140 ℃, and continuously fractionating a fraction at 64-70 ℃ in the reaction process;
s2: filtering the obtained product in the step S1 to remove the catalyst, washing for 3 times, and then collecting the fraction at 174-178 ℃ under the pressure of 1.1kPa to obtain isooctyl salicylate;
the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The molar concentration of NaCl and KCl is respectively 0.675mol/L, 0.03mol/L, 0.055mol/L, 0.5mol/L, 0.24mol/L and 0.34mol/L, and then the mixture is immersed for 3.5 hours, dried for 1.5 hours at the temperature of 85 ℃, and calcined for 1.5 hours at the temperature of 550 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 6
A process for the preparation of a salicylate comprising the steps of:
s1: 152kg of methyl salicylate (1000 mol), 260kg of isooctanol (2000 mol) and 2.06kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst are mixed and stirred uniformly, and N is introduced 2 Protecting, reacting for 9 hours at the temperature of 150 ℃, and continuously fractionating a fraction at the temperature of 64-70 ℃ in the reaction process;
s2: filtering the obtained product in the step S1 to remove the catalyst, washing for 3 times, and then collecting the fraction at 174-178 ℃ under the pressure of 1.2kPa to obtain isooctyl salicylate;
the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The molar concentration of NaCl and KCl is respectively 0.7mol/L, 0.04mol/L, 0.06mol/L, 0.55mol/L, 0.26mol/L and 0.36mol/L, and then the mixture is immersed in the mixed solution for 5 hours, dried for 2 hours at 90 ℃, and calcined for 2 hours at 600 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 7
A process for the preparation of a salicylate comprising the steps of:
s1: 152kg of methyl salicylate (1000 mol), 173.4kg of N-hexanol (1700 mol) and 0.3254kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst are mixed and stirred uniformly, and N is introduced 2 Protecting, reacting for 6 hours at 140 ℃, and continuously fractionating a fraction at 64-70 ℃ in the reaction process;
s2: filtering the obtained product in the step S1 to remove the catalyst, washing the product for 2 times, and then collecting fractions at 167-168 ℃ under the pressure of 1.6kPa to obtain hexyl salicylate;
the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The molar concentration of NaCl and KCl is respectively 0.65mol/L, 0.02mol/L, 0.05mol/L, 0.45mol/L, 0.22mol/L and 0.32mol/L, and then the mixture is immersed in the mixed solution for 2 hours, dried for 1 hour at 80 ℃, and calcined for 1 hour at 500 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 8
A process for the preparation of a salicylate comprising the steps of:
s1: 152kg of methyl salicylate (1000 mol), 188.7kg of n-hexanol (1850 mol) were addedMixing with 1.0221kg Sn-Rh-La-Mg-Na-K/dolomite catalyst, stirring, and introducing N 2 Protecting, reacting for 8 hours at the temperature of 165 ℃, and continuously fractionating a fraction at the temperature of 64-70 ℃ in the reaction process;
s2: filtering the obtained product in the step S1 to remove the catalyst, washing for 3 times, and then collecting fractions at 167-168 ℃ under the pressure of 1.7kPa to obtain hexyl salicylate;
the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The molar concentration of NaCl and KCl is respectively 0.675mol/L, 0.03mol/L, 0.055mol/L, 0.5mol/L, 0.24mol/L and 0.34mol/L, and then the mixture is immersed for 3.5 hours, dried for 1.5 hours at the temperature of 85 ℃, and calcined for 1.5 hours at the temperature of 550 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 9
A process for the preparation of a salicylate comprising the steps of:
s1: 152kg of methyl salicylate (1000 mol), 204kg of N-hexanol (2000 mol) and 0.712kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst are mixed and stirred uniformly, and N is introduced 2 Protecting, reacting for 10 hours at the temperature of 190 ℃, and continuously fractionating a fraction at the temperature of 64-70 ℃ in the reaction process;
s2: filtering the product obtained in the step S1 to remove the catalyst, washing for 3 times, and then collecting fractions at 167-168 ℃ under the pressure of 1.8kPa to obtain hexyl salicylate;
the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The molar concentration of NaCl and KCl is respectively 0.7mol/L, 0.04mol/L, 0.06mol/L, 0.55mol/L, 0.26mol/L and 0.36mol/L, and then the mixture is immersed in the mixed solution for 5 hours, dried for 2 hours at 90 ℃, and calcined for 2 hours at 600 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 10
The process for the preparation of salicylate differs from example 2 in that: the catalyst used was one which had been recycled 5 times under the conditions of example 2.
Example 11
The process for the preparation of salicylate differs from example 5 in that: the catalyst used was one which had been recycled 7 times under the conditions of example 5.
Example 12
A process for the preparation of a salicylate, which differs from example 8 in that: the catalyst used was one which had been recycled 10 times under the conditions of example 8.
Comparative example 1
The difference from example 2 is that: in the step S1, concentrated sulfuric acid is adopted to replace Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Comparative example 2
The difference from example 5 is that: in the step S1, concentrated sulfuric acid is adopted to replace Sn-Rh-La-Mg-Na-K/dolomite catalyst, and the rest are the same.
Comparative example 3
The difference from example 8 is that: in the step S1, concentrated sulfuric acid is adopted to replace Sn-Rh-La-Mg-Na-K/dolomite catalyst, and the rest are the same.
Comparative example 4
The difference from example 2 is that: in the Sn-Rh-La-Mg-Na-K/dolomite catalyst, dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The mixture was immersed in a solution mixture having molar concentrations of NaCl and KCl of 0.35mol/L, 0.09mol/L, 0.03mol/L, 0.6mol/L, 0.2mol/L and 0.4mol/L, respectively.
Comparative example 5
The difference from example 5 is that: in the Sn-Rh-La-Mg-Na-K/dolomite catalyst, dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 Molarity of NaCl and KClImmersing the mixture in the mixed solution of 0.8mol/L, 0.01mol/L, 0.12mol/L, 0.3mol/L and 0.9 mol/L.
Comparative example 6
The difference from example 8 is that: in the Sn-Rh-La-Mg-Na-K/dolomite catalyst, dolomite powder is added in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 The mixture was immersed in a solution mixture having molar concentrations of NaCl and KCl of 0.4mol/L, 0.13mol/L, 0.02mol/L, 0.7mol/L, 0.1mol/L and 0.5mol/L, respectively.
Comparative example 7
The difference from example 2 is that: 800mol (86.4 kg) of benzyl alcohol was used, and the rest was the same.
Comparative example 8
The difference from example 5 is that: isooctanol is 900mol (117 kg), the remainder being the same.
Comparative example 9
The difference from example 8 is that: the n-hexanol was 2500mol (255 kg), the remainder being the same.
Comparative example 10
The difference from example 2 is that: 0.15kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst and the balance thereof are the same.
Comparative example 11
The difference from example 5 is that: the Sn-Rh-La-Mg-Na-K/dolomite catalyst is 2.78kg, and the rest are the same.
Comparative example 12
The difference from example 8 is that: 0.14kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst is used, and the rest are the same.
Performance detection
The yields and purities of the salicylates prepared in examples 1 to 12 and comparative examples 1 to 12 were measured and calculated.
TABLE 1
| Project | Product amount (kg) | Product yield (%) | Purity (%) |
| Example 1 | 217.28 | 90.3 | 99.5 |
| Example 2 | 218.42 | 89.8 | 99.7 |
| Example 3 | 216.60 | 88.0 | 99.6 |
| Example 4 | 239.00 | 91.6 | 99.4 |
| Example 5 | 239.75 | 90.9 | 99.5 |
| Example 6 | 238.50 | 87.4 | 99.4 |
| Example 7 | 211.12 | 89.1 | 99.5 |
| Example 8 | 212.68 | 90.8 | 99.7 |
| Example 9 | 211.57 | 91.3 | 99.4 |
| Example 10 | 215.00 | 87.3 | 99.6 |
| Example 11 | 235.25 | 88.1 | 99.9 |
| Example 12 | 208.01 | 87.7 | 99.1 |
| Comparative example 1 | 197.45 | 76.6 | 97.5 |
| Comparative example 2 | 214.75 | 75.9 | 97.8 |
| Comparative example 3 | 191.59 | 76.3 | 97.1 |
| Comparative example 4 | 199.50 | 77.5 | 99.2 |
| Comparative example 5 | 219.75 | 72.9 | 99.5 |
| Comparative example 6 | 189.59 | 70.4 | 99.4 |
| Comparative example 7 | 191.29 | 73.9 | 99.1 |
| Comparative example 8 | 209.00 | 69.6 | 99.2 |
| Comparative example 9 | 189.14 | 78.2 | 98.9 |
| Comparative example 10 | 187.19 | 72.1 | 99.1 |
| Comparative example 11 | 208.00 | 73.2 | 99.3 |
| Comparative example 12 | 176.71 | 79.6 | 99.4 |
As can be seen from Table 1, the yields of benzyl salicylate, isooctyl salicylate and hexyl salicylate prepared in examples 1-9 of the present application are above 87%, the purity is above 99.4%, and the product has good fragrance, which indicates that the yields of salicylate prepared in the preparation methods of examples 1-9 of the present application are higher, the transesterification reaction is more thoroughly carried out, and the conversion rate of methyl salicylate is higher.
The yields of the products of examples 10-12 are 87.3%, 88.1% and 87.7%, respectively, which are smaller than those of corresponding examples 2, 5 and 8, respectively, which indicates that the catalyst of the application can still maintain higher catalytic performance after multiple uses, and can be recycled repeatedly.
The yields of the products of comparative examples 1-3 are respectively smaller than those of examples 2, 5 and 8, which shows that the catalyst has higher alkali strength and higher catalytic activity, and can improve the conversion rate of methyl salicylate, thereby improving the yield of the products.
The yields of the products of comparative examples 4-6 are less than those of examples 2, 5 and 8, respectively, indicating that the molar concentrations of the ions in the Sn-Rh-La-Mg-Na-K/dolomite catalyst are lower or higher than the ranges herein, both reduce the conversion of methyl salicylate and thus the yield.
The yields of the products of comparative examples 7-9 are less than examples 2, 5 and 8, respectively, indicating that a molar ratio of methyl salicylate to alcohol below or above the ranges set forth herein, both reduce the conversion of methyl salicylate and thus the yield of salicylate.
The yields of the products of comparative examples 10-12 are less than those of examples 2, 5 and 8, respectively, indicating that the addition of Sn-Rh-La-Mg-Na-K/dolomite catalyst in amounts below or above the ranges of the present application, both reduce the conversion of methyl salicylate and thus the yield of salicylate.
The embodiments of the present invention are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in this way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (8)
1. A process for the preparation of a salicylate, said process comprising the steps of:
s1: mixing and stirring methyl salicylate, alcohol and a catalyst uniformly, and reacting for 5-10 h at the temperature of 130-190 ℃;
wherein, the mol ratio of the methyl salicylate to the alcohol is 1: (1.7-2.0); the catalyst adopts an Sn-Rh-La-Mg-Na-K/dolomite catalyst, and the dosage of the Sn-Rh-La-Mg-Na-K/dolomite catalyst is 0.1-0.5% of the total mass of methyl salicylate and alcohol;
s2: filtering the obtained product in the step S1 to remove the catalyst, washing with water, then carrying out reduced pressure distillation under the pressure of 0.93-1.8 kPa, and collecting fractions to obtain a product;
the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
mixing dolomite powder with Sn 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + Soaking in the mixed solution for 2-5 h, drying, and then at 500-600 DEG CCalcining for 1-2 h at the temperature to obtain a Sn-Rh-La-Mg-Na-K/dolomite catalyst;
sn in the mixed solution 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The ion molar concentration of the catalyst is 0.65-0.70 mol/L, 0.02-0.04 mol/L, 0.05-0.06 mol/L, 0.45-0.55 mol/L, 0.22-0.26 mol/L and 0.32-0.36 mol/L respectively.
2. The method for producing a salicylate according to claim 1, wherein: the alcohol in the step S1 adopts benzyl alcohol; the reaction temperature of the methyl salicylate and the benzyl alcohol is 160-190 ℃ and the reaction time is 6-8 h; and in the step S2, collecting the fraction at 170-175 ℃ under the pressure of 0.93-0.95 kPa to obtain benzyl salicylate.
3. The method for producing a salicylate according to claim 1, wherein: the alcohol in the step S1 adopts isooctyl alcohol; the reaction temperature of methyl salicylate and isooctyl alcohol is 130-150 ℃ and the reaction time is 5-9 h; and in the step S2, collecting the fraction at 174-178 ℃ under the pressure of 1.0-1.2 kPa to obtain isooctyl salicylate.
4. The method for producing a salicylate according to claim 1, wherein: the alcohol in the step S1 adopts n-hexanol; the reaction temperature of methyl salicylate and n-hexanol is 140-190 ℃, and the reaction time is 6-10 h; and in the step S2, collecting the fraction at 167-168 ℃ under the pressure of 1.6-1.8 kPa to obtain the hexyl salicylate.
5. The method for producing a salicylate according to claim 1, wherein: in the preparation method of the Sn-Rh-La-Mg-Na-K/dolomite catalyst, the drying condition is that the Sn-Rh-La-Mg-Na-K/dolomite catalyst is dried for 1-2 hours at the temperature of 80-90 ℃.
6. The method for preparing salicylate according to any one of claims 1 to 4, wherein: in the step S1, N is introduced in the reaction process 2 And (5) protecting.
7. The method for preparing salicylate according to any one of claims 1 to 4, wherein: in the step S1, the fraction at 64-70 ℃ is continuously fractionated in the reaction process.
8. The method for preparing salicylate according to any one of claims 1 to 4, wherein: in the step S2, the washing times are 2-3 times.
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| CN110903186A (en) * | 2018-09-18 | 2020-03-24 | 天津大加化工有限公司 | Process for producing benzyl salicylate by using supported catalyst |
| CN110903185A (en) * | 2018-09-18 | 2020-03-24 | 天津大加化工有限公司 | Production method of benzyl salicylate |
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| CN102408338A (en) * | 2011-10-27 | 2012-04-11 | 杭州友邦香料香精有限公司 | Method for synthesizing salicylate |
| CN102775311A (en) * | 2012-08-13 | 2012-11-14 | 江苏普源化工有限公司 | Preparation method of isooctyl salicylate |
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| CN110903186A (en) * | 2018-09-18 | 2020-03-24 | 天津大加化工有限公司 | Process for producing benzyl salicylate by using supported catalyst |
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