CN114956994A - Preparation method of salicylate - Google Patents
Preparation method of salicylate Download PDFInfo
- Publication number
- CN114956994A CN114956994A CN202110221168.5A CN202110221168A CN114956994A CN 114956994 A CN114956994 A CN 114956994A CN 202110221168 A CN202110221168 A CN 202110221168A CN 114956994 A CN114956994 A CN 114956994A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- salicylate
- alcohol
- dolomite
- methyl salicylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229960001860 salicylate Drugs 0.000 title claims abstract description 29
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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 95
- 239000010459 dolomite Substances 0.000 claims abstract description 80
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 80
- 229960001047 methyl salicylate Drugs 0.000 claims abstract description 60
- 229910003251 Na K Inorganic materials 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 53
- 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 18
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 89
- 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 21
- 239000011259 mixed solution Substances 0.000 claims description 17
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 claims description 16
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 16
- 150000003902 salicylic acid esters Chemical class 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 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 8
- DUKPKQFHJQGTGU-UHFFFAOYSA-N Hexyl salicylic acid Chemical compound CCCCCCOC(=O)C1=CC=CC=C1O DUKPKQFHJQGTGU-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 26
- 150000002148 esters Chemical class 0.000 description 26
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000011780 sodium chloride Substances 0.000 description 13
- 238000001354 calcination Methods 0.000 description 12
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 8
- 229960004889 salicylic acid Drugs 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012847 fine chemical Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 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
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000834 fixative Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 235000001553 Betula platyphylla Nutrition 0.000 description 1
- 241001313086 Betula platyphylla Species 0.000 description 1
- 235000017595 Callicarpa japonica Nutrition 0.000 description 1
- 240000003690 Callicarpa japonica 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 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
- 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle 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
- -1 salicylate ester Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The application relates to a preparation method of salicylate, belonging to the technical field of chemical industry, and the method comprises the following steps: s1: mixing and stirring methyl salicylate, alcohol and a catalyst uniformly, and reacting for 5-10 hours at the temperature of 130-190 ℃; wherein the molar ratio of methyl salicylate to alcohol is 1: (1.7-2.0); the catalyst adopts 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 the methyl salicylate and the alcohol; s2: and (4) filtering the product obtained 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 effects of simple process, high product yield, high 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, exists in willow bark, beautyberry leaves and Betula platyphylla in nature, and is an important fine chemical raw material. The salicylate synthesized by salicylic acid as raw material is widely used in perfume industry and daily chemical industry, and is an important fine chemical product.
Generally, salicylic acid ester is synthesized by heating salicylic acid and alcohol under the catalysis of sulfuric acid and performing esterification reaction mainly by using an esterification method. However, salicylic acid is easily subjected to side reactions during the reaction, so that the salicylic acid is oxidized to change color or generate peculiar smell, and the salicylic acid is not easy to recover once the salicylic acid is deteriorated. Therefore, the salicylic ester is generally synthesized industrially by transesterification, i.e. by using methyl salicylate and other alcohols except methanol under the catalytic heating of a catalyst to generate new salicylic ester. The inventor finds that the conversion rate of the process for synthesizing the salicylate by the ester exchange method still needs to be improved.
Disclosure of Invention
In order to simplify the process and improve the yield of the product, so that the product has better fragrance, the application provides a preparation method of the salicylate.
The preparation method of the salicylate adopts the following technical scheme:
a method for preparing salicylate comprises the following steps:
s1: mixing and stirring methyl salicylate, alcohol and a catalyst uniformly, and reacting for 5-10 hours at the temperature of 130-190 ℃;
wherein the molar ratio of methyl salicylate to alcohol is 1: (1.7-2.0); the catalyst adopts 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 the methyl salicylate and the alcohol;
s2: and (4) filtering the product obtained in the step S1 to remove the catalyst, washing with water, then distilling under reduced pressure at the pressure of 0.93-1.8 kPa, and collecting fractions to obtain the product.
By adopting the technical scheme, the methyl salicylate and the alcohol in a specific molar ratio range are subjected to ester exchange reaction under the catalytic action of a specific catalyst, and the temperature and the time in the ester exchange reaction process are controlled to be in a specific range, so that the ester exchange reaction of the methyl salicylate and the alcohol is more thorough, the reaction is promoted to be carried out in the forward direction, and the conversion rate of the methyl salicylate is improved.
The method controls the molar ratio range of the methyl salicylate and the alcohol, and because the ester exchange reaction is a reversible reaction, the addition amount of the alcohol is higher than the methyl salicylate within a certain range according to the luxatel principle, so that the ester exchange reaction 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 alcohol added exceeds the range of the present application, the time for recovering the alcohol by vacuum distillation may be increased, which may cause side reactions, and since part of the methyl salicylate is azeotropically taken away during vacuum distillation of the alcohol, the amount of the methyl salicylate azeotropically distilled with the alcohol is increased by increasing the amount of the alcohol added, which may result in a decrease in the conversion of the methyl salicylate, thereby lowering the yield.
Meanwhile, the reaction temperature in the ester exchange reaction process is controlled within a specific range and is higher than the boiling point of methanol, so that the methanol is evaporated, products produced by the reaction are reduced, the reaction is carried out towards the forward direction, 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, so that the quality of the product is influenced.
The reaction time of the ester exchange reaction process is controlled within a specific range, 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 increase of the reaction time does not increase the conversion rate of the methyl salicylate, but increases the production cost.
The method adopts Sn-Rh-La-Mg-Na-K/dolomite as the catalyst for the ester exchange reaction, controls the addition amount of the catalyst within a specific range, and fully catalyzes the ester exchange reaction, so that the ester exchange reaction is more thorough, and the conversion rate of the methyl salicylate is improved. If the addition amount of the catalyst is lower than the range, the catalyst is in too little contact with materials, so that the reaction speed is influenced; however, if the amount of the catalyst added is higher than this range, agglomeration is likely to occur, but the surface area of the catalyst in contact with the material is reduced, and the effect of improving the conversion rate cannot be achieved, and the production cost is increased.
Meanwhile, Sn-Rh-La-Mg-Na-K/dolomite is a solid alkaline catalyst, the catalytic activity is high, and a lot of flaky substances are stacked 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 promoted to be in full contact with reactants, and the conversion rate of ester exchange reaction is improved. Meanwhile, the Sn-Rh-La-Mg-Na-K/dolomite solid alkali catalyst has excellent reusability, is easy to separate from a product, can still keep higher catalytic activity after being used for many times, reduces the production cost and meets the requirement of green production. Meanwhile, the Sn-Rh-La-Mg-Na-K/dolomite solid alkali catalyst has little influence on the fragrance of the salicylate.
In conclusion, the salicylic acid ester prepared by the preparation method has high yield and high purity, and the prepared salicylic acid ester has good fragrance.
Preferably, the alcohol in 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 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 subjected to ester exchange reaction at a specific reaction temperature and within a specific reaction time, and benzyl salicylate is collected by reduced pressure fractionation under a specific pressure condition and a specific temperature condition, has sweet fragrance and is commonly used as a fragrance fixative for cosmetics and soap essence. The proper reaction condition promotes the forward reaction, so that the ester exchange reaction is carried out more fully, and the conversion rate of the methyl salicylate is improved, thereby improving the yield and the purity of the benzyl salicylate.
Preferably, the alcohol in step S1 is isooctyl alcohol; the reaction temperature of the methyl salicylate and the 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 the isooctyl salicylate.
By adopting the technical scheme, the isooctyl alcohol and the methyl salicylate are subjected to ester exchange reaction at a specific reaction temperature and within a specific reaction time, and the isooctyl salicylate is collected by reduced pressure fractionation under a specific pressure condition and a specific temperature condition, has good fragrance, and is a commonly used fine chemical raw material. The reaction forward is promoted under proper reaction conditions, so that the ester exchange reaction is carried out more fully, the conversion rate of the methyl salicylate is improved, and the yield and the purity of the isooctyl salicylate are improved.
Preferably, the alcohol in step S1 is n-hexanol; the reaction temperature of the methyl salicylate and the n-hexanol is 140-190 ℃, and the reaction time is 6-10 h; and in the step S2, collecting a fraction at 167-168 ℃ under the pressure of 1.6-1.8 kPa to obtain the hexyl salicylate.
By adopting the technical scheme, the hexyl alcohol and the methyl salicylate are subjected to ester exchange reaction at a specific reaction temperature and in a specific reaction time, and the hexyl salicylate is collected by reduced pressure fractionation under a specific pressure condition and a specific temperature condition, has the characteristic of flower fragrance and fruit fragrance, is accompanied with soft and sweet herbal fragrance, and is a fragrance fixative for common cosmetic perfumes. The reaction forward is promoted by proper reaction conditions, so that the ester exchange reaction is carried out more fully, the conversion rate of the methyl salicylate is improved, and the yield and the purity of the hexyl salicylate are improved.
Preferably, the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
adding dolomite powder to Sn 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The mixed solution is soaked for 2-5 hours, dried and then calcined for 1-2 hours 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 an immersion method 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The ions are loaded on the dolomite powder. The dolomite powder is prepared by calcining Sn 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, smaller calcium oxide particles are beneficial to full contact of active ingredients of the catalyst and reactants, and the conversion rate of methyl salicylate is improved.
And Sn 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + After ions are loaded on the 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 ester exchange reaction is enhanced, the catalytic performance of the catalyst is improved, and therefore, the methyl salicylate is improvedThe conversion of (2).
Meanwhile, the dolomite powder is controlled to be Sn 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The dipping 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 is in the mixed solution 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The ion molar concentration of the metal oxide 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 scheme, Sn in the mixed solution is strictly controlled 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The molar concentration of the metal ions is within a specific range, so that each metal ion can be well attached to dolomite powder, and the Sn-Rh-La-Mg-Na-K/dolomite catalyst has high alkali strength, high catalytic activity, excellent reusability, easy separation from a product, high catalytic activity after repeated use, reduced production cost and capability of meeting the requirement of green production.
Preferably, the drying condition is drying for 1-2 hours at the temperature of 80-90 ℃.
By adopting the technical scheme, the mixed solution is dried at a specific temperature range, moisture is removed, the possibility of interference of the moisture on subsequent calcination is reduced, 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, in the step S1, N is introduced during the reaction 2 And (6) protecting.
By adopting the technical scheme, N is introduced in the process of ester exchange reaction 2 Protection of the reaction, possibly excluding the inverseOxygen in the system should reduce the possibility of thermal oxidative degradation at high temperatures due to the presence of oxygen. At the same time, N 2 The existence of the catalyst can improve the pressure intensity in the system, promote the forward reaction and improve the conversion rate of the methyl salicylate.
Preferably, in the step S1, the fraction at 64 to 70 ℃ is continuously fractionated during the reaction.
By adopting the technical scheme, the distillate at 64-70 ℃ is continuously fractionated in the ester exchange reaction process, so that the methanol generated in the ester exchange reaction is continuously fractionated in a reaction system, the amount of the methanol generated in the reaction is continuously reduced, the forward proceeding of the reaction is promoted, and the conversion rate of the methyl salicylate is increased.
Preferably, in the step S2, the number of washing times is 2 to 3.
Through adopting above-mentioned technical scheme, this application will filter the gained thing washing certain number of times for the unreacted material in gained thing surface is fully got rid of, reduces impurity, has improved the purity of other esters of salicylic acid that the ester exchange reaction generated.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the preparation method disclosed by the application has the advantages that the conversion rate of methyl salicylate is high, so that the yield of the prepared salicylate is high, and the product has high purity;
2. the catalyst in the preparation method has high catalytic activity, is easy to separate from the raw materials, can be recycled, can still maintain high catalytic activity after being used for many times, and does not influence the fragrance 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 will be described in further detail with reference to examples.
In the following examples and comparative examples:
methyl salicylate was purchased from Beijing Beida Zhengyuan science and technology, Inc.;
benzyl alcohol was purchased from Shandong Yiwei Anhua Kogyo Co., Ltd;
isooctanol was purchased from jinan grong guang chemical ltd;
n-hexanol was purchased from dennay chemical ltd;
SnCl 2 purchased from Henan hong chemical products, Inc.;
Rh(NO 3 ) 3 purchased from Shanghai Jiu Iridium New Material science and technology, Inc.;
La(NO 3 ) 3 purchased from Hubeixing science and technology Co., Ltd;
Mg(NO 3 ) 2 purchased from shanxi wencheng chemical limited;
NaCl and KCl were purchased from Jinan Kunfeng chemical Co., Ltd.
Example 1
A method for preparing salicylate, comprising the following steps:
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 the temperature of 160 ℃, and continuously fractionating fractions at 64-70 ℃ in the reaction process;
s2: filtering the product obtained in the step S1 to remove the catalyst, washing the product for 2 times, and collecting fractions 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:
adding dolomite powder into SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And the molar concentrations of NaCl and KCl are respectively 0.65mol/L, 0.02mol/L, 0.05mol/L, 0.45mol/L, 0.22mol/L and 0.32mol/L, soaking for 2 hours in a mixed solution, then drying for 1 hour at the temperature of 80 ℃, and then calcining for 1 hour at the temperature of 500 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 2
A method for preparing salicylate, comprising the following steps:
s1: 152kg of methyl salicylate (1000 mol), 199 were added.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 fractions at the temperature of 64-70 ℃ in the reaction process;
s2: filtering the product obtained in the step S1 to remove the catalyst, washing the product for 2 times, and collecting fractions 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:
adding dolomite powder in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And respectively soaking the NaCl and the KCl into mixed solution with the molar concentrations of 0.675mol/L, 0.03mol/L, 0.055mol/L, 0.5mol/L, 0.24mol/L and 0.34mol/L for 3.5 hours, drying at the temperature of 85 ℃ for 1.5 hours, and calcining at the temperature of 550 ℃ for 1.5 hours to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 3
A method for preparing salicylate, comprising the following steps:
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 fractions at 64-70 ℃ in the reaction process;
s2: filtering the product obtained in the step S1 to remove the catalyst, washing the product with water for 3 times, and collecting fractions 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:
adding dolomite powder into SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And the molar concentrations of NaCl and KCl are respectively 0.7mol/L, 0.04mol/L, 0.06mol/L, 0.55mol/L, 0.26mol/L and 0.36mol/L, soaking for 5 hours in the mixed solution, then drying for 2 hours at the temperature of 90 ℃, and then calcining for 2 hours at the temperature of 600 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 4
A method for preparing salicylate, comprising the following steps:
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 evenly, and N is introduced 2 Protecting, reacting for 5 hours at the temperature of 130 ℃, and continuously fractionating fractions at 64-70 ℃ in the reaction process;
s2: filtering the product obtained in the step S1 to remove the catalyst, washing the product 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:
adding dolomite powder into SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And the molar concentrations of NaCl and KCl are respectively 0.65mol/L, 0.02mol/L, 0.05mol/L, 0.45mol/L, 0.22mol/L and 0.32mol/L, soaking for 2 hours in a mixed solution, then drying for 1 hour at the temperature of 80 ℃, and then calcining for 1 hour at the temperature of 500 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 5
A method for preparing salicylate, comprising the following steps:
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 evenly, and N is introduced 2 Protecting, reacting for 7 hours at the temperature of 140 ℃, and continuously fractionating fractions at 64-70 ℃ in the reaction process;
s2: filtering the product obtained in the step S1 to remove the catalyst, washing the product with water for 3 times, and 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:
adding dolomite powder into 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 and 0055mol/L, 0.5mol/L, 0.24mol/L, 0.34mol/L, drying at 85 ℃ for 1.5h, and calcining at 550 ℃ for 1.5h to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 6
A method for preparing salicylate comprises the following steps:
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 evenly, and N is introduced 2 Protecting, reacting for 9 hours at the temperature of 150 ℃, and continuously fractionating fractions at the temperature of 64-70 ℃ in the reaction process;
s2: filtering the product obtained in the step S1 to remove the catalyst, washing the product with water for 3 times, and 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:
adding dolomite powder into SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And the molar concentrations of NaCl and KCl are respectively 0.7mol/L, 0.04mol/L, 0.06mol/L, 0.55mol/L, 0.26mol/L and 0.36mol/L, soaking for 5 hours in the mixed solution, then drying for 2 hours at the temperature of 90 ℃, and then calcining for 2 hours at the temperature of 600 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 7
A method for preparing salicylate, comprising the following steps:
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 the temperature of 140 ℃, and continuously fractionating fractions at 64-70 ℃ in the reaction process;
s2: filtering the product obtained in the step S1 to remove the catalyst, washing for 2 times, and collecting fraction 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:
adding dolomite powder into SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And the molar concentrations of NaCl and KCl are respectively 0.65mol/L, 0.02mol/L, 0.05mol/L, 0.45mol/L, 0.22mol/L and 0.32mol/L, soaking for 2 hours in a mixed solution, then drying for 1 hour at the temperature of 80 ℃, and then calcining for 1 hour at the temperature of 500 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 8
A method for preparing salicylate, comprising the following steps:
s1: 152kg of methyl salicylate (1000 mol), 188.7kg of hexanol (1850 mol) and 1.0221kg of Sn-Rh-La-Mg-Na-K/dolomite catalyst are mixed and stirred evenly, and N is introduced 2 Protecting, reacting for 8 hours at the temperature of 165 ℃, and continuously fractionating fractions at 64-70 ℃ in the reaction process;
s2: filtering the product obtained in the step S1 to remove the catalyst, washing the product with water for 3 times, and collecting fraction 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:
adding dolomite powder into SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And the molar concentrations of NaCl and KCl are respectively 0.675mol/L, 0.03mol/L, 0.055mol/L, 0.5mol/L, 0.24mol/L and 0.34mol/L, the mixed solution is soaked for 3.5 hours, then the mixed solution is dried for 1.5 hours at the temperature of 85 ℃, and then the mixed solution is calcined for 1.5 hours at the temperature of 550 ℃, so that the Sn-Rh-La-Mg-Na-K/dolomite catalyst is obtained.
Example 9
A method for preparing salicylate, comprising the following steps:
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 fractions at 64-70 ℃ in the reaction process;
s2: filtering the product obtained in the step S1 to remove the catalyst, washing the product with water for 3 times, and collecting fraction 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:
adding dolomite powder in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And respectively soaking the NaCl and the KCl in mixed solution with the molar concentrations of 0.7mol/L, 0.04mol/L, 0.06mol/L, 0.55mol/L, 0.26mol/L and 0.36mol/L for 5 hours, drying at the temperature of 90 ℃ for 2 hours, and calcining at the temperature of 600 ℃ for 2 hours to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
Example 10
A method for preparing a salicylate, which is different from example 2 in that: the catalyst used was a catalyst which was recycled 5 times under the conditions of example 2.
Example 11
A method for preparing a salicylate, which differs from example 5 in that: the catalyst used was a catalyst which was recycled 7 times under the conditions of example 5.
Example 12
A method of preparing a salicylate ester, differing from example 8 in that: the catalyst used was a catalyst which was 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 a 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 used to replace Sn-Rh-La-Mg-Na-K/dolomite catalyst, and the rest is the same.
Comparative example 3
The difference from example 8 is that: in the step S1, concentrated sulfuric acid is used to replace Sn-Rh-La-Mg-Na-K/dolomite catalyst, and the rest is the same.
Comparative example 4
The difference from example 2 is that: in the Sn-Rh-La-Mg-Na-K/dolomite catalyst, the dolomite is addedPowdered in SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And NaCl and KCl at molar concentrations 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 into SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And NaCl and KCl at molar concentrations of 0.8mol/L, 0.01mol/L, 0.12mol/L, 0.3mol/L and 0.9mol/L, respectively.
Comparative example 6
The difference from example 8 is that: in the Sn-Rh-La-Mg-Na-K/dolomite catalyst, dolomite powder is added into SnCl 2 、Rh(NO 3 ) 3 、La(NO 3 ) 3 、Mg(NO 3 ) 2 And NaCl and KCl at molar concentrations 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: benzyl alcohol 800mol (86.4 kg), the rest being identical.
Comparative example 8
The difference from example 5 is that: the amount of isooctanol was 900mol (117 kg), the rest being the same.
Comparative example 9
The difference from example 8 is that: n-hexanol was 2500mol (255 kg), the rest being the same.
Comparative example 10
The difference from example 2 is that: the weight ratio of Sn-Rh-La-Mg-Na-K/dolomite catalyst is 0.15kg, and the rest is the same.
Comparative example 11
The difference from example 5 is that: the Sn-Rh-La-Mg-Na-K/dolomite catalyst accounts for 2.78kg, and the rest is the same.
Comparative example 12
The difference from example 8 is that: the weight ratio of Sn-Rh-La-Mg-Na-K/dolomite catalyst is 0.14kg, and the rest is the same.
Performance detection
The yields and purities of the salicylates prepared by the preparation methods of examples 1 to 12 and comparative examples 1 to 12 were measured and calculated.
TABLE 1
| Item | 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 benzyl salicylate, isooctyl salicylate and hexyl salicylate prepared in examples 1-9 of the present application have a yield of 87% or more and a purity of 99.4% or more, and the products have good fragrance, which indicates that the salicylic acid esters prepared by the preparation methods of examples 1-9 of the present application have high yield, the transesterification reaction is thorough, and the conversion rate of methyl salicylate is high.
The yields of the products of examples 10-12 are 87.3%, 88.1% and 87.7%, respectively, and are slightly different from those of corresponding examples 2, 5 and 8, respectively, which indicates that the catalyst of the present application can still maintain high catalytic performance after being used for many times, and can be recycled.
The yield of the products of comparative examples 1-3 is respectively less than that 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 were less than those of examples 2, 5 and 8, respectively, and show that molar concentrations of each ion in the Sn-Rh-La-Mg-Na-K/dolomite catalyst below or above the range of the present application all reduced the conversion of methyl salicylate, thereby reducing the yield.
The yields of the products of comparative examples 7-9 are less than in examples 2, 5 and 8, respectively, indicating that a molar ratio of methyl salicylate to alcohol below or above the range of the present application reduces the conversion of methyl salicylate, and thus the yield of salicylate.
The yields of the products of comparative examples 10 to 12 are lower than those of example 2, example 5 and example 8, respectively, and show that the addition of Sn-Rh-La-Mg-Na-K/dolomite catalyst in amounts below or above the range of the present application reduces the conversion of methyl salicylate, and thus the yield of salicylate.
The embodiments of the present invention are preferred embodiments of the present application, and the scope of protection of the present application is not limited by the embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. A method for preparing a salicylate, the method comprising the steps of:
s1: mixing and stirring methyl salicylate, alcohol and a catalyst uniformly, and reacting for 5-10 hours at the temperature of 130-190 ℃;
wherein the molar ratio of methyl salicylate to alcohol is 1: (1.7-2.0); the catalyst adopts 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 the methyl salicylate and the alcohol;
s2: and (4) filtering the product obtained in the step S1 to remove the catalyst, washing with water, then distilling under reduced pressure at the pressure of 0.93-1.8 kPa, and collecting fractions to obtain the product.
2. The method for preparing salicylic acid ester according to claim 1, wherein the method comprises the following steps: 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 with the temperature of 170-175 ℃ under the pressure of 0.93-0.95 kPa to obtain the benzyl salicylate.
3. The method for preparing salicylic acid esters according to claim 1, wherein the method comprises the steps of: the alcohol in the step S1 is isooctyl alcohol; the reaction temperature of the methyl salicylate and the 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 the isooctyl salicylate.
4. The method for preparing salicylic acid ester according to claim 1, wherein the method comprises the following steps: the alcohol in the step S1 is n-hexanol; the reaction temperature of the methyl salicylate and the n-hexanol is 140-190 ℃, and the reaction time is 6-10 h; and in the step S2, collecting fraction at 167-168 ℃ under the pressure of 1.6-1.8 kPa to obtain the hexyl salicylate.
5. The method for preparing a salicylic acid ester according to any one of claims 1-4, wherein the method comprises the following steps: the Sn-Rh-La-Mg-Na-K/dolomite catalyst is prepared by the following method:
adding dolomite powder to Sn 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The mixed solution is soaked for 2-5 hours, dried and then calcined for 1-2 hours at the temperature of 500-600 ℃ to obtain the Sn-Rh-La-Mg-Na-K/dolomite catalyst.
6. A process according to claim 5The preparation method of the salicylate is characterized in that: sn in the mixed solution 2+ 、Rh 3+ 、La 3+ 、Mg 2+ 、Na + 、K + The ion molar concentration of the metal oxide 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.
7. The method for preparing salicylic acid ester according to claim 5, wherein the method comprises the following steps: and the drying condition is drying for 1-2 h at the temperature of 80-90 ℃.
8. The method for preparing salicylic acid esters according to any one of claims 1-4, wherein the method comprises the steps of: in the step S1, N is introduced in the reaction process 2 And (6) performing protection.
9. The method for preparing a salicylic acid ester according to any one of claims 1-4, wherein the method comprises the following steps: in the step S1, the fraction at 64-70 ℃ is continuously fractionated in the reaction process.
10. The method for preparing a salicylic acid ester according to any one of claims 1-4, wherein the method comprises the following steps: in the step S2, the number of washing times is 2-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110221168.5A CN114956994B (en) | 2021-02-27 | 2021-02-27 | Preparation method of salicylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110221168.5A CN114956994B (en) | 2021-02-27 | 2021-02-27 | Preparation method of salicylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114956994A true CN114956994A (en) | 2022-08-30 |
| CN114956994B CN114956994B (en) | 2024-02-02 |
Family
ID=82972996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110221168.5A Active CN114956994B (en) | 2021-02-27 | 2021-02-27 | Preparation method of salicylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114956994B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060058547A1 (en) * | 2004-09-07 | 2006-03-16 | Kao Corporation | Process for producing salicylic esters |
| 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 |
| CN105541634A (en) * | 2014-11-04 | 2016-05-04 | 南京秾康生物科技有限公司 | Synthetic method of homosalate |
| CN109912409A (en) * | 2019-04-13 | 2019-06-21 | 天津大加化工有限公司 | A kind of production method of isoamyl salicylate |
| CN110903185A (en) * | 2018-09-18 | 2020-03-24 | 天津大加化工有限公司 | Production method of benzyl salicylate |
| 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 |
-
2021
- 2021-02-27 CN CN202110221168.5A patent/CN114956994B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060058547A1 (en) * | 2004-09-07 | 2006-03-16 | Kao Corporation | Process for producing salicylic esters |
| 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 |
| CN105541634A (en) * | 2014-11-04 | 2016-05-04 | 南京秾康生物科技有限公司 | Synthetic method of homosalate |
| CN110903185A (en) * | 2018-09-18 | 2020-03-24 | 天津大加化工有限公司 | Production method of benzyl salicylate |
| 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 |
| CN109912409A (en) * | 2019-04-13 | 2019-06-21 | 天津大加化工有限公司 | A kind of production method of isoamyl salicylate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114956994B (en) | 2024-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113582965B (en) | Method for preparing lactide based on catalytic cracking of organic guanidine complex | |
| CN107721821B (en) | Method for preparing 1, 3-propylene glycol | |
| JP2009519286A (en) | Method for producing glycerin carbonate | |
| AU2008271501A1 (en) | Method for producing (Meth)acrylates | |
| CN103209951A (en) | Ketocarboxylic acids, ketocarboxylic esters, methods of manufacture and uses thereof | |
| EP1687264B1 (en) | Process for the production of metal salts of trifluoromethane sulphonic acid | |
| CN105646570A (en) | Novel organic titanate butanediol titanium, and synthesis method and application thereof | |
| CN1687003A (en) | Method for synthesizing phenyloxalate from dicthyl oxalate and phenol | |
| AU2008271500B2 (en) | Method for producing butanediol dimethacrylates | |
| CN114956994A (en) | Preparation method of salicylate | |
| US8962882B2 (en) | Lactic acid direct synthesis process | |
| CN108043454A (en) | A kind of mesoporous basic catalyst and preparation method and application | |
| CN102267903B (en) | Manufacturing method for (methyl) acrylic acid hydroxyalkyl ester | |
| CN102557889A (en) | Method for synthesizing polyglycerol by using load type sodium hydroxide solid alkali catalyst | |
| CN101735055A (en) | Method for producing plasticizer tirbutyl citrate | |
| JP3763076B2 (en) | Method for producing α-hydroxycarboxylic acid ester | |
| WO2004007422A1 (en) | Process for producing diol derivative | |
| CN1120049C (en) | Supported type heteropolya cid catalyst in synthesis of ethylene glycol series monoethers acetate | |
| CN113289631A (en) | Supported metal oxide catalyst for synthesizing isobutyraldehyde by methanol and ethanol one-step method and preparation method and application thereof | |
| CN109678651B (en) | Preparation method of high-purity alpha, alpha-dichloroethyl cyclopropane | |
| CN102030633A (en) | Manufacturing method of ester plasticizers | |
| FR3010329A1 (en) | USE OF CERTAIN PLANTS CONTAINING ALKALI OR ALKALINE-EARTH METALS FOR THE IMPLEMENTATION OF ORGANIC CHEMICAL REACTIONS | |
| CN102503823A (en) | Synthesis process for fatty acyl citrate compound | |
| CN110845311A (en) | Preparation method of p-hydroxyacetophenone | |
| CN100595186C (en) | Method for synthesizing diaryl carbonic acid ester and dimethyl ether by one-step method and catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |