CN108863758B - Method for preparing 5-hexenoic acid - Google Patents
Method for preparing 5-hexenoic acid Download PDFInfo
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- CN108863758B CN108863758B CN201810884224.1A CN201810884224A CN108863758B CN 108863758 B CN108863758 B CN 108863758B CN 201810884224 A CN201810884224 A CN 201810884224A CN 108863758 B CN108863758 B CN 108863758B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
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- 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
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Abstract
The invention discloses a method for preparing 5-hexenoic acid, which adopts a catalyst comprising ferric hexafluorophosphate salt, a titanium-silicon molecular sieve containing rare earth and perfluorosulfonic acid resin to catalyze cyclohexanone and peroxide to carry out oxidation reaction to prepare the 5-hexenoic acid.
Description
Technical Field
The invention relates to the technical field of preparation of 5-hexenoic acid, in particular to a method for preparing 5-hexenoic acid.
Background
5-hexenoic acid is an important chemical raw material, and the 5-hexenoic acid coupling can be used for preparing delta-caprolactone with high selectivity (relevant documents such as Tetrahedron, 2009, 6510334-10338; WO2007/007084A 2). The delta-caprolactone is colorless to faint yellow oily liquid, can be used as a biodegradable material and preparation of a medical operation line after polymerization, and is also used for edible essence and tobacco essence. 5-hexenoic acid can also be used to prepare sebacic acid by olefin metathesis, which is widely used in the manufacture of cold-resistant plasticizers, synthetic nylons 610, 1010, and synthetic higher lubricants dioctyl and dibutyl sebacate.
For the oxidation of cyclohexanone to prepare 5-hexenoic acid, a process using hydrogen peroxide and ferrous sulfate-copper sulfate is provided in documents (Russian Chemical Bulletin, International Edition, 2006, 55, 2016-2019; or Japanese oil chemistry, 1992, 41, 385-390), the reaction yield is less than 40%, and the post-treatment is difficult due to the presence of ferrous sulfate-copper sulfate and inorganic acid used in the reaction.
A preparation method of a perfluorosulfonic acid/SiO 2 catalyst is mentioned in a document (applied chemistry, 2006, 23, 390-393), but experiments show that the perfluorosulfonic acid/SiO 2 catalyst has less than 50% of selectivity when used for catalyzing cyclohexanone to oxidize and prepare 5-hexenoic acid.
How to develop a method for preparing 5-hexenoic acid by oxidizing cyclohexanone with high selectivity and simple post-treatment is one of the technical difficulties which need to be broken through in the field.
Disclosure of Invention
The invention provides a method for preparing 5-hexenoic acid by catalyzing cyclohexanone to oxidize in order to make up the defects of the prior art. The catalyst of the invention is used for preparing 5-hexenoic acid by catalysis, has higher selectivity and simple post-treatment, and the used catalyst can be recycled.
In order to achieve the purpose, the invention adopts the following technical scheme:
in the presence of a catalyst, cyclohexanone is subjected to oxide oxidation reaction to generate 5-hexenoic acid, wherein the catalyst comprises ferric hexafluorophosphate salt, a titanium-silicon molecular sieve containing rare earth and perfluorosulfonic acid resin, the mass fraction of the ferric hexafluorophosphate salt in the catalyst is preferably 0.02-0.15%, the mass fraction of the perfluorosulfonic acid resin in the catalyst is preferably 30-50%, and the balance is the titanium-silicon molecular sieve containing rare earth.
Preferably, the dosage of the catalyst is 0.01 to 0.5 times of the mass of the cyclohexanone, more preferably 0.3 to 0.5 times of the mass of the cyclohexanone, the catalyst is wasted when the dosage of the catalyst is too much, and the reaction rate and the conversion rate are relatively reduced when the dosage of the catalyst is too little.
The optimized catalyst dosage is adopted, so that the reaction rate and the conversion rate are high, and the use cost of the catalyst is relatively lower.
Preferably, cyclohexanone and peroxide are subjected to oxidation reaction to prepare the 5-hexenoic acid, and the peroxide can be selected from inorganic peroxide or organic peroxide. The peroxide is preferably at least one of hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene peroxide, 2-dihydropropane peroxide, 2, 5-dimethyl-2, 5-dihydrohexane peroxide, 2-bis- (tert-butyl peroxide) propane, 2-bis- (tert-butyl peroxide) butane, 2, 5-dimethyl-2, 5-bis- (tert-butyl peroxide) hexane and 2, 2-bis- (4, 4-di-tert-butylperoxycyclohexyl) propane, and more preferably at least one of hydrogen peroxide and tert-butyl hydroperoxide, so that the safety and the cost can be both satisfied, and a preferable reaction result can be obtained.
Preferably, the peroxide may be used in an amount of 0.5 to 3 times the amount of cyclohexanone species. The low peroxide utilization rate and the increased safety risk are easily caused by the excessive peroxide consumption, the incomplete oxidation of the cyclohexanone is easily caused by the excessive peroxide consumption, the energy consumption for cyclic utilization of the cyclohexanone is high, and the economical efficiency is poor;
more preferably, the amount of the peroxide is 0.5 to 1.05 times of the amount of the cyclohexanone substance.
In the method for preparing 5-hexenoic acid, as a preferred embodiment, the temperature of the oxidation reaction is preferably 20-100 ℃, and more preferably 60-80 ℃. The reaction temperature is too low, the reaction time is long, and the productivity of the device is low; the reaction temperature is too high, the decomposition rate of the peroxide is increased, the utilization rate of the peroxide is reduced, the process safety is also reduced, and the optimal reaction temperature can give consideration to the reaction efficiency, the safety and the utilization rate of the peroxide. In a preferred embodiment, the reaction time may be 2 to 10 hours, and more preferably 3 to 5 hours.
Preferably, the ion exchange capacity of the perfluorosulfonic acid resin in the catalyst is 0.87-1.1, preferably 0.92-1.1.
Preferably, the mass ratio of the rare earth element to the titanium element in the titanium-silicon molecular sieve containing the rare earth is 0.005-0.5: 1, more preferably 0.01-0.1: 1, and particularly preferably 0.02-0.05: 1. The rare earth element and the titanium element in such a ratio can further improve the catalytic activity of the rare earth-containing titanium silicalite molecular sieve of the invention.
In order to further enhance the catalytic oxidation activity of the rare earth-containing titanium silicalite molecular sieve of the present invention, it is preferred that the rare earth element is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, rice, thulium, ytterbium, lutetium, scandium, and yttrium, and it is particularly preferred that the rare earth element is selected from one or more of lanthanum, cerium, praseodymium, neodymium, europium, scandium, and yttrium.
A process for preparing a catalyst as hereinbefore described comprising the steps of:
1) mixing and dissolving ferric hexafluorophosphate and perfluorosulfonic acid resin to form a mixed solution;
2) under the condition of hydrolysis glue making, a silicon source, a titanium source, a rare earth source and the mixture of the mixed solution prepared in the step 1) are contacted with a mixture of a template agent to obtain a gel mixture; preferably, the mixing time can be 0.5-3 h, and more preferably 1-3 h;
3) and crystallizing the gel mixture under a crystallization condition, filtering a crystallized product, drying a filtered solid, and removing the template agent to obtain the catalyst.
Further, in the step 1), mixing and dissolving iron hexafluorophosphate salt and perfluorosulfonic acid resin with alcohol; preferably, the dissolving temperature is 180-220 ℃; preferably, the mass ratio of the perfluorosulfonic acid resin to the total mass of the perfluorosulfonic acid resin and the alcohol is 10 to 15%; preferably, the alcohol is a monohydric alcohol; more preferably at least one of methanol, ethanol, propanol and isopropanol. The dosage of the rare earth-containing titanium silicalite molecular sieve is 0.01-0.5% (by mass) of the dosage of the perfluorosulfonic acid resin, and more preferably 0.1-0.3%, so as to improve the solubility of the rare earth-containing titanium silicalite molecular sieve in a system and obtain a catalyst with better catalytic activity.
Further, the selectable range of the conditions for hydrolysis and glue making in the step 2) is wide, and for the invention, the preferable conditions for hydrolysis and glue making comprise: the contact temperature is 20-90 ℃, preferably 50-90 ℃; the contact time is 0.1-72 h, preferably 0.5-36 h.
The hydrolysis glue-making conditions also comprise adding water or not adding water for hydrolysis according to the needs, if the water carried by the silicon source, the titanium source, the template agent for preparing the titanium-silicon molecular sieve and the rare earth source can meet the required water dosage, the hydrolysis can be carried out without additionally adding water, otherwise, the hydrolysis can be carried out with additionally adding water, and the technicians in the field can know the conditions.
The silicon source is one or more of silica gel, silica sol and organosilicate; the titanium source is inorganic titanium salt and/or organic titanate; the template agent is one or more of tetraalkyl ammonium hydroxide, alcohol amine and alkylamine.
Further, in step 3), the optional range of the crystallization conditions is wide, and for the present invention, the crystallization conditions preferably include: the crystallization temperature under the closed condition is 80-200 ℃, preferably 100-180 ℃, and more preferably 110-175 ℃; the time is 6-96 h, preferably 24-96 h.
The invention has the advantages that:
1. the catalyst of the invention is used for catalyzing cyclohexanone oxidation, 5-hexenoic acid can be prepared with high selectivity, the product is easy to separate, and the selectivity of 5-hexenoic acid is more than 90% by peroxide.
2. The catalyst of the invention is used for replacing the prior ferrous-inorganic acid catalyst, the problem of more free radical polymerization byproducts does not exist in the ring opening process of the cyclohexanone, the selectivity of the cyclohexanone for preparing 5-hexenoic acid reaches more than 90 percent, the catalyst can be directly recycled, and the problem of post-treatment of ferrous sulfate-copper sulfate and inorganic acid does not exist.
3. The catalyst plays a unique assisting role in the ring opening process of the cyclohexanone, and the selectivity of preparing the 5-hexenoic acid by catalyzing the oxidation of the cyclohexanone is more than 92 percent.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
[ example 1 ]
S1 preparation of catalyst
1) Mixing and dissolving ferric hexafluorophosphate and perfluorosulfonic acid resin to form a mixed solution; mixing and dissolving ferric hexafluorophosphate salt and perfluorinated sulfonic acid resin with ethanol; the dissolving temperature is 180 ℃; the mass ratio of the perfluorosulfonic acid resin to the total mass of the perfluorosulfonic acid resin and the ethanol is 10%;
2) under the condition of hydrolysis gel preparation, contacting the mixture of silica gel, titanium chloride, lanthanum nitrate and the mixed solution prepared in the step 1) with a mixture of tetrabutylammonium hydroxide to obtain a gel mixture; the contact temperature is 20 ℃; the contact time is 36 h;
3) crystallizing the gel mixture under crystallization conditions, wherein the crystallization conditions comprise: the crystallization temperature under the closed condition is 100 ℃; the time is 24 h. Then filtering the product obtained by crystallization, drying the solid obtained by filtering, and removing the template agent to obtain the catalyst, wherein the mass fraction of the rare earth-containing titanium silicalite in the catalyst is preferably 70%, and the mass fraction of the perfluorinated sulfonic acid resin in the catalyst is preferably 30%; the mass ratio of lanthanum to titanium element was 0.02: 1.
Preparation of S2, 5-hexenoic acid
Adding 9.8g of cyclohexanone, 17.56g of 55 wt% of tert-butyl hydroperoxide (the dosage of the tert-butyl hydroperoxide is 1.05 times of the molar weight of the cyclohexanone) and 3g of the catalyst prepared in the step into a reaction kettle respectively; the reaction temperature is 80 ℃; the reaction time is 5h, the product is rectified after the catalyst is separated by filtration to obtain 11.1g of product, and the HPLC purity is 96.4%.
[ example 2 ]
S1 preparation of catalyst
1) Mixing and dissolving ferric hexafluorophosphate and perfluorosulfonic acid resin to form a mixed solution; mixing and dissolving ferric hexafluorophosphate salt and perfluorinated sulfonic acid resin with ethanol; the dissolving temperature is 180 ℃; the mass ratio of the perfluorosulfonic acid resin to the total mass of the perfluorosulfonic acid resin and the ethanol is 10%;
2) under the condition of hydrolysis gel preparation, contacting the mixture of silica gel, titanium chloride, cerium nitrate and tetrabutylammonium hydroxide prepared in the step 1) with a mixture of tetrabutylammonium hydroxide to obtain a gel mixture; the contact temperature is 20 ℃; the contact time is 36 h;
3) crystallizing the gel mixture under crystallization conditions, wherein the crystallization conditions comprise: the crystallization temperature under the closed condition is 110 ℃; the time is 24 h. Then filtering the product obtained by crystallization, drying the solid obtained by filtering, and removing the template agent to obtain a catalyst C2, wherein the mass percentage of the titanium-silicon molecular sieve containing rare earth is 40% based on the total weight of the catalyst, and the mass fraction of the perfluorinated sulfonic acid resin in the catalyst is preferably 60%; the mass ratio of cerium to titanium is 0.02: 1.
Preparation of S2, 5-hexenoic acid
Adding 9.8g of cyclohexanone, 17.56g of 55 wt% of tert-butyl hydroperoxide (the dosage of the tert-butyl hydroperoxide is 1.05 times of the molar weight of the cyclohexanone) and 3g of the catalyst prepared in the step into a reaction kettle respectively; the reaction temperature is 65 ℃; the reaction time is 5h, the product is rectified after the catalyst is separated by filtration to obtain 11.3g of product, and the HPLC purity is 95.4%.
[ example 3 ]
S1 preparation of catalyst
1) Mixing and dissolving ferric hexafluorophosphate and perfluorosulfonic acid resin to form a mixed solution; mixing and dissolving ferric hexafluorophosphate salt and perfluorinated sulfonic acid resin with ethanol; the dissolving temperature is 180 ℃; the mass ratio of the perfluorosulfonic acid resin to the total mass of the perfluorosulfonic acid resin and the ethanol is 10%;
2) under the condition of hydrolysis gel preparation, contacting the mixture of silica gel, titanium chloride, europium nitrate and tetrabutylammonium hydroxide in the step 1) with a mixture of tetrabutylammonium hydroxide to obtain a gel mixture; the temperature of the contact is 50 ℃; the contact time is 36 h;
3) crystallizing the gel mixture under crystallization conditions, wherein the crystallization conditions comprise: the crystallization temperature under the closed condition is 110 ℃; the time is 24 h. Then filtering the product obtained by crystallization, drying the solid obtained by filtering, and removing the template agent to obtain a catalyst C1, wherein the mass fraction of the titanium-silicon molecular sieve containing rare earth is preferably 50%, the mass fraction of the perfluorinated sulfonic acid resin is 50%, and the mass ratio of europium to titanium is 0.02: 1;
preparation of S2, 5-hexenoic acid
Adding 9.8g of cyclohexanone, 17.56g of 55 wt% of tert-butyl hydroperoxide (the dosage of the tert-butyl hydroperoxide is 1.05 times of the molar weight of the cyclohexanone) and 3g of the catalyst prepared in the step into a reaction kettle respectively; the reaction temperature is 75 ℃; the reaction time is 5h, the product is rectified after the catalyst is separated by filtration to obtain 11.2g of product, and the HPLC purity is 95.3%.
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.
Claims (3)
1. A method of preparing 5-hexenoic acid comprising the steps of: respectively adding 9.8g of cyclohexanone, 17.56g of 55 wt% of tert-butyl hydroperoxide and 3g of catalyst into a reaction kettle, reacting at the temperature of 80 ℃ for 5 hours, filtering and separating the catalyst from the product, and rectifying to obtain 11.1g of product with the HPLC purity of 96.4%;
the preparation method of the catalyst comprises the following steps:
1) mixing and dissolving ferric hexafluorophosphate and perfluorosulfonic acid resin to form a mixed solution: mixing and dissolving ferric hexafluorophosphate salt and perfluorinated sulfonic acid resin with ethanol; the dissolving temperature is 180 ℃; the mass ratio of the perfluorosulfonic acid resin to the total mass of the perfluorosulfonic acid resin and the ethanol is 10%;
2) under the condition of hydrolysis gel preparation, contacting the mixture of silica gel, titanium chloride, lanthanum nitrate and the mixed solution prepared in the step 1) with a mixture of tetrabutylammonium hydroxide to obtain a gel mixture; the contact temperature is 20 ℃; the contact time is 36 h;
3) crystallizing the gel mixture under crystallization conditions, wherein the crystallization conditions comprise: the crystallization temperature under the closed condition is 100 ℃; the time is 24 h; then filtering the product obtained by crystallization, drying the solid obtained by filtering, and removing the template agent to obtain the catalyst, wherein the mass fraction of the rare earth-containing titanium silicalite in the catalyst is 70%, and the mass fraction of the perfluorinated sulfonic acid resin in the catalyst is 30%; the mass ratio of lanthanum to titanium element was 0.02: 1.
2. A method of preparing 5-hexenoic acid comprising the steps of: adding 9.8g of cyclohexanone, 17.56g of 55 wt% of tert-butyl hydroperoxide and 3g of catalyst into a reaction kettle respectively; the reaction temperature is 65 ℃; the reaction time is 5h, the product is rectified after being filtered and separated from the catalyst to obtain 11.3g of product, and the HPLC purity is 95.4%;
the preparation method of the catalyst comprises the following steps:
1) mixing and dissolving ferric hexafluorophosphate and perfluorosulfonic acid resin to form a mixed solution: mixing and dissolving ferric hexafluorophosphate salt and perfluorinated sulfonic acid resin with ethanol; the dissolving temperature is 180 ℃; the mass ratio of the perfluorosulfonic acid resin to the total mass of the perfluorosulfonic acid resin and the ethanol is 10%;
2) under the condition of hydrolysis gel preparation, contacting the mixture of silica gel, titanium chloride, cerium nitrate and tetrabutylammonium hydroxide prepared in the step 1) with a mixture of tetrabutylammonium hydroxide to obtain a gel mixture; the contact temperature is 20 ℃; the contact time is 36 h;
3) crystallizing the gel mixture under crystallization conditions, wherein the crystallization conditions comprise: the crystallization temperature under the closed condition is 110 ℃; the time is 24 h; then filtering the product obtained by crystallization, drying the solid obtained by filtering, and removing the template agent to obtain the catalyst, wherein the mass percent of the titanium-silicon molecular sieve containing rare earth is 40% and the mass percent of the perfluorinated sulfonic acid resin in the catalyst is 60% based on the total weight of the catalyst; the mass ratio of cerium to titanium is 0.02: 1.
3. A method of preparing 5-hexenoic acid comprising the steps of: adding 9.8g of cyclohexanone, 17.56g of 55 wt% of tert-butyl hydroperoxide and 3g of catalyst into a reaction kettle respectively; the reaction temperature is 75 ℃; the reaction time is 5h, the product is rectified after being filtered and separated from the catalyst to obtain 11.2g of product, and the HPLC purity is 95.3%;
the preparation method of the catalyst comprises the following steps:
1) mixing and dissolving ferric hexafluorophosphate and perfluorosulfonic acid resin to form a mixed solution: mixing and dissolving ferric hexafluorophosphate salt and perfluorinated sulfonic acid resin with ethanol; the dissolving temperature is 180 ℃; the mass ratio of the perfluorosulfonic acid resin to the total mass of the perfluorosulfonic acid resin and the ethanol is 10%;
2) under the condition of hydrolysis gel preparation, contacting the mixture of silica gel, titanium chloride, europium nitrate and tetrabutylammonium hydroxide in the step 1) with a mixture of tetrabutylammonium hydroxide to obtain a gel mixture; the temperature of the contact is 50 ℃; the contact time is 36 h;
3) crystallizing the gel mixture under crystallization conditions, wherein the crystallization conditions comprise: the crystallization temperature under the closed condition is 110 ℃; the time is 24 h; and then filtering the product obtained by crystallization, drying the solid obtained by filtering, and removing the template agent to obtain the catalyst, wherein the mass fraction of the titanium-silicon molecular sieve containing rare earth is 50%, the mass fraction of the perfluorinated sulfonic acid resin is 50%, and the mass ratio of europium to titanium is 0.02:1 based on the total mass of the catalyst.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183760A (en) * | 1995-04-07 | 1998-06-03 | 罗纳.布朗克纤维和树脂中间体公司 | Method for oxidising hydrocarbons, alcohols or ketones using heterogeneous catalyst |
| WO2016102343A1 (en) * | 2014-12-22 | 2016-06-30 | Rhodia Operations | Cycloalkane oxidation catalysts and method to produce alcohols and ketones |
| CN107737611A (en) * | 2017-10-24 | 2018-02-27 | 万华化学集团股份有限公司 | A kind of composite catalyst and the method that 5 hexenoic acids are prepared using the composite catalyst |
| CN107963968A (en) * | 2016-10-20 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of method for preparing phenylacetate |
-
2018
- 2018-08-06 CN CN201810884224.1A patent/CN108863758B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183760A (en) * | 1995-04-07 | 1998-06-03 | 罗纳.布朗克纤维和树脂中间体公司 | Method for oxidising hydrocarbons, alcohols or ketones using heterogeneous catalyst |
| WO2016102343A1 (en) * | 2014-12-22 | 2016-06-30 | Rhodia Operations | Cycloalkane oxidation catalysts and method to produce alcohols and ketones |
| CN107963968A (en) * | 2016-10-20 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of method for preparing phenylacetate |
| CN107737611A (en) * | 2017-10-24 | 2018-02-27 | 万华化学集团股份有限公司 | A kind of composite catalyst and the method that 5 hexenoic acids are prepared using the composite catalyst |
Non-Patent Citations (1)
| Title |
|---|
| E. K. Starostin et al..Synthesis of unsaturated dibasic acid esters from five-, six-, and seven-membered cycloalkanones*.《Russian Chemical Bulletin》.2016,第55卷(第11期),第2016-2019页. * |
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