CN102212055A - Method for preparing epsilon-caprolactone by virtue of catalytic oxidation of cyclohexanone - Google Patents
Method for preparing epsilon-caprolactone by virtue of catalytic oxidation of cyclohexanone Download PDFInfo
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- CN102212055A CN102212055A CN2010101413802A CN201010141380A CN102212055A CN 102212055 A CN102212055 A CN 102212055A CN 2010101413802 A CN2010101413802 A CN 2010101413802A CN 201010141380 A CN201010141380 A CN 201010141380A CN 102212055 A CN102212055 A CN 102212055A
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Abstract
The invention relates to a method for preparing epsilon-caprolactone by virtue of catalytic oxidation of cyclohexanone. The method comprises the following steps: S1, according to the use amount determined in advance, adding a raw material (anhydride) into a reaction container filled with a raw material (aqueous hydrogen peroxide solution) and a catalyst, and controlling the temperature of a reaction system at 5-20 DEG C so as to prepare organic peracid; and S2, adding the generated organic peracid into the cyclohexanone, evenly mixing, controlling the temperature of the reaction system at 30-100 DEG C, continuously reacting for 1-15 hours, cooling and separating after reaction is finished so as to obtain the finished epsilon-caprolactone. According to the method, in the catalytic oxidation process, the selectivity of the catalyst and the yield of the epsilon-caprolactone are still improved even though water exists in the reaction system; in the reaction process, the water in the reaction system dose not need to be removed, thus the reaction condition is reduced so that the reaction process is mild and is easy to control; the reaction is high in safety and environmentally-friendly while the high yield and selectivity can be achieved, and the used catalyst is cheap and available, is easy to prepare, has no halogen elements and is high in stability.
Description
[technical field]
The present invention relates to the Industrial Catalysis field of petrochemical industry, relate in particular to a kind of method that cyclohexanone by catalytic oxidation prepares 6-caprolactone that is used for.
[background technology]
6-caprolactone is a kind of important organic synthesis intermediate, be mainly used in synthetic poly-epsilon-caprolactone and with other copolymerization of ester class or blending and modifying; 6-caprolactone can also dissolve many fluoropolymer resins as a kind of strong solvent, to the solvency power that the resin of some indissolubles is done well, can dissolve the urethane resin of chlorinated polyolefin resin and " ESTANE " as it.Wherein, poly-epsilon-caprolactone (PCL) is the linear aliphatic adoption ester by 6-caprolactone (CL) ring-opening polymerization gained.
There is the difficult problem of the aspects such as stability of the security of raw materials quality, production and product in 6-caprolactone synthetic, so its synthetic technology difficulty is big, have only seldom several companies of states such as American and Britain, day producing at present, and China mainly relies on import.
6-caprolactone just synthesized successfully in the laboratory as far back as the thirties in 20th century.Present industrial 6-caprolactone synthesis technique is synthetic through the Baeyer-Villiger reaction by pimelinketone, and the key of this technology is the preparation of Peracetic Acid.Because oxygen to directly oxidize acetaldehyde process must be strict controlled in temperature about 0 ℃, when temperature is higher than 20 ℃, acetaldehyde is oxidized to acetate, and what is more important will generate a kind of dangerously explosive intermediate product in oxidising process.In recent years, along with the continuous expansion of 6-caprolactone Application Areas, the market requirement also constantly increases thereupon, and the exploitation of 6-caprolactone synthetic technology is also more and more come into one's own.The synthetic method of the 6-caprolactone that present document has been reported also comprises employing peroxy acid oxidation style, lower concentration H
2O
2, O
2/ air etc. are synthetic lactone of oxygenant oxidation pimelinketone and biological oxidation process, but these methods have the following disadvantages: activity of such catalysts is low, the productive rate of 6-caprolactone and selectivity is relatively poor, catalyzer is not easy to be recycled, or the like.
At the deficiency of existing 6-caprolactone synthesis technique, industry is just being put forth effort on and is being designed and developed out high reactivity, highly selective, low/pimelinketone oxidation pollution-free and that have strong development prospect prepares the effective catalyst and the novel process of 6-caprolactone.
[summary of the invention]
Goal of the invention of the present invention provides and a kind ofly prepares the method for 6-caprolactone by cyclohexanone by catalytic oxidation, to overcome above-mentioned defective of the prior art.
For reaching goal of the invention, the present invention proposes following technical scheme:
A kind ofly prepare the method for 6-caprolactone, comprise following step by cyclohexanone by catalytic oxidation:
S1 adds the raw material acid anhydrides by pre-determined consumption in the reaction vessel that fills raw material aqueous hydrogen peroxide solution and catalyzer, the temperature of control reaction system makes organic peroxide acid at 5-20 ℃;
S2 joins the organic peroxide acid that generates in the pimelinketone, mixes, and the temperature of control reaction system was reacted lasting 1-15 hour at 30-100 ℃, after reaction finishes, promptly gets the 6-caprolactone finished product through cooling, separation.
Preferably, among the above-mentioned preparation method, described acid anhydrides is diacetyl oxide, propionic anhydride or butyryl oxide.
Preferably, among the above-mentioned preparation method, described catalyzer is to be selected from least a in metal oxide, nitrate, the acetate.
Preferably, among the above-mentioned preparation method, the mol ratio of hydrogen peroxide and acid anhydrides is 0.5-5 in the described reaction system: 1.
Preferably, among the above-mentioned preparation method, the mol ratio of catalyzer and acid anhydrides is 0.001-0.1 in the described reaction system: 1.
Preferably, among the above-mentioned preparation method, the mol ratio of organic peroxide acid and pimelinketone is 0.2-5 in the described reaction system: 1.
Preferably, among the above-mentioned preparation method, described metal oxide is potassium oxide, chromic oxide, titanium oxide, aluminum oxide, zirconium white, cerium oxide, lanthanum trioxide, magnesium oxide, bismuth oxide or stannic oxide.
Preferably, among the above-mentioned preparation method, described acetate is ammonium acetate, magnesium acetate, lanthanum acetate, calcium acetate, Potassium ethanoate or barium acetate.
Preferably, among the above-mentioned preparation method, described nitrate is ammonium nitrate, magnesium nitrate, lanthanum nitrate, nitrocalcite, saltpetre or nitrate of baryta.
Preferably, among the above-mentioned preparation method, in step S2, the temperature of control reaction system is at 40-70 ℃ and sustained reaction 2-10 hour.
The method for preparing 6-caprolactone by cyclohexanone by catalytic oxidation provided by the present invention, in catalytic oxidation process, the productive rate of selectivity of catalyst and 6-caprolactone still is improved in the reaction system even water is present in, and in reaction process, need not the water in the reaction system is carried out fractionation by distillation, reduced reaction conditions, made that the reaction process gentleness is easy to control; Obtaining higher productive rate and optionally simultaneously, reaction safety height, environmental protection, and catalyst system therefor is cheap and easy to get, preparation simply, not halogen-containing element, stability height.
[embodiment]
The present invention will be further described below in conjunction with embodiments of the invention and comparative example:
Embodiment 1
In three mouthfuls of vials, add 30wt% hydrogen peroxide 1730 grams and lanthanum trioxide 25 grams successively, mixed solution is cooled to about 5-20 ℃, add diacetyl oxide 1196 grams, Peracetic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 60 ℃ of reactions 4 hours, obtain 6-caprolactone 685 grams through separating then.
Embodiment 2
In three mouthfuls of vials, add 30wt% hydrogen peroxide 1000 grams and bismuth oxide 10 grams successively, mixed solution is cooled to about 5-20 ℃, add propionic anhydride 2190 grams, Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed after 3 hours 5-20 ℃ of stirring, 50 ℃ of reactions 4 hours, obtain 6-caprolactone 600 grams through separating then.
Embodiment 3
In three mouthfuls of vials, add 30wt% hydrogen peroxide 3500 grams and stannic oxide 100 grams successively, mixed solution is cooled to about 5-20 ℃, add butyryl oxide 2400 grams, Perbutyric Acid and the 1000 gram pimelinketone that generate are mixed after 3 hours 5-20 ℃ of stirring, 50 ℃ of reactions 4 hours, obtain 6-caprolactone 750 grams through separating then.
Embodiment 4
In three mouthfuls of vials, add 30wt% hydrogen peroxide 3500 grams and lanthanum acetate 25 grams successively, mixed solution is cooled to about 5-20 ℃, add butyryl oxide 2400 grams, Perbutyric Acid and the 1000 gram pimelinketone that generate are mixed after 3 hours 5-20 ℃ of stirring, 50 ℃ of reactions 4 hours, obtain 6-caprolactone 800 grams through separating then.
Embodiment 5
In three mouthfuls of vials, add 30wt% hydrogen peroxide 3000 grams and lanthanum nitrate 25 grams successively, mixed solution is cooled to about 5-20 ℃, add diacetyl oxide 600 grams, Peracetic Acid and the 1000 gram pimelinketone that generate are mixed after 3 hours 5-20 ℃ of stirring, 70 ℃ of reactions 3 hours, obtain 6-caprolactone 405 grams through separating then.
Embodiment 6
In three mouthfuls of vials, add 30wt% hydrogen peroxide 3500 grams and Potassium ethanoate 50 grams successively, mixed solution is cooled to about 5-20 ℃, add propionic anhydride 6000 grams, Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed after 3 hours 5-20 ℃ of stirring, 75 ℃ of reactions 1 hour, obtain 6-caprolactone 820 grams through separating then.
Embodiment 7
In three mouthfuls of vials, add 30wt% hydrogen peroxide 7000 grams and sodium-acetate 50 grams successively, mixed solution is cooled to about 5-20 ℃, add propionic anhydride 6000 grams, Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed after 3 hours 5-20 ℃ of stirring, 70 ℃ of reactions 2 hours, obtain 6-caprolactone 769 grams through separating then.
Embodiment 8
In 10 liters of three mouthfuls of vials, add 30wt% hydrogen peroxide 2000 grams and sodium-acetate 50 grams successively, mixed solution is cooled to about 5-20 ℃, add diacetyl oxide 1200 grams, Peracetic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 40 ℃ of reactions 13 hours, obtain 6-caprolactone 674 grams through separating then.
Embodiment 9
In three mouthfuls of vials, add 30wt% hydrogen peroxide 1000 grams and magnesium nitrate 100 grams successively, mixed solution is cooled to about 5-20 ℃, add propionic anhydride 1200 grams, Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 35 ℃ of reactions 15 hours, obtain 6-caprolactone 666 grams through separating then.
Embodiment 10
In three mouthfuls of vials, add propionic anhydride 6000 grams and nitrocalcite 100 grams successively, mixed solution is cooled to about 5-20 ℃, add 30wt% hydrogen peroxide 5000 grams, Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 30 ℃ of reactions 15 hours, obtain 6-caprolactone 856 grams through separating then.
Embodiment 11
In three mouthfuls of vials, add 30wt% hydrogen peroxide 2000 grams, nitrocalcite 50 grams, calcium acetate 10 grams successively, mixed solution is cooled to about 5-20 ℃, add propionic anhydride 2000 grams, Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 45 ℃ of reactions 15 hours, obtain 6-caprolactone 752 grams through separating then.
Embodiment 12
In three mouthfuls of vials, add 30wt% hydrogen peroxide 2000 grams, chromic oxide 15 grams, ammonium acetate 10 grams successively, mixed solution is cooled to about 5-20 ℃, add propionic anhydride 2500 grams, Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 55 ℃ of reactions 5 hours, obtain 6-caprolactone 700 grams through separating then.
Embodiment 13
In 10 liters of three mouthfuls of vials, add 25wt% hydrogen peroxide 2400 grams, titanium oxide 2 grams, ammonium nitrate 10 grams successively, mixed solution is cooled to about 5-20 ℃, add diacetyl oxide 2000 grams, Peracetic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 55 ℃ of reactions 5 hours, obtain 6-caprolactone 688 grams through separating then.
Embodiment 14
In three mouthfuls of vials, add 30wt% hydrogen peroxide 2000 grams, titanium oxide 1 gram, ammonium nitrate 3 grams, magnesium acetate 5 grams successively, mixed solution is cooled to about 5-20 ℃, add diacetyl oxide 1500 grams, Peracetic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 60 ℃ of reactions 2 hours, obtain 6-caprolactone 728 grams through separating then.
Embodiment 15
In 10 liters of three mouthfuls of vials, add 30wt% hydrogen peroxide 2000 grams, magnesium oxide 4 grams, magnesium acetate 5 grams successively, mixed solution is cooled to about 5-20 ℃, add propionic anhydride 1500 grams, Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 60 ℃ of reactions 2 hours, obtain 6-caprolactone 765 grams through separating then.
Embodiment 16
In 10 liters of three mouthfuls of vials, add 25wt% hydrogen peroxide 1500 grams, cerium oxide 35 grams successively, mixed solution is cooled to about 5-20 ℃, add diacetyl oxide 1300 grams, Peracetic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 60 ℃ of reactions 1 hour, obtain 6-caprolactone 745 grams through separating then.
Embodiment 17
In 10 liters of three mouthfuls of vials, add 33wt% hydrogen peroxide 1640 grams, sodium-acetate 4 grams, magnesium acetate 15 grams successively, mixed solution is cooled to about 5-20 ℃, add diacetyl oxide 1200 grams, Peracetic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 60 ℃ of reactions 1 hour, obtain 6-caprolactone 647 grams through separating then.
Embodiment 18
In 10 liters of three mouthfuls of vials, add 33wt% hydrogen peroxide 1640 grams, saltpetre 5 grams, magnesium acetate 25 grams successively, mixed solution is cooled to about 5-20 ℃, add diacetyl oxide 1200 grams, Peracetic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 65 ℃ of reactions 1 hour, obtain 6-caprolactone 713 grams through separating then.
Embodiment 19
In 10 liters of three mouthfuls of vials, add 30wt% hydrogen peroxide 5000 grams, lanthanum nitrate 8 grams, magnesium acetate 2 grams successively, mixed solution is cooled to about 5-20 ℃, add diacetyl oxide 3600 grams, Peracetic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 65 ℃ of reactions 1 hour, obtain 6-caprolactone 703 grams through separating then.
Embodiment 20
In 10 liters of three mouthfuls of vials, add 30wt% hydrogen peroxide 3000 grams, lanthanum nitrate 8 grams, magnesium acetate 2 grams successively, mixed solution is cooled to about 5-10 ℃, add propionic anhydride 3600 grams, Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 65 ℃ of reactions 1 hour, obtain 6-caprolactone 783 grams through separating then.
Embodiment 21
In three mouthfuls of vials, add 30wt% hydrogen peroxide 3000 grams successively, sodium oxide 150 grams, mixed solution is cooled to about 5-20 ℃, add propionic anhydride 3000 grams, Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 75 ℃ of reactions 2 hours, obtain 6-caprolactone 724 grams through separating then.
In order to further specify the superiority of catalyzer of the present invention, select following catalyzer for use as a comparison case.
Comparative example 1
In three mouthfuls of vials, add 33wt% hydrogen peroxide 1640 grams, it is cooled to about 5-20 ℃, adds diacetyl oxide 1200 grams, after 1 hour Peracetic Acid and the 1000 gram pimelinketone that generate are mixed 5-20 ℃ of stirring, 60 ℃ of reactions 1 hour, obtain 6-caprolactone 277 grams through separating then.
Comparative example 2
In 10 liters of three mouthfuls of vials, add 30wt% hydrogen peroxide 5000 grams, it is cooled to about 5-20 ℃, add diacetyl oxide 3600 grams, Peracetic Acid and the 1000 gram pimelinketone that generate are mixed after 1 hour 5-20 ℃ of stirring, 65 ℃ of reactions 1 hour, obtain 6-caprolactone 323 grams through separating then.
Comparative example 3
In three mouthfuls of vials, add 30wt% hydrogen peroxide 3000 grams, it is cooled to about 5-20 ℃, adds propionic anhydride 3000 grams, after 1 hour Perpropionic Acid and the 1000 gram pimelinketone that generate are mixed 5-10 ℃ of stirring, 65 ℃ of reactions 1 hour, obtain 6-caprolactone 284 grams through separating then.
Can find out by the foregoing description and comparative example, do not adopt in the catalyzer Comparative Examples of the present invention, can react just after needing in the reaction process moisture in intermediate product peroxy acid distillation removed that (this is because under conventional catalytic condition with pimelinketone, if the too high levels of water in the system of peroxy acid and pimelinketone reaction, cause the 6-caprolactone of generation further hydrolysis reaction to take place and generate hexahydroxy-acetate easily, reaction product needs further purification just can obtain target product, increased the technical process of reaction like this, the selectivity of catalyzed reaction is low, the yield of 6-caprolactone is also low), and in still-process, along with scattering and disappearing of moisture, peroxy acid concentration in the reaction system improves thereupon, the possibility that reaction system is blasted also improves thereupon, reaction process control is difficulty more, and is also just higher to the requirement of reaction vessel.And technical scheme provided by the present invention has adopted metal oxide, acetate, nitrate as catalyzer, in catalytic oxidation process, need not to isolate the water in the reaction system, the productive rate of selectivity of catalyst and 6-caprolactone still is improved in the reaction system even water is present in (being compared to Comparative Examples improves more than 100%), save the distilation steps in the reaction process especially, reduced reaction conditions, made that the reaction process gentleness is easy to control; Cheap and easy to get, the preparation of this catalyzer simultaneously simply, not halogen-containing element, stability be high, and can be repeatedly used and reduce cost.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. one kind prepares the method for 6-caprolactone by cyclohexanone by catalytic oxidation, comprises following step:
S1 adds the raw material acid anhydrides by pre-determined consumption in the reaction vessel that fills raw material aqueous hydrogen peroxide solution and catalyzer, the temperature of control reaction system makes organic peroxide acid at 5-20 ℃;
S2 joins the organic peroxide acid that generates in the pimelinketone, mixes, and the temperature of control reaction system was reacted lasting 1-15 hour at 30-100 ℃, after reaction finishes, promptly gets the 6-caprolactone finished product through cooling, separation.
2. according to claim 1ly prepare the method for 6-caprolactone, it is characterized in that described acid anhydrides is diacetyl oxide, propionic anhydride or butyryl oxide by cyclohexanone by catalytic oxidation.
3. according to claim 1ly prepare the method for 6-caprolactone by cyclohexanone by catalytic oxidation, it is characterized in that, described catalyzer is to be selected from least a in metal oxide, nitrate, the acetate.
4. according to claim 1ly prepare the method for 6-caprolactone, it is characterized in that the mol ratio of hydrogen peroxide and acid anhydrides is 0.5-5 in the described reaction system: 1 by cyclohexanone by catalytic oxidation.
5. according to claim 1ly prepare the method for 6-caprolactone, it is characterized in that the mol ratio of catalyzer and acid anhydrides is 0.001-0.1 in the described reaction system: 1 by cyclohexanone by catalytic oxidation.
6. according to claim 1ly prepare the method for 6-caprolactone, it is characterized in that the mol ratio of organic peroxide acid and pimelinketone is 0.2-5 in the described reaction system: 1 by cyclohexanone by catalytic oxidation.
7. the method for preparing 6-caprolactone by cyclohexanone by catalytic oxidation according to claim 1, it is characterized in that described metal oxide is potassium oxide, chromic oxide, titanium oxide, aluminum oxide, zirconium white, cerium oxide, lanthanum trioxide, magnesium oxide, bismuth oxide or stannic oxide.
8. according to claim 1ly prepare the method for 6-caprolactone, it is characterized in that described acetate is ammonium acetate, magnesium acetate, lanthanum acetate, calcium acetate, Potassium ethanoate or barium acetate by cyclohexanone by catalytic oxidation.
9. according to claim 4ly prepare the method for 6-caprolactone, it is characterized in that described nitrate is ammonium nitrate, magnesium nitrate, lanthanum nitrate, nitrocalcite, saltpetre or nitrate of baryta by cyclohexanone by catalytic oxidation.
10. describedly prepare the method for 6-caprolactone according to any one of claim 1-9, it is characterized in that in step S2, the temperature of control reaction system is at 40-70 ℃ and sustained reaction 2-10 hour by cyclohexanone by catalytic oxidation.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351836A (en) * | 2011-10-14 | 2012-02-15 | 厦门大学 | Method for preparing caprolactone from cyclohexanone through catalytic oxidation |
| CN102603446A (en) * | 2012-02-13 | 2012-07-25 | 湖南大学 | Method for preparing organic lactone by catalyzing and oxidizing organic ketone with carbon materials |
| CN102603447A (en) * | 2012-02-13 | 2012-07-25 | 湖南大学 | Method for preparing organic lactone |
| CN103274883A (en) * | 2013-06-08 | 2013-09-04 | 中山大学 | Method for preparing lactone through catalyzing oxidation of ketone compound |
| CN105566278A (en) * | 2016-03-07 | 2016-05-11 | 南京工业大学 | Method for continuously preparing epsilon-caprolactone by utilizing micro-reaction device |
| CN105646436A (en) * | 2014-11-10 | 2016-06-08 | 中国石油化工股份有限公司 | Method for increasing yield of caprolactone |
| CN105801520A (en) * | 2016-04-07 | 2016-07-27 | 南京工业大学 | Method for preparing epoxy fatty acid ester by using microreactor |
| CN109879853A (en) * | 2019-01-27 | 2019-06-14 | 台州市源众药业有限公司 | A kind of Fe2O3/CeO2The method that catalysis of pimelinketone oxidation prepares 6-caprolactone |
| CN115057998A (en) * | 2022-07-07 | 2022-09-16 | 武汉理工大学 | Method for joint production of epsilon-caprolactone and poly (butylene succinate) |
-
2010
- 2010-04-08 CN CN2010101413802A patent/CN102212055A/en active Pending
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351836A (en) * | 2011-10-14 | 2012-02-15 | 厦门大学 | Method for preparing caprolactone from cyclohexanone through catalytic oxidation |
| CN102603446A (en) * | 2012-02-13 | 2012-07-25 | 湖南大学 | Method for preparing organic lactone by catalyzing and oxidizing organic ketone with carbon materials |
| CN102603447A (en) * | 2012-02-13 | 2012-07-25 | 湖南大学 | Method for preparing organic lactone |
| CN102603446B (en) * | 2012-02-13 | 2014-08-06 | 湖南大学 | Method for preparing organic lactone by catalyzing and oxidizing organic ketone with carbon materials |
| CN103274883A (en) * | 2013-06-08 | 2013-09-04 | 中山大学 | Method for preparing lactone through catalyzing oxidation of ketone compound |
| CN105646436A (en) * | 2014-11-10 | 2016-06-08 | 中国石油化工股份有限公司 | Method for increasing yield of caprolactone |
| CN105646436B (en) * | 2014-11-10 | 2019-01-22 | 中国石油化工股份有限公司 | A method of improving caprolactone yield |
| CN105566278A (en) * | 2016-03-07 | 2016-05-11 | 南京工业大学 | Method for continuously preparing epsilon-caprolactone by utilizing micro-reaction device |
| CN105801520A (en) * | 2016-04-07 | 2016-07-27 | 南京工业大学 | Method for preparing epoxy fatty acid ester by using microreactor |
| CN109879853A (en) * | 2019-01-27 | 2019-06-14 | 台州市源众药业有限公司 | A kind of Fe2O3/CeO2The method that catalysis of pimelinketone oxidation prepares 6-caprolactone |
| CN115057998A (en) * | 2022-07-07 | 2022-09-16 | 武汉理工大学 | Method for joint production of epsilon-caprolactone and poly (butylene succinate) |
| CN115057998B (en) * | 2022-07-07 | 2023-07-25 | 武汉理工大学 | Method for jointly producing epsilon-caprolactone and polybutylene succinate |
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Application publication date: 20111012 |