CN108558819A - A method of preparing 6-caprolactone using carbon nanotube - Google Patents

A method of preparing 6-caprolactone using carbon nanotube Download PDF

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CN108558819A
CN108558819A CN201810370114.3A CN201810370114A CN108558819A CN 108558819 A CN108558819 A CN 108558819A CN 201810370114 A CN201810370114 A CN 201810370114A CN 108558819 A CN108558819 A CN 108558819A
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cyclohexanone
reaction
catalyst
caprolactone
methacrylaldehyde
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余皓
杨利情
曹永海
王红娟
彭峰
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
    • C07D313/02—Seven-membered rings
    • C07D313/04—Seven-membered rings not condensed with other rings
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • 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 kind of methods preparing ε caprolactones using carbon nanotube.This method is in a certain amount of organic solvent, cyclohexanone, pro-oxidant and a certain amount of catalyst is added, using molecular oxygen as oxidant, the pro-oxidant is methacrylaldehyde, the catalyst is carbon material, under conditions of pressure is 0.1 ~ 2MPa and temperature is 50~90 DEG C, it is stirred to react 0.1~for 24 hours.The present invention has pro-oxidant efficient, and ε caprolactones and acrylic acid selectivity are high, and catalyst is easy recycling, and oxidant is environmentally protective, easy to operate, it is at low cost the advantages that.

Description

A method of preparing 6-caprolactone using carbon nanotube
Technical field
The present invention relates to the preparation fields of 6-caprolactone, and in particular to a kind of side preparing 6-caprolactone using carbon nanotube Method.
Background technology
6-caprolactone is a kind of important organic synthesis intermediate and new polyester monomer, is mainly used for synthesizing poly- ε-in oneself Ester and with other esters copolymerization or blending and modifying, to improve its glossiness, the transparency and antistick characteristic etc..6-caprolactone open loop is poly- The linear aliphatic adoption ester for closing gained is polycaprolactone (PCL), and PCL has good thermoplasticity, molding processibility and environmental protection Property.With the enhancing of people's environmental consciousness, it will also be expected to substitute existing common plastics, largely enter non-returnable container material and Mulch market.Plurality of advantages based on itself and wide application prospect, monomer 6-caprolactone will also have huge market Potentiality.Currently, having reported the synthetic method of more 6-caprolactone, wherein the side of cyclohexanone B-V oxidative synthesis 6-caprolactones Method has become hot spot.
Oxidant employed in reaction is different, and oxidizing cyclohexanone method can be divided into four kinds：Peroxide acid oxidation, H2O2 Oxidizing process, biological oxidation process and molecular oxygen oxidation method.Molecular oxygen overcomes other three kinds of method for oxidation danger as oxidant The disadvantage high, yield is low, of high cost, molecular oxygen have safe, cheap and easy to get, by-product as the oxidant that oxidizing cyclohexanone reacts The advantages that object is few and environmental pollution is small, but since the oxidability of molecular oxygen is weaker, directly utilize molecular oxygen oxidation cyclohexanone It is unable to get satisfied as a result, aldehydes co-oxidants and catalyst appropriate need to usually be added during the reaction can just play oxygen Change the effect of cyclohexanone.
Pro-oxidant in cyclohexanone molecular oxygen oxidation method mainly uses aldehydes, common aldehydes pro-oxygenic agent include acetaldehyde, Positive propionic aldehyde, isobutylaldehyde, isopentyl aldehyde, benzaldehyde, p-tolyl aldehyde etc., wherein benzaldehyde or p-tolyl aldehyde is the most commonly used. But one side benzaldehyde efficiency (conversion ratio of yield/benzaldehyde of 6-caprolactone) is relatively low.For example, Nabae (ACS Catalysis,2013,3:230-236) et al. the peak efficiency of the benzaldehyde of report is 0.77.On the other hand, benzaldehyde is anti- Benzoic acid should be changed into the process, value reduces.Therefore, low molecular weight, efficient pro-oxygenic agent are probed into for raising process Economy be of great significance.Meanwhile high activated catalyst is developed for optimization catalyst system and catalyzing also with vital work With.
Different according to the catalyst taken in reaction, the type of catalyst can substantially be divided into two classes：Metallic catalyst And C catalyst.Patent CN201110298626 uses metal porphyrins for catalyst, can obtain preferably reacting knot Fruit, but the price is rather stiff of metal porphyrins, industrialization are beyond affordability.Ruiz etc. (Tetrahedron, 2006,62, 11697) catalysis behaviors of the MgO in cyclohexanone B-V reactions is reported, but the conversion ratio of cyclohexanone only has 63%.It is nonmetallic Carbon material have the characteristics that stability is good and catalytic activity is high, always be catalysis scholar primary study object.Li Yuefang(Carbon,2013,55:It 269-275) et al. finds at normal temperatures, graphite catalysis oxidation cyclohexanone, high conversion rate Up to 92.5%, the selectivity of 6-caprolactone is 100%.Ji Hongbing(Molecular Catalysis,2017,48:152- Et al. 158) multi-walled carbon nanotube catalysis of pimelinketone oxidative synthesis 6-caprolactone is utilized, it is found that it is good multi-walled carbon nanotube has Catalytic activity, yclohexanone conversion ratio are up to 94%, and the high selectivity of 6-caprolactone is up to 100%.Patent CN106397386A reports Nitrogen doped carbon nanotube is used for catalysis of pimelinketone oxidative synthesis 6-caprolactone, but the conversion ratio of methacrylaldehyde is not high, using not filling Point.Therefore, the carbon material for developing different doped forms, it is meaningful to improve catalytic activity.The present invention is by carbon fluoride nano-tube The catalyst of 6-caprolactone is prepared as cyclohexanone B-V oxidations.
Invention content
It is an object of the invention to develop the carbon material of different doped forms to improve the catalytic activity of carbon material, and solve Certainly existing cyclohexanone Baeyer-Villiger oxidation reactions O2In/aldehyde system, pro-oxidant benzaldehyde efficiency is low, of high cost Problem provides a kind of pro-oxidant-methacrylaldehyde, in conjunction with carbon fluoride nano-tube as non-metallic catalyst, provides a kind of catalysis effect Rate is high, catalyst is easy recycling, the method for synthesis 6-caprolactone at low cost.
The purpose of the present invention is achieved through the following technical solutions.
A method of 6-caprolactone being prepared using carbon nanotube, is included the following steps：
In organic solvent, cyclohexanone, pro-oxidant and catalyst is added, using molecular oxygen as oxidant, 50~90 It is stirred to react at DEG C, obtains 6-caprolactone；The pro-oxidant is methacrylaldehyde, and the catalyst is carbon fluoride nano-tube (FCNT), one or more of sulphur carbon nanotube (SCNT) and p-doped carbon nanotube (PCNT) are mixed.
Preferably, the organic solvent is in 1,2- dichloroethanes, carbon tetrachloride, acetonitrile, dichloromethane and toluene More than one.
Preferably, the organic solvent is 1,2- dichloroethanes.
Preferably, the temperature of the reaction is 80 DEG C.
Preferably, the mass ratio of the organic solvent and cyclohexanone is (6~799)：1.
Preferably, the molar ratio of the methacrylaldehyde and cyclohexanone is (0.25~100)：1.
It is further preferred that the molar ratio of the methacrylaldehyde and cyclohexanone is 4：1.
Preferably, the mass ratio of the catalyst and cyclohexanone is (0.01~2)：1.
Preferably, the pressure of the reaction is 0.1~2MPa.
It is further preferred that the pressure of the reaction is 1MPa.
Preferably, the time of the reaction be 0.1~for 24 hours.
It is further preferred that the time of the reaction is 4h.
Compared with prior art, the present invention having the following advantages that：
(1) present invention obtains the acrylic acid with higher industrial value, carries using methacrylaldehyde as pro-oxidant after reaction The high economic feasibility of process.The efficiency (the ratio between the yield of 6-caprolactone and the conversion ratio of methacrylaldehyde) of methacrylaldehyde is rubbed in aldehyde ketone You can reach 100% than being more than after 4, can substantially reduce the consumption of pro-oxygenic agent.Meanwhile relative to common pro-oxidant benzene The oxidation product acrylic acid of formaldehyde, methacrylaldehyde differs bigger with the boiling point of 6-caprolactone, is more advantageous to the Separation ＆ Purification of product.
(2) for the present invention using carbon fluoride nano-tube as catalyst, catalytic activity is high, is easy recycling, environmental-friendly.
(3) present invention has the carbon nanotube (such as NCNTs) than Traditional dopant using carbon fluoride nano-tube as catalyst Higher catalytic activity.
Description of the drawings
Fig. 1 is the gas chromatogram of reaction solution after embodiment 1 is reacted.
Fig. 2 is the scanning electron microscope diagram (SEM) of carbon fluoride nano-tube of the present invention.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is described further, but protection scope of the present invention is not limited to In embodiment statement.
The scanning electron microscope diagram (SEM) and XPS spectrum datas such as Fig. 2 of carbon fluoride nano-tube of the present invention, Shown in table 1, the results showed that, F contents are 53.78at%.Wherein, carbon fluoride nano-tube of the present invention is by business way What diameter was commercially available.
Table 1
Title In conjunction with energy Half-peak breadth Peak area Atomic mass score
F 1s 686.92 1.95 139805.15 53.78
O 1s 533.46 0.5 1187.56 0.62
C 1s 288.29 1.5 32522.04 45.6
Selectivity in relation to cyclohexanone and acrolein conversion rate (%) and 6-caprolactone and acrylic acid in following example (%) is measured by gas chromatograph (GC) analysis, and GC detects computational methods and uses internal standard method, using o-dichlorohenzene as internal standard Object, by drawing four kinds of corresponding standard curves of substance respectively, the GC detections in conjunction with reaction solution are calculated.
Examples 1 to 3
By 17mL 1,2- dichloroethanes, 1.3g o-dichlorohenzenes (internal standard compound), 0.59g cyclohexanone, 1.35g methacrylaldehyde and 50mg catalyst as shown in Table 2 is added sequentially to be heated with stirring to 80 DEG C in autoclave, is passed through oxygen, starts timing, And it is 1MPa to maintain its pressure during the reaction, after reacting 4h, stops timing, reaction kettle is cooled to room temperature, filtered fluid is solid Phase mixture obtains solid catalyst and the liquid phase mixture containing unreacted reactant and reaction product.The liquid phase mixes Object is detected analysis with gas chromatograph (GC) (see Fig. 1).GC testing results are shown in Table 2, and (different carbon materials are to cyclohexanone The influence of Baeyer-Villiger oxidation reactions).
It mixes sulphur carbon nanotube, p-doped carbon nanotube, nitrogen doped carbon nanotube used by the present embodiment to make by oneself, by chemical gas Phase sedimentation is made, and specific preparation method is as follows：
The preparation of nitrogen doped carbon nanotube：With Fe-Mo/Al2O3As catalyst, aniline is passed through ammonia as presoma (nitrogen source) Gas atmosphere prepares synthesis.(1) 5g catalyst is weighed with electronic balance to be placed in molybdenum boat, be positioned over long 3m in horizontal pipe furnace, In the quartz ampoule of diameter 0.25m, in N2By diamond heating to 500 DEG C under atmosphere, it is passed through the H that volumetric concentration is 30%2Reduction half Hour, then again in N2By diamond heating to 800 DEG C in atmosphere, whole process gas flow is set as 10L/min；(2) exist When the temperature that tube furnace places porcelain boat position reaches 800 DEG C, it is passed through NH3, aniline is injected with the flow velocity of 5mL/min with syringe pump Flow velocity is switched into 2mL/min into quartz ampoule, after reaction 2h and reacts 3h.(3) 10min after precursor injection, is closed The heat preservation of stopped pipe type stove is arranged, and gained sample is can be taken off when furnace temperature drops to 100 DEG C.
P-doped carbon nanotube and the preparation for mixing sulphur carbon nanotube：Preparation method is similar to the above.(1) p-doped carbon nanotube It prepares：Triphenylphosphine is dissolved in toluene, the triphenylphosphine solution of 50wt.% is formed, using this solution as phosphorus source, remaining operation Method is consistent with nitrogen doped carbon nanotube is made.(2) preparation of sulphur carbon nanotube is mixed：Using thiophene solution as sulphur source, remaining operation Method is consistent with nitrogen doped carbon nanotube is made.
All material used herein is washed with the ratio of 100mg/mL with concentrated hydrochloric acid long agitation using preceding To remove remaining metallic catalyst in carbon material preparation process, waits after washing, filtered to neutrality, be put into deionized water Irritated in 110 DEG C of baking ovens to stay overnight, pack is spare.
Table 2
As can be seen from Table 2, carbon fluoride nano-tube shows optimal catalytic performance.
Embodiment 4~7
By solvent as shown in table 3 17mL, 1.3g o-dichlorohenzenes (internal standard compound), 0.59g cyclohexanone, 1.35g methacrylaldehyde and 50mg carbon fluoride nano-tubes (F contents are 53.78at%) are added sequentially to be heated with stirring to 80 DEG C in autoclave, are passed through oxygen Gas starts timing, and it is 1MPa to maintain its pressure during the reaction, after reacting 4h, stops timing, reaction kettle is cooled to room Temperature, filtered fluid solid-phase mixture obtain solid catalyst and the liquid phase mixture containing unreacted reactant and reaction product. The liquid phase mixture is detected analysis with gas chromatograph (GC).GC testing results are shown in Table 3, and (different solvents are to cyclohexanone The influence of Baeyer-Villiger oxidation reactions).
Table 3
Embodiment 1 4 5 6 7
Different solvents 1,2- dichloroethanes Carbon tetrachloride Acetonitrile Dichloromethane Toluene
Yclohexanone conversion ratio (%) 54.3 30 20 15 13
6-caprolactone selectivity (%) 100 57 66 70 45
Acrolein conversion rate (%) 53.4 30 31 40 23
Acrylic acid selectivity (%) 100 100 100 100 100
Methacrylaldehyde efficiency 1 0.57 0.43 0.26 0.25
As shown in Table 3, when 1,2- dichloroethanes is as solvent, the effect of the selectivity and methacrylaldehyde of 6-caprolactone and acrylic acid Rate is best.
Embodiment 8~11
By 17mL 1,2- dichloroethanes, 1.3g o-dichlorohenzenes (internal standard compound), 0.59g cyclohexanone, 1.35g methacrylaldehyde and 50mg carbon fluoride nano-tubes (F contents are 53.78at%) are added sequentially to be heated with stirring in autoclave warm shown in table 4 Degree is passed through oxygen, starts timing, and it is 1MPa to maintain its pressure during the reaction.After reacting 4h, stops timing, will react Kettle is cooled to room temperature, filtered fluid solid-phase mixture, obtains solid catalyst and containing unreacted reactant and reaction product Liquid phase mixture.The liquid phase mixture is detected analysis with gas chromatograph (GC).The gas phase of reaction solution after embodiment 1 is reacted Chromatogram is as shown in Figure 1.GC testing results are shown in Table 4 (shadows of the reaction temperature to cyclohexanone Baeyer-Villiger oxidation reactions It rings).
Table 4
Embodiment 8 9 10 1 11
Reaction temperature (DEG C) 50 60 70 80 90
Yclohexanone conversion ratio (%) 1.5 18 30.8 54.3 69.1
6-caprolactone selectivity (%) 80.5 91.2 100 100 70.0
Acrolein conversion rate (%) 7 30.2 45.5 53.4 79
Acrylic acid selectivity (%) 100 100 100 100 100
Methacrylaldehyde efficiency 0.17 0.54 0.68 1 0.61
As can be seen from Table 4, temperature increases the oxidation for being conducive to cyclohexanone, but when temperature reaches 80 DEG C, in conversion ratio While raising, the selectivity of 6-caprolactone and acrylic acid, especially 6-caprolactone substantially reduces, and therefore, is ensureing ε-in oneself Under the premise of ester selectivity 100% and acrylic acid high income, optimal temperature is 80 DEG C.
Embodiment 12~18
By 17mL 1,2- dichloroethanes, 1.3g o-dichlorohenzenes (internal standard compound), 0.59g cyclohexanone, 1.35g methacrylaldehyde and 50mg carbon fluoride nano-tubes (F contents are 53.78at%) are added sequentially to be heated with stirring to 80 DEG C in autoclave, are passed through oxygen Gas starts timing, and it is 1MPa to maintain its pressure during the reaction.After reaction to the time shown in table 5, stop timing, it will Reaction kettle is cooled to room temperature, filtered fluid solid-phase mixture, is obtained solid catalyst and is produced containing unreacted reactant and reaction The liquid phase mixture of object.The liquid phase mixture is detected analysis with gas chromatograph (GC).GC testing results are shown in Table 5 (reactions Influence of the time to cyclohexanone Baeyer-Villiger oxidation reactions).
Table 5
Data in analytical table 5 it is found that the conversion ratio extension at any time of cyclohexanone and increase, the efficiency of methacrylaldehyde is at any time Extension first increase and decline again, and the selectivity of 6-caprolactone and the efficiency of methacrylaldehyde are substantially reduced after 4h, are ensureing ε- Under the premise of caprolactone selectivity 100% and methacrylaldehyde efficiency are 1, in the time range that table 4 is studied, 4h is optimal.
Embodiment 19~22
By 17mL 1,2- dichloroethanes, 1.3g o-dichlorohenzenes (internal standard compound), 0.59g cyclohexanone, 1.35g methacrylaldehyde and 50mg carbon fluoride nano-tubes (F contents are 53.78at%) are added sequentially to be heated with stirring to 80 DEG C in autoclave, are passed through oxygen Gas starts timing, and it is after reacting 4h, to stop timing shown in table 6, reaction kettle is cooled down to maintain its pressure during the reaction To room temperature, filtered fluid solid-phase mixture, obtains solid catalyst and the liquid phase containing unreacted reactant and reaction product is mixed Close object.The liquid phase mixture is detected analysis with gas chromatograph (GC).GC testing results are shown in Table 6, and (reaction pressure is to hexamethylene The influence of ketone Baeyer-Villiger oxidation reactions).
Table 6
Embodiment 19 20 1 21 22
Reaction pressure (MPa) 0.1 0.5 1 1.5 2
Yclohexanone conversion ratio (%) 13 26.8 54.3 63.8 74.1
6-caprolactone selectivity (%) 88 90.4 100 88.5 78.2
Acrolein conversion rate (%) 14.1 29.4 53.4 66.1 78.0
Acrylic acid selectivity (%) 100 100 100 100 100
Methacrylaldehyde efficiency 0.81 0.82 1 0.85 0.74
Data in analytical table 6 are it is found that the conversion ratio of cyclohexanone increases with the increase of pressure, and the efficiency of methacrylaldehyde is then with pressure The increase of power first increases to be declined again, and the selectivity of 6-caprolactone is substantially reduced after pressure is more than 1MPa, is ensureing ε-in oneself Under the premise of the selectivity of ester and the efficiency of methacrylaldehyde are 1, in the pressure limit of table 5,1MPa is optimal.
Embodiment 23~27
By 17mL 1,2- dichloroethanes, 1.3g o-dichlorohenzenes (internal standard compound), 0.59g cyclohexanone, 1.35g methacrylaldehyde and such as The carbon fluoride nano-tube (F contents are 53.78at%) of the amount of Table 7 is added sequentially to be heated with stirring to 80 in autoclave DEG C, it is passed through oxygen, starts timing, and it is 1MPa to maintain its pressure during the reaction, after reacting 4h, stops timing, will react Kettle is cooled to room temperature, filtered fluid solid-phase mixture, obtains solid catalyst and containing unreacted reactant and reaction product Liquid phase mixture.The liquid phase mixture is detected analysis with gas chromatograph (GC).It is (different amounts of that GC testing results are shown in Table 7 Influence of the carbon fluoride nano-tube to cyclohexanone Baeyer-Villiger oxidation reactions).
Table 7
Embodiment 23 24 25 1 26 27
The amount (mg) of carbon fluoride nano-tube 0 10 30 50 70 100
Yclohexanone conversion ratio (%) 1 18.1 30.5 54.3 60.2 63.6
6-caprolactone selectivity (%) - 81 90.4 100 95.2 91.7
Acrolein conversion rate (%) 1 20.1 33.4 53.4 60.7 62.9
Acrylic acid selectivity (%) - 100 100 100 100 100
Methacrylaldehyde efficiency - 0.73 0.83 1 0.94 0.93
As shown in Table 7, when the amount of catalyst is 50mg, while the selectivity for ensureing 6-caprolactone is 100%, ε- The yield of caprolactone and acrylic acid is highest, and the efficiency of methacrylaldehyde is also maximum.
Embodiment 28~35
By 1,2- dichloroethanes (ensureing that the mass ratio of solvent and cyclohexanone is 6~799), the 1.3g neighbour's dichloro of certain volume Methacrylaldehyde and the cyclohexanone (dosage of cyclohexanone wherein in embodiment 29~31 of benzene (internal standard compound), as shown in table 8 various molar ratios Be 6mmol, the dosage of methacrylaldehyde is 24mmol in embodiment 32~36), (F contents are for the carbon fluoride nano-tube of 50mg It 53.78at%) is added sequentially to be heated with stirring to 80 DEG C in autoclave, is passed through oxygen, start timing, and in reaction process Middle its pressure of maintenance is 1MPa, after reacting 4h, stops timing, reaction kettle is cooled to room temperature, filtered fluid solid-phase mixture obtains Solid catalyst and liquid phase mixture containing unreacted reactant and reaction product.The liquid phase mixture gas chromatograph (GC) it is detected analysis.GC testing results are shown in Table 8, and (different aldehyde ketone molar ratios are anti-to cyclohexanone Baeyer-Villiger oxidations The influence answered).
Table 8
Data in analytical table 8 it is found that cyclohexanone conversion ratio with aldehyde ketone than increase and increase, and when aldehyde ketone ratio be 4 when, Methacrylaldehyde efficiency is 1, and after aldehyde ketone ratio is more than 4, the efficiency of methacrylaldehyde maintains 1, is selectively in guarantee 6-caprolactone 100% and methacrylaldehyde efficiency be 100% under the premise of, best aldehyde ketone molar ratio be 4.00.

Claims (10)

1. a kind of method preparing 6-caprolactone using carbon nanotube, which is characterized in that include the following steps：
In organic solvent, cyclohexanone, pro-oxidant and catalyst is added, using molecular oxygen as oxidant, at 50~90 DEG C It is stirred to react, obtains 6-caprolactone；The pro-oxidant is methacrylaldehyde, and the catalyst is carbon fluoride nano-tube, mixes sulphur carbon nanometer One or more of pipe and p-doped carbon nanotube.
2. according to the method described in claim 1, it is characterized in that, the organic solvent is 1,2- dichloroethanes, four chlorinations One or more of carbon, acetonitrile, dichloromethane and toluene.
3. according to the method described in claim 1, it is characterized in that, the temperature of the reaction is 80 DEG C.
4. according to the method described in claim 1, it is characterized in that, the molar ratio of the methacrylaldehyde and cyclohexanone is（0.25~ 100）：1.
5. according to the method described in claim 4, it is characterized in that, the molar ratio of the methacrylaldehyde and cyclohexanone is 4：1.
6. according to the method described in claim 1, it is characterized in that, the mass ratio of the catalyst and cyclohexanone is（0.01~ 2）：1.
7. according to the method described in claim 1, it is characterized in that, the pressure of the reaction is 0.1~2 MPa.
8. the method according to the description of claim 7 is characterized in that the pressure of the reaction is 1MPa.
9. according to the method described in claim 1, it is characterized in that, the time of the reaction is 0.1~24 h.
10. according to the method described in claim 9, it is characterized in that, the time of the reaction is 4 h.
CN201810370114.3A 2018-04-24 2018-04-24 A method of preparing 6-caprolactone using carbon nanotube Pending CN108558819A (en)

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CN111018823A (en) * 2019-12-12 2020-04-17 河南能源化工集团研究总院有限公司 Process for preparing epsilon-caprolactone and co-producing methacrylic acid by cyclohexanone
US10710974B2 (en) * 2016-09-13 2020-07-14 South China University Of Technology Method for preparing epsilon-caprolactone
CN111482191A (en) * 2020-05-13 2020-08-04 厦门大学 Nickel-based catalyst, preparation method and application thereof, and method for preparing organic ester by catalytic oxidation of organic ketone
CN112920159A (en) * 2021-01-20 2021-06-08 华南理工大学 Method for preparing epsilon-caprolactone from cyclohexane
CN115286611A (en) * 2022-08-22 2022-11-04 华南理工大学 Method for simultaneously preparing epsilon-caprolactone and propionic acid

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