CN103848807B - A kind of method adopting solid peroxygen acid oxidase pimelinketone to synthesize 6-caprolactone - Google Patents

A kind of method adopting solid peroxygen acid oxidase pimelinketone to synthesize 6-caprolactone Download PDF

Info

Publication number
CN103848807B
CN103848807B CN201410103050.2A CN201410103050A CN103848807B CN 103848807 B CN103848807 B CN 103848807B CN 201410103050 A CN201410103050 A CN 201410103050A CN 103848807 B CN103848807 B CN 103848807B
Authority
CN
China
Prior art keywords
caprolactone
synthesis
sno
mgo
liquid
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.)
Active
Application number
CN201410103050.2A
Other languages
Chinese (zh)
Other versions
CN103848807A (en
Inventor
张光旭
张红波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Dongwei Chemical New Material Co ltd
Original Assignee
Wuhan University of Technology WUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN201410103050.2A priority Critical patent/CN103848807B/en
Publication of CN103848807A publication Critical patent/CN103848807A/en
Application granted granted Critical
Publication of CN103848807B publication Critical patent/CN103848807B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a kind of with MgO/SnO 2/ WO 3oxide compound or MgO/SnO 2/ ZrO 2oxide compound is the method for catalyst preparing 6-caprolactone: MgO/SnO 2/ WO 3oxide compound or MgO/SnO 2/ ZrO 2oxide compound is catalyzer, and the hydrogen peroxide using 50% can obtain Peracetic Acid as oxidizing acetic acid, hydrogen peroxide and catalyst mixture, uses it for peroxyester synthesis 6-caprolactone and has higher yield and selectivity.The present invention uses MgO/SnO 2/ WO 3oxide compound is catalyzer, and this method for preparing catalyst is simple, has very high activity and selectivity, water resisting property strong with reaction liquid by simple filtration and separable, and can reclaim and recycled by roasting again.Production cost is low, and reaction yield is high, and industrially has actual using value.

Description

A kind of method adopting solid peroxygen acid oxidase pimelinketone to synthesize 6-caprolactone
Technical field
The invention belongs to a kind of synthesis 6-caprolactone, is exactly adopt H specifically 2o 2indirect oxidation pimelinketone two step synthesis 6-caprolactone also realizes the technique of catalyst recycling.
Technical background
6-caprolactone is a kind of important organic synthesis intermediate, be mainly used in synthesis polycaprolactone or with other copolymerization of ester class or blending and modifying, wherein polycaprolactone has unique biocompatibility and degradation property, and good perviousness, has a wide range of applications at Material Field.But 6-caprolactone synthesis still also exists a difficult problem for the aspect such as the security of production, the stability of product, makes its synthetic technology difficulty large.Only have at present American and Britain, Deng state several companies in production, and China mainly relies on import.Therefore, the exploitation of 6-caprolactone compound probability technology can not only fill up domestic blank technically, and has huge economic outlook.
From report in 1988, under the catalysis of the vitriol oil, adopt Peracetic Acid as oxygenant, synthesized 6-caprolactone through Baeyer-Villiger peroxyester.At present, Peracetic Acid peroxyester synthesis 6-caprolactone remains topmost synthetic method.Although the method for this classics can carry out large-scale industrialization, but in actual mechanical process, also there is a lot of shortcoming, as: cost is high, easily the explosive superoxide of high density is produced in production process, a large amount of organic acid by-product that simultaneously can produce, causes the pollution that environment is serious.Therefore, the focus of research both at home and abroad is in recent years become using oxygen or hydrogen peroxide as the technique of oxidizing pimelinketone synthesis 6-caprolactone.The research of catalyzer is mainly concentrated at present using oxygen or hydrogen peroxide as the technique of oxidizing pimelinketone synthesis 6-caprolactone, the large young pathbreaker of activity because of catalyzer directly affects the speed of oxidizing reaction and the yield of product, determines whether this reaction has industrial application value.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of method adopting solid peroxygen acid oxidase pimelinketone to synthesize 6-caprolactone, the method utilizes MgO/SnO 2/ WO 3oxide compound or MgO/SnO 2/ ZrO 2oxide compound carrys out catalysis peroxy acid peroxyester synthesis 6-caprolactone, to solve in traditional technology use the vitriol oil to do corrosion that catalyzer causes equipment and the not high problem of transformation efficiency.
The present invention solves its technical problem and adopts following technical scheme:
The present invention is to provide a kind of method adopting solid peroxygen acid oxidase pimelinketone to synthesize 6-caprolactone, specifically a kind of employing MgO/SnO 2/ WO 3oxide compound or MgO/SnO 2/ ZrO 2oxide compound be catalyzer to synthesize the method for 6-caprolactone, described catalyzer utilizes the precipitator method to make, under this catalyst condition, adopt 50% hydrogen peroxide indirect oxidation pimelinketone, two step synthesis 6-caprolactone.
The method of above-mentioned synthesis 6-caprolactone provided by the invention, can comprise the following steps:
(1) MgO/SnO 2/ WO 3oxide compound or MgO/SnO 2/ ZrO 2the preparation of oxide catalyst:
Get the MgCl of 1-200g 26H 2the SnCl of O and 1-100g 45H 2o dissolves in 250ml distilled water and obtains liquid 1 at mechanical stirring, 5-70 DEG C; Separately get distilled water 250ml, and by (the NH of 1-400g 4) 2cO 3, the H of 1-20g 2wO 4or the ZrCl of 1-100g 4be dissolved at mechanical stirring, 10-30 DEG C and wherein obtain liquid 2; Under mechanical stirring, 10-30 DEG C condition, liquid 2 is joined in liquid 1 slowly, constantly have Precipitation, after liquid 2 all adds, continue stirring 1 hour, temperature is raised to 100 DEG C, liquid is steamed thick, put into baking oven 80 ~ 300 DEG C of dry 6-72 hours; It is Powdered through being ground to that gained dries sample, and in retort furnace, roasting 1-5 hour under 200 ~ 800 DEG C of conditions, obtains described catalyzer;
(2) preparation of organic peroxide acid:
Get the acetic acid of 52.5g and the hexanaphthene of 35g, the 2-picoline of 0.1g, the MgO/SnO of 1.5g 2/ WO 3oxide compound or MgO/SnO 2/ ZrO 2oxide catalyst; At negative pressure 0.4-0.7MPa, reflux of cyclohexane band water under magnetic force vigorous stirring, 50 DEG C of conditions; Then the hydrogen peroxide getting 50% of 25g, in constant pressure funnel, dropwise added in synthesis reaction solvent in 30 minutes, often reacts for some time and water in water-and-oil separator is poured out weighing; Temperature of reaction is 30-70 DEG C, and the time is, after 1-5 hour, temperature is adjusted downward to 45 DEG C, is constantly separated by hexanaphthene, and it is organic peroxide acid that reaction terminates rear gained mixing liquid;
(3) synthesis of 6-caprolactone:
Under normal pressure, above-mentioned organic peroxy slow acid is added in pimelinketone, react at 30-70 DEG C and within 1-5 hour, obtain the 6-caprolactone solution that mass concentration is 15%-24%.
Described in above-mentioned steps (1), catalyst preparing desired substance mass ratio can be: MgCl 26H 2o:SnCl 45H 2o:(NH 4) 2cO 3: H 2wO 4=(1-200): (1-100): (1-400): (1-20), or MgCl 26H 2o:SnCl 45H 2o:(NH 4) 2cO 3: ZrCl 4=(1-200): (1-100): (1-400): (1-100).
Hexanaphthene described in above-mentioned steps (2) can be anamorphic zone aqua, and band water negative pressure is 0.6Mpa.
Acetic acid described in above-mentioned steps (2) can be synthesis reaction solvent.
Catalyst filtration after synthesis 6-caprolactone in liquid can reclaim by the present invention, and drying and roasting obtains the catalyzer of catalytic activity and the high regeneration of selectivity again.
Described catalyzer can pass through filtered and recycled, dry 6-72 hour, then after retort furnace roasting, obtains the catalyzer regenerated.
Describedly through retort furnace sinter process condition can be again: maturing temperature 300-700 DEG C, roasting time 0.5-5 hour.
The present invention compared with prior art has following main advantage:
1. adopt high-performance solid acid catalyst, pass through H 2o 2the technique of indirect oxidation pimelinketone synthesizes 6-caprolactone, overcomes traditional technology subsequent disposal difficulty, makes preparation method simple, reduces production cost.
2. in synthesis peroxy acid and 6-caprolactone process, the high-performance solid acid catalyst used has very high reactivity and selectivity and good water resisting property, this not only avoids and use the vitriol oil to do the corrosion that catalyzer causes equipment, and easily reclaim, recyclable regeneration.
3. overcome the drawback that single stage method cannot obtain 6-caprolactone, and the solid acid catalyst adopted substantially increases the yield of 6-caprolactone, industrially have actual using value.
Accompanying drawing explanation
Fig. 1 is the structural representation that the present invention adopts two-step approach Reactive Synthesis 6-caprolactone.
In figure: 1.U type differential manometer; 2. heat tape; 3. there-necked flask; 4. constant pressure funnel; 5. thermometer; 6. separating funnel; 7. serpentine condenser; 8. surge flask; 9. vacuum pump.
Embodiment
In the method for employing peroxide organic acid oxidation pimelinketone synthesis 6-caprolactone provided by the invention, the synthesis of the synthesis of peroxide organic acid realization and 6-caprolactone in common negative pressure equipment realizes in common atmospheric pressure device, the structure of this device as shown in Figure 1, comprise U-shaped differential manometer 1, heat tape 2, there-necked flask 3, constant pressure funnel 4, thermometer 5, separating funnel 6, serpentine condenser 7, surge flask 8, vacuum pump 9.Wherein: U-shaped differential manometer 1 is fixed on iron stand, and it is connected with prolong by rubber hose.Heat tape 2 is placed on the testing table of level, places the there-necked flask 3 be fixed on iron stand above.The left side mouth of there-necked flask 3 connects constant pressure funnel 4, the right mouth connects thermometer 5, middle port connects separating funnel 6, separating funnel connects serpentine condenser 7, serpentine condenser 7 is connected with surge flask 8 by rubber hose, and surge flask 8 is connected with vacuum pump 9 by rubber hose.
Described reactor is there-necked flask 3, and volume is 250ml, adopts the mode of magnetic agitation to stir.The middle part bottleneck of this there-necked flask docks with bottom serpentine condenser 7, and in the bottleneck of both sides, one is install 5, one, thermometer to dock with bottom constant pressure funnel 4.
The parameter of above-mentioned parts is only for reference, and it can in the light of actual conditions change.
Below in conjunction with embodiment, method provided by the invention is described further, but is not limited to described content below.
Embodiment 1: the preparation of catalyzer
Described catalyzer MgO/SnO 2/ WO 3oxide compound or MgO/SnO 2/ ZrO 2oxide compound.
Get the MgCl of 1-200g 26H 2the SnCl of O and 1-100g 45H 2o is dissolved in 250ml distilled water and obtains liquid 1 at mechanical stirring, 5-70 DEG C; Separately get distilled water 250ml, and by (the NH of 1-400g 4) 2cO 3, the H of 1-20g 2wO 4or the ZrCl of 1-100g 4mechanical stirring ,≤30 DEG C at be dissolved in and wherein obtain liquid 2; Then under mechanical stirring ,≤30 DEG C of conditions, liquid 2 is joined in liquid 1 slowly, constantly have Precipitation, after liquid 2 all adds, continue stirring 1 hour, temperature is raised to 100 DEG C, liquid is steamed thick, put into baking oven 80 ~ 300 DEG C of dry 6-72 hours; Gained is dried sample and is ground to Powdered through size reduction machinery (adopting Type B Universalpulverizer), and in retort furnace, roasting 1-5 hour under 200 ~ 800 DEG C of conditions, obtains described catalyzer.
Described catalyzer is used for following examples.
Embodiment 2
First catalyzer 1.5g coprecipitation method prepared, lutidine 4,35g hexanaphthene and 52.5g acetic acid are added by entrance 4, be 600-1500 rev/min in temperature 50 C, maintenance stir speed (S.S.), and retaining ring hexane backflow under vacuum tightness is 0.4-0.7Mpa, by 25gH 2o 2slowly added by constant pressure funnel 4.The water that hexanaphthene is taken out of is constantly isolated by water-and-oil separator 6, back flow reaction 3 hours (in the meantime and be finally separated by hexanaphthene).Then the U-shaped differential manometer 1 of detaching device, water-and-oil separator 6, surge flask 8, vacuum pump 9.At 50 DEG C, under magnetic agitation, 28g pimelinketone is slowly added by constant pressure funnel 4, back flow reaction 3 hours, obtains mixing liquid and organic peroxide acid 80g, under normal pressure, add in pimelinketone by this organic peroxy slow acid, at 50 DEG C, reaction obtains the 6-caprolactone solution that mass concentration is 15% for 2 hours.
Through sampling, analyzed by gas chromatograph, pimelinketone transformation efficiency can arrive 91.00%, and 6-caprolactone can reach 90.14%, and selectivity can reach 92.29%.
Embodiment 3
First catalyzer 1.5g coprecipitation method prepared, lutidine 4,35g hexanaphthene and 52.5g acetic acid are added by entrance 4, be 600-1500 rev/min in temperature 50 C, maintenance stir speed (S.S.), and retaining ring hexane backflow under vacuum tightness is 0.4-0.7Mpa, by 25gH 2o 2slowly added by constant pressure funnel 4.The water that hexanaphthene is taken out of is constantly isolated by water-and-oil separator 6, back flow reaction 3 hours (in the meantime and be finally separated by hexanaphthene).Then the U-shaped differential manometer 1 of detaching device, water-and-oil separator 6, surge flask 8, vacuum pump 9.At 50 DEG C, under magnetic agitation, 28g pimelinketone is slowly added by constant pressure funnel 4, back flow reaction 3 hours, obtain mixing liquid 82g, through sampling, analyzed by gas chromatograph, pimelinketone transformation efficiency can arrive 92.11%, and 6-caprolactone can reach 91.04%, and selectivity can reach 93.28%.
Embodiment 4
First catalyzer 1.5g coprecipitation method prepared, lutidine 4,35g hexanaphthene and 52.5g acetic acid are added by entrance 4, be 600-1500 rev/min in temperature 50 C, maintenance stir speed (S.S.), and retaining ring hexane backflow under vacuum tightness is 0.4-0.7Mpa, by the H of 25g 2o 2slowly added by constant pressure funnel 4.The water that hexanaphthene is taken out of is constantly isolated by water-and-oil separator 6, back flow reaction 3 hours (in the meantime and be finally separated by hexanaphthene).Then the U-shaped differential manometer 1 of detaching device, water-and-oil separator 6, surge flask 8, vacuum pump 9.At 50 DEG C, under magnetic agitation, the pimelinketone of 28g is slowly added by constant pressure funnel 4, back flow reaction 3 hours, obtain mixing liquid 78g, through sampling, analyzed by gas chromatograph, pimelinketone transformation efficiency can arrive 89.34%, and 6-caprolactone can reach 88.29%, and selectivity can reach 90.41%.
Embodiment 5
First catalyzer 1.5g coprecipitation method prepared, lutidine 4, the hexanaphthene of 35g and the acetic acid of 52.5g are added by entrance 4, be 600-1500 rev/min in temperature 50 C, maintenance stir speed (S.S.), and retaining ring hexane backflow under vacuum tightness is 0.4-0.7Mpa, by 25gH 2o 2slowly added by constant pressure funnel 4.The water that hexanaphthene is taken out of is constantly isolated by water-and-oil separator 6, back flow reaction 3 hours (in the meantime and be finally separated by hexanaphthene).Then the U-shaped differential manometer 1 of detaching device, water-and-oil separator 6, surge flask 8, vacuum pump 9.At 50 DEG C, under magnetic agitation, the pimelinketone of 28g is slowly added by constant pressure funnel 4, back flow reaction 3 hours, obtain mixing liquid 79g, through sampling, analyzed by gas chromatograph, pimelinketone transformation efficiency can arrive 90.28%, and 6-caprolactone can reach 89.19%, and selectivity can reach 91.32%.
Embodiment 6
First catalyzer 1.5g coprecipitation method prepared, lutidine 4, the hexanaphthene of 35g and the acetic acid of 52.5g are added by entrance 4, be 600-1500 rev/min in temperature 50 C, maintenance stir speed (S.S.), and retaining ring hexane backflow under vacuum tightness is 0.4-0.7Mpa, by the H of 25g 2o 2slowly added by constant pressure funnel 4.The water that hexanaphthene is taken out of is constantly isolated by water-and-oil separator 6, back flow reaction 3 hours (in the meantime and be finally separated by hexanaphthene).Then the U-shaped differential manometer 1 of detaching device, water-and-oil separator 6, surge flask 8, vacuum pump 9.At 50 DEG C, under magnetic agitation, the pimelinketone of 28g is slowly added by constant pressure funnel 4, back flow reaction 3 hours, obtain mixing liquid 80g, through sampling, analyzed by gas chromatograph, pimelinketone transformation efficiency can arrive 91.13%, and 6-caprolactone can reach 90.09%, and selectivity can reach 92.23%.

Claims (7)

1. adopt solid peroxygen acid oxidase pimelinketone to synthesize a method for 6-caprolactone, it is characterized in that a kind of employing MgO/SnO 2/ WO 3oxide compound or MgO/SnO 2/ ZrO 2oxide compound be catalyzer to synthesize the method for 6-caprolactone, described catalyzer utilizes the precipitator method to make, under this catalyst condition, adopt 50% hydrogen peroxide indirect oxidation pimelinketone, two step synthesis 6-caprolactone;
The method adopts the method comprised the following steps:
(1) MgO/SnO 2/ WO 3oxide compound or MgO/SnO 2/ ZrO 2the preparation of oxide catalyst:
Get the MgCl of 1-200g 26H 2the SnCl of O and 1-100g 45H 2o dissolves in 250ml distilled water and obtains liquid 1 at mechanical stirring, 5-70 DEG C; Separately get distilled water 250ml, and by (the NH of 1-400g 4) 2cO 3, the H of 1-20g 2wO 4or the ZrCl of 1-100g 4be dissolved at mechanical stirring, 10-30 DEG C and wherein obtain liquid 2; Under mechanical stirring, 10-30 DEG C condition, liquid 2 is joined in liquid 1 slowly, constantly have Precipitation, after liquid 2 all adds, continue stirring 1 hour, temperature is raised to 100 DEG C, liquid is steamed thick, put into baking oven 80 ~ 300 DEG C of dry 6-72 hours; It is Powdered through being ground to that gained dries sample, and in retort furnace, roasting 1-5 hour under 200 ~ 800 DEG C of conditions, obtains described catalyzer;
(2) preparation of organic peroxide acid:
Get the acetic acid of 52.5g and the hexanaphthene of 35g, the 2-picoline of 0.1g, the MgO/SnO of 1.5g 2/ WO 3oxide compound or MgO/SnO 2/ ZrO 2oxide catalyst; At negative pressure 0.4-0.7MPa, reflux of cyclohexane band water under magnetic force vigorous stirring, 50 DEG C of conditions; Then the hydrogen peroxide getting 50% of 25g, in constant pressure funnel, dropwise added in synthesis reaction solvent in 30 minutes, often reacts for some time and water in water-and-oil separator is poured out weighing; Temperature of reaction is 30-70 DEG C, and the time is, after 1-5 hour, temperature is adjusted downward to 45 DEG C, is constantly separated by hexanaphthene, and it is organic peroxide acid that reaction terminates rear gained mixing liquid;
(3) synthesis of 6-caprolactone:
Under normal pressure, above-mentioned organic peroxy slow acid is added in pimelinketone, react at 30-70 DEG C and within 1-5 hour, obtain the 6-caprolactone solution that mass concentration is 15%-24%.
2. the method for synthesis 6-caprolactone as claimed in claim 1, is characterized in that the catalyst filtration in liquid after synthesis 6-caprolactone to reclaim, and drying and roasting obtains the catalyzer of catalytic activity and the high regeneration of selectivity again.
3. the method for synthesis 6-caprolactone as claimed in claim 2, is characterized in that; By filtering recovering catalyst, dry 6-72 hour, then through retort furnace roasting, obtain the catalyzer regenerated.
4. the method for synthesis 6-caprolactone as claimed in claim 3, is characterized in that: describedly through retort furnace sinter process condition be again: maturing temperature 300-700 DEG C, roasting time 0.5-5 hour.
5. the method for synthesis 6-caprolactone as claimed in claim 1, is characterized in that described in step (1), catalyst preparing desired substance mass ratio is: MgCl 26H 2o:SnCl 45H 2o:(NH 4) 2cO 3: H 2wO 4=(1-200): (1-100): (1-400): (1-20), or MgCl 26H 2o:SnCl 45H 2o:(NH 4) 2cO 3: ZrCl 4=(1-200): (1-100): (1-400): (1-100).
6. the method for synthesis 6-caprolactone as claimed in claim 1, is characterized in that: described in step (2), hexanaphthene is anamorphic zone aqua, and band water negative pressure is 0.6Mpa.
7. the method for synthesis 6-caprolactone as claimed in claim 1, is characterized in that: described in step (2), acetic acid is synthesis reaction solvent.
CN201410103050.2A 2014-03-19 2014-03-19 A kind of method adopting solid peroxygen acid oxidase pimelinketone to synthesize 6-caprolactone Active CN103848807B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410103050.2A CN103848807B (en) 2014-03-19 2014-03-19 A kind of method adopting solid peroxygen acid oxidase pimelinketone to synthesize 6-caprolactone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410103050.2A CN103848807B (en) 2014-03-19 2014-03-19 A kind of method adopting solid peroxygen acid oxidase pimelinketone to synthesize 6-caprolactone

Publications (2)

Publication Number Publication Date
CN103848807A CN103848807A (en) 2014-06-11
CN103848807B true CN103848807B (en) 2016-01-06

Family

ID=50856968

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410103050.2A Active CN103848807B (en) 2014-03-19 2014-03-19 A kind of method adopting solid peroxygen acid oxidase pimelinketone to synthesize 6-caprolactone

Country Status (1)

Country Link
CN (1) CN103848807B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107597099B (en) * 2017-10-16 2020-08-14 河南能源化工集团研究总院有限公司 Forming method of Mg/Sn/W composite oxide catalyst
CN114054083A (en) * 2021-10-22 2022-02-18 浙江大学衢州研究院 Catalyst for preparing epsilon-caprolactone by cyclohexanone oxidation rearrangement and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1449394A (en) * 2000-08-24 2003-10-15 联合碳化化学及塑料技术公司 Processes for the manufacture of lactones
CN102731465A (en) * 2012-07-09 2012-10-17 武汉理工大学 Method for synthesizing epsilon-caprolactone

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1449394A (en) * 2000-08-24 2003-10-15 联合碳化化学及塑料技术公司 Processes for the manufacture of lactones
CN102731465A (en) * 2012-07-09 2012-10-17 武汉理工大学 Method for synthesizing epsilon-caprolactone

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
环己酮Baver－Villiger 氧化反应制备ε －己内酯的研究进展;章亚东 等;《河南化工》;20131231;第30卷(第5期);22-27 *
高活性MgO/SnO2 复合金属氧化物催化剂的合成及其在双氧水选择氧化环己酮制ε-己内酯反应中的应用;李静霞 等;《化学学报》;20081231;第66卷(第1期);5-9页 *

Also Published As

Publication number Publication date
CN103848807A (en) 2014-06-11

Similar Documents

Publication Publication Date Title
CN102861572A (en) Catalyst for preparing cyclohexene, preparation method of catalyst, preparation method of cyclohexene and preparation device of cyclohexene
CN103122045A (en) Nano composite quaternary phosphonium salt resin
CN104447312A (en) Dimethyl carbonate synthesis method
CN103848807B (en) A kind of method adopting solid peroxygen acid oxidase pimelinketone to synthesize 6-caprolactone
CN108250069A (en) A kind of preparation method of isooctyl acid
CN106582666B (en) Gamma-valerolactone hydrogenation catalyst, preparation method and the method for being used to prepare 1,4- pentanediol and 2- methyltetrahydrofuran
CN103143381A (en) Carbon nitride material immobilized heteropolyacid catalyst and olefin epoxy synthesizing method
CN105622386A (en) Green process for synthesizing adipic acid from cyclohexanone
CN103316696B (en) Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method
CN102921463A (en) Nano zinc sulfide metalloporphyrin catalyst and preparation method and application thereof
CN107602369A (en) A kind of preparation method of acrylic acid or acrylate
CN106588819B (en) A kind of preparation method of highly selective epoxypinane
CN103055939A (en) Preparation method for porous biomimetic catalytic material and application thereof
CN103709010A (en) Method for synthesizing cyclohexanol by reacting cyclohexene, carboxylic acid and water
CN102649055A (en) Catalyst for oxidative dehydrogenation of raw materials containing CO (carbon monoxide) gas
CN102001931A (en) Method for preparing adipate
CN105457682B (en) The preparation method and applications of vulcanized lead immobilized four (pentafluorophenyl group) catalysis of metalloporphyrin agent
CN103787272A (en) Hydrogen manufacturing method implemented by using iron-based oxide through enhancement of magnetic field
CN102942548A (en) Delta-dodecalactone synthesis method
CN109225281B (en) Catalyst containing multivalent copper active component, preparation method and application
CN104646053B (en) A kind of preparation method and applications of solid super acid catalyst
CN106045864A (en) Production process for preparing 4-chloro-2,5-dimethoxyaniline with hydrazine hydrate catalytic reduction method
CN105503529A (en) Method for preparation of ethylene glycol by ethylene carbonate hydrolysis
CN106391006B (en) A kind of preparation method of high temperature resistant anti-coking load type gold nanocatalyst
CN105854915B (en) A kind of catalyst and preparation method thereof for preparing low-carbon olefin

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20221010

Address after: 414000 Hunan Dongwei Chemical New Materials Co., Ltd., Yunxi Green Chemical Industrial Park, Yueyang City, Hunan Province

Patentee after: HUNAN DONGWEI CHEMICAL NEW MATERIAL Co.,Ltd.

Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122

Patentee before: WUHAN University OF TECHNOLOGY