CN102335624A - Method for preparing caprolactone and adipic acid - Google Patents
Method for preparing caprolactone and adipic acid Download PDFInfo
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- CN102335624A CN102335624A CN201010227171XA CN201010227171A CN102335624A CN 102335624 A CN102335624 A CN 102335624A CN 201010227171X A CN201010227171X A CN 201010227171XA CN 201010227171 A CN201010227171 A CN 201010227171A CN 102335624 A CN102335624 A CN 102335624A
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- cyclohexanone
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- adipic acid
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Abstract
The invention discloses a method for preparing caprolactone and adipic acid. The method is characterized in that a soluble zinc salt-modified silicon molecular sieve is utilized as a catalyst; cyclohexanone, oxidants, solvents and the catalyst undergo a reaction under the conditions of a temperature of 40 to 150 DEG C and pressure of 0.1 to 3MPa, wherein in the reaction, a molar ratio of cyclohexanone to the oxidants is 1: (1 to 20) and a mass ratio of the solvents to the catalyst is (1 to 200): 1; caprolactone and adipic acid are obtained simultaneously after separation of the reaction products; and unreacted cyclohexanone and the like can be recycled directly without purification separation. Under the condition of high total selectivity of epsilon-caprolactone and adipic acid, the method can realize a high effective utilization rate of an oxidant, and good catalytic oxidation activity and catalytic activity stability.
Description
Technical field
The invention relates to a kind of method for preparing caprolactone and adipic acid, further saying so about a kind of HTS with the soluble zinc salt modification is the method that catalyst oxidation cyclohexanone prepares caprolactone and adipic acid.
Background technology
6-caprolactone is a kind of important organic synthesis intermediate compound, and its heating can generate dimer or macromolecule polyester, adds the heat energy depolymerization under certain condition.6-caprolactone is mainly used in produces polycaprolactone, epsilon-caprolactams, adhesive, elastomer etc.6-caprolactone can also be as a kind of strong solvent, and the dissolving power that the resin of some indissolubles is done well is as can the dissolve polyurethane resin etc.In addition, 6-caprolactone still is a kind of raw materials for production of important degradation plastic, and the biocompatibility that it has, avirulence, biodegradable and the good property of medicine of oozing make it in biomedical sector, obtain extensive use.Simultaneously, because 6-caprolactone has favorable environment protection, also can be used for producing once-used degradeable plastic tableware, high added value packaging material etc.The enhancing of Along with people's environmental consciousness, 6-caprolactone are expected to substitute existing common plastics, get into non-returnable container material and mulch film market in a large number.
The synthetic problems such as raw materials quality, security and product stability that exist of 6-caprolactone, the synthetic technology difficulty is big, have only in the developed countries such as U.S.A, day several companies producing at present, and China mainly relies on import.In recent years, along with the continuous expansion of application, the market demand also constantly increases thereupon, and the exploitation of its synthetic technology is also more and more come into one's own.Therefore in recent years, synthetic and the suitability for industrialized production of 6-caprolactone receive domestic and international extensive concern.At present, the synthetic method of bibliographical information comprises peroxy acid oxidizing process, low concentration hydrogen peroxide, O
2/ air is an oxidant oxidation cyclohexanone method, and biological oxidation process, bionic catalysis oxidizing process etc.But the deficiency that these methods exist mainly is: catalyst activity is low, 6-caprolactone productive rate and poor selectivity, catalyst recovery difficulty etc.
Adipic acid is the principal monomer of synthetic fibers-nylon 66 and the primary raw material of nylon engineering plastic.Adipic acid is the primary raw material of synthesis of polyurethane foam, synthetic leather (PU), synthetic rubber and film simultaneously.Adipic acid can be used as food acidulant, ester plasticizer and textile treating agent, also can be used for the production of medicine, agricultural chemicals, spices, adhesive and scaling powder etc.In traditional Production Processes of Adipic Acid, mainly be to be initiation material with benzene, hydrogenation preparing cyclohexane at first, air oxidation of cyclohexane becomes cyclohexanol and cyclohexanone (being commonly called as K-A oil) then, then with nitric acid K-A oil is oxidized to adipic acid.This route accounts for more than 90% of global aggregated capacity.The method that industry is at present gone up through cyclohexanol and cyclohexanone oxidation production adipic acid is derived from Du Pont's technology in the 1940's; Promptly at 70-90 ℃ of following red fuming nitric acid (RFNA) and copper, vanadium catalyst catalytic oxidation cyclohexanol and Cyclohexanone Production adipic acid with 40-60%; Yield is about about 80%; Reaction needed is used red fuming nitric acid (RFNA), and is seriously polluted to equipment corrosion, and can produce the nitrogen-containing compound that environment is had severe contamination.
Summary of the invention
The objective of the invention is the deficiency to prior art, providing a kind of is the method that oxidizer catalytic oxidation cyclohexanone prepares caprolactone and adipic acid simultaneously with the hydrogen peroxide.
The method for preparing caprolactone and adipic acid provided by the invention; It is characterized in that the HTS with the soluble zinc salt modification is a catalyst; Being 40～150 ℃ in temperature is under the condition of 0.1～3MPa with pressure; Is 1: 1～20 with cyclohexanone, oxidant, solvent and catalyst according to the mol ratio of cyclohexanone and oxidant, and the mass ratio of solvent and catalyst is to react under 1～200: 1 the ratio, and product promptly obtains caprolactone and adipic acid after separating simultaneously; Unreacted cyclohexanone need not separate purification with solvent etc., directly recycles.
Catalytic oxidation cyclohexanone provided by the invention prepares the method for caprolactone and adipic acid, has overcome problems such as traditional processing technology complicacy, equipment corrosion and noxious emission; Make it in the reaction of oxidation cyclohexanone, under high 6-caprolactone and adipic acid overall selectivity situation, have higher oxidant effective rate of utilization, its catalytic oxidation activity and stability of catalytic activity are better simultaneously.
Method provided by the invention has following advantage:
1, Preparation of Catalyst is simple, and dry after the soluble Zn saline solution is mixed with HTS, roasting promptly gets good reproducibility;
2, under high 6-caprolactone and adipic acid overall selectivity situation, its catalytic oxidation activity and stability of catalytic activity are better simultaneously;
3, this method oxidants hydrogen peroxide effective rate of utilization improves;
4, this preparation method is a green synthesis process, the whole process of production environmental friendliness, and no special producing equipment requirements, production process is simple, is beneficial to suitability for industrialized production and application.
The specific embodiment
In the method provided by the invention, said HTS is one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48, is preferably titanium-silicon molecular sieve TS-1.
In the method provided by the invention, said soluble zinc salt is one or more in trbasic zinc phosphate, zinc nitrate, zinc chloride, zinc sulfate, zinc gluconate, zinc acetate, zinc bromide, zinc fluoride, the zinc hydrogen phosphate.
In the method provided by the invention, HTS in the said catalyst (in titanium) is 0.1～10: 1 with the mol ratio of soluble zinc salt (in zinc).
In the method provided by the invention; The HTS of said soluble zinc salt modification; Can get by dry behind soluble Zn saline solution and the HTS mixing, roasting, wherein drying, roasting condition are well known to those skilled in the art, at this and have no special requirements; Drying generally is in air atmosphere, in ℃ scope of room temperature～200, handles 1～8h.Roasting generally is in air or nitrogen atmosphere, in 350～800 ℃ of scopes, handles 1～12h.
In method provided by the invention, said oxidant is hydrogen peroxide, TBHP, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid, Perpropionic Acid etc.
In the method provided by the invention, the raw material optimum ratio is following: the mol ratio of cyclohexanone and oxidant is preferably 1: 2～and 15, the mass ratio of solvent and catalyst is preferably 2～150: 1.
In the method provided by the invention, the amount between raw material cyclohexanone and the catalyst does not have clear and definite qualification, can realize that the present invention gets final product, and the mass ratio of general cyclohexanone and catalyst is 0.5～150: 1.
In the method provided by the invention, reaction temperature is preferably 40～120 ℃, and reaction pressure is preferably 0.1～2.5MPa.
In the method provided by the invention; Said solvent is selected from nitrile or organic acid or their mixing such as acetate, propionic acid such as alcohols such as water or methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, the tert-butyl alcohol, isobutanol or ketone such as acetone, butanone or acetonitrile, propionitrile, benzene acetonitrile; Be preferably acetonitrile, acetone, methyl alcohol, acetate, water or their mixing, more preferably acetonitrile, acetone.
In the method provided by the invention, reinforced order does not have special requirement yet, can add cyclohexanone earlier, can add oxidant or solvent earlier yet.
Product can adopt the method for common distillation or rectifying, isolate target product after, unreacted cyclohexanone etc. need not be separated purification, directly turn back to again and continue reaction in the reaction unit.
Following embodiment will do explanation further to the present invention, but therefore not limit content of the present invention.
In embodiment and the Comparative Examples, used reagent is commercially available chemically pure reagent, and wherein oxidants hydrogen peroxide is 30% the aqueous solution.Used HTS (TS-1) is by prior art Zeolites, 1992, and (TS-1) sieve sample that the method described in the 943rd～950 page of the Vol.12 is prepared.
Its preparation process of the titanium-silicon molecular sieve catalyst of soluble zinc salt modification is among the embodiment; At normal temperatures and pressures, soluble Zn saline solution and HTS are mixed, then under air atmosphere; Change 120 ℃ of dry 5h in the baking oven over to, at last at 550 ℃ of roasting 5h of Muffle furnace.HTS in the wherein preparation process (in titanium) sees each embodiment for details with the mol ratio of soluble zinc salt (in zinc).
In Comparative Examples and embodiment:
Comparative Examples 1
Is 1: 2 with cyclohexanone, hydrogen peroxide and solvent according to the mol ratio of cyclohexanone and hydrogen peroxide, and wherein the solvent methanol quality is 20g, is that 60 ℃ of pressure are to react under the 1.5MPa in temperature.
React after 4 hours, the conversion ratio of cyclohexanone is 0.8%, and 6-caprolactone and adipic acid overall selectivity are 0.2%.
Comparative Examples 2
Is 2: 7 with cyclohexanone, hydrogen peroxide, solvent and TS-1 according to the mol ratio of cyclohexanone and hydrogen peroxide, and the mass ratio of solvent methanol and catalyst is 20, and the mass ratio of cyclohexanone and catalyst is 10, is that 80 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 13.2%; Effective utilization ratio of hydrogen peroxide is 35%; 6-caprolactone and adipic acid overall selectivity are 13%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 11.1%; Effective utilization ratio of hydrogen peroxide is 23%; 6-caprolactone and adipic acid overall selectivity are 12%.
Comparative Examples 3
Is 1: 6 with cyclohexanone, hydrogen peroxide, solvent and catalyst (trbasic zinc phosphate) according to the mol ratio of cyclohexanone and hydrogen peroxide; The mass ratio of solvent acetone and catalyst is 50; The mass ratio of cyclohexanone and catalyst is 50, is that 60 ℃ of pressure are to react under the 2.5MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 7.3%; Effective utilization ratio of hydrogen peroxide is 51%; 6-caprolactone and adipic acid overall selectivity are 21%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 6.5%; Effective utilization ratio of hydrogen peroxide is 32%; 6-caprolactone and adipic acid overall selectivity are 17%.
Embodiment 1
Is 1: 2 with cyclohexanone, hydrogen peroxide, solvent and catalyst (mol ratio 0.2 of zinc nitrate and HTS) according to the mol ratio of cyclohexanone and hydrogen peroxide; The mass ratio of solvent acetonitrile and catalyst is 20; The mass ratio of cyclohexanone and catalyst is 100, is that 90 ℃ of pressure are to react under the 1.0MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 86%; Effective utilization ratio of hydrogen peroxide is 72%; 6-caprolactone and adipic acid overall selectivity are 91%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 75%; Effective utilization ratio of hydrogen peroxide is 71%; 6-caprolactone and adipic acid overall selectivity are 90%.
Embodiment 2
Is 1: 10 with cyclohexanone, hydrogen peroxide, solvent and catalyst (mol ratio 1 of trbasic zinc phosphate and HTS) according to the mol ratio of cyclohexanone and hydrogen peroxide; The mass ratio of solvent acetone and catalyst is 50; The mass ratio of cyclohexanone and catalyst is 1, is that 60 ℃ of pressure are to react under the 2.5MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 89%; Effective utilization ratio of hydrogen peroxide is 75%; 6-caprolactone and adipic acid overall selectivity are 93%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 87%; Effective utilization ratio of hydrogen peroxide is 73%; 6-caprolactone and adipic acid overall selectivity are 91%.
Embodiment 3
Is 1: 3 with cyclohexanone, hydrogen peroxide, solvent and catalyst (mol ratio 0.1 of zinc sulfate and HTS) according to the mol ratio of cyclohexanone and hydrogen peroxide; The mass ratio of solvent propionitrile and catalyst is 150; The mass ratio of cyclohexanone and catalyst is 2, is that 50 ℃ of pressure are to react under the 0.5MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 81%; Effective utilization ratio of hydrogen peroxide is 73%; 6-caprolactone and adipic acid overall selectivity are 91%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 67%; Effective utilization ratio of hydrogen peroxide is 66%; 6-caprolactone and adipic acid overall selectivity are 89%.
Embodiment 4
Is 1: 13 with cyclohexanone, hydrogen peroxide, solvent and catalyst (mol ratio 2 of trbasic zinc phosphate and HTS) according to the mol ratio of cyclohexanone and hydrogen peroxide; The mass ratio of solvent methanol and catalyst is 80; The mass ratio of cyclohexanone and catalyst is 130, is that 40 ℃ of pressure are to react under the 0.2MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 72%; Effective utilization ratio of hydrogen peroxide is 75%; 6-caprolactone and adipic acid overall selectivity are 94%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 63%; Effective utilization ratio of hydrogen peroxide is 69%; 6-caprolactone and adipic acid overall selectivity are 91%.
Embodiment 5
Is 1: 8 with cyclohexanone, hydrogen peroxide, solvent and catalyst (mol ratio 5 of zinc chloride and HTS) according to the mol ratio of cyclohexanone and hydrogen peroxide; The mass ratio of solvent benzol acetonitrile and catalyst is 100; The mass ratio of cyclohexanone and catalyst is 8, is that 70 ℃ of pressure are to react under the 0.1MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 69%; Effective utilization ratio of hydrogen peroxide is 65%; 6-caprolactone and adipic acid overall selectivity are 96%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 65%; Effective utilization ratio of hydrogen peroxide is 58%; 6-caprolactone and adipic acid overall selectivity are 95%.
Embodiment 6
Is 1: 5 with cyclohexanone, hydrogen peroxide, solvent and catalyst (mol ratio 0.5 of trbasic zinc phosphate and HTS) according to the mol ratio of cyclohexanone and hydrogen peroxide; The mass ratio of solvent acetic acid and catalyst is 20; The mass ratio of cyclohexanone and catalyst is 80, is that 110 ℃ of pressure are to react under the 1.5MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 93%; Effective utilization ratio of hydrogen peroxide is 76%; 6-caprolactone and adipic acid overall selectivity are 93%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 85%; Effective utilization ratio of hydrogen peroxide is 68%; 6-caprolactone and adipic acid overall selectivity are 93%.
Embodiment 7
Is 1: 7 with cyclohexanone, hydrogen peroxide, solvent and catalyst (mol ratio 0.7 of zinc nitrate and HTS) according to the mol ratio of cyclohexanone and hydrogen peroxide; Solvent (equal-volume is than acetone and acetonitrile) is 2 with the mass ratio of catalyst; The mass ratio of cyclohexanone and catalyst is 110, is that 60 ℃ of pressure are to react under the 2.0MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 74%; Effective utilization ratio of hydrogen peroxide is 76%; 6-caprolactone and adipic acid overall selectivity are 95%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 66%; Effective utilization ratio of hydrogen peroxide is 73%; 6-caprolactone and adipic acid overall selectivity are 92%.
Embodiment 8
Is 1: 11 with cyclohexanone, hydrogen peroxide, solvent and catalyst (mol ratio 2.2 of zinc gluconate and HTS) according to the mol ratio of cyclohexanone and hydrogen peroxide; The mass ratio of solvent acetone and catalyst is 5; The mass ratio of cyclohexanone and catalyst is 30, is that 80 ℃ of pressure are to react under the 0.2MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 71%; Effective utilization ratio of hydrogen peroxide is 82%; 6-caprolactone and adipic acid overall selectivity are 93%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 65%; Effective utilization ratio of hydrogen peroxide is 79%; 6-caprolactone and adipic acid overall selectivity are 91%.
Embodiment 9
Is that the mass ratio of 1: 4 solvent acetonitrile and catalyst is 10 with cyclohexanone, hydrogen peroxide, solvent and catalyst (mol ratio 0.2 of zinc bromide and HTS) according to the mol ratio of cyclohexanone and hydrogen peroxide; The mass ratio of cyclohexanone and catalyst is 10, is that 40 ℃ of pressure are to react under the 0.3MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 52%; Effective utilization ratio of hydrogen peroxide is 77%; 6-caprolactone and adipic acid overall selectivity are 94%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 47%; Effective utilization ratio of hydrogen peroxide is 73%; 6-caprolactone and adipic acid overall selectivity are 94%.
Embodiment 10
Is 1: 15 with cyclohexanone, hydrogen peroxide, solvent and catalyst (mol ratio 0.9 of zinc hydrogen phosphate and HTS) according to the mol ratio of cyclohexanone and hydrogen peroxide; Solvent (equal-volume is than water and acetonitrile) is 120 with the mass ratio of catalyst; The mass ratio of cyclohexanone and catalyst is 0.5, is that 90 ℃ of pressure are to react under the 0.2MPa in temperature.
The result who reacts 2 hours is following: the cyclohexanone conversion ratio is 89%; Effective utilization ratio of hydrogen peroxide is 78%; 6-caprolactone and adipic acid overall selectivity are 96%.
The result who reacts 12 hours is following: the cyclohexanone conversion ratio is 85%; Effective utilization ratio of hydrogen peroxide is 72%; 6-caprolactone and adipic acid overall selectivity are 92%.
Can find out from embodiment 1-10 and Comparative Examples 1-3: it is that activity of such catalysts is apparently higher than comparative sample such as unmodified HTSs that production method of the present invention adopts the HTS of soluble zinc salt modification; 6-caprolactone and adipic acid overall selectivity increase, and especially stability of catalytic activity is better.
Claims (10)
1. method for preparing caprolactone and adipic acid; It is characterized in that the HTS with the soluble zinc salt modification is a catalyst; Being 40～150 ℃ in temperature is under the condition of 0.1～3MPa with pressure; Is 1: 1～20 with cyclohexanone, oxidant, solvent and catalyst according to the mol ratio of cyclohexanone and oxidant, and the mass ratio of solvent and catalyst is to react under 1～200: 1 the ratio, and product promptly obtains caprolactone and adipic acid after separating simultaneously; The separation of need not purifying such as unreacted cyclohexanone directly recycles.
2. according to the method for claim 1, it is characterized in that said HTS is one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48.
3. according to the method for claim 1, it is characterized in that said HTS is TS-1.
4. according to the method for claim 1, it is characterized in that said soluble zinc salt is one or more in trbasic zinc phosphate, zinc nitrate, zinc chloride, zinc sulfate, zinc gluconate, zinc acetate, zinc bromide, zinc fluoride, the zinc hydrogen phosphate.
5. according to the process of claim 1 wherein, the mol ratio of HTS and soluble zinc salt is 0.1～10: 1, and HTS is in titanium, and soluble zinc salt is in zinc.
6. according to the method for claim 1 or 5, wherein, the HTS of said soluble zinc salt modification is obtained by dry behind soluble Zn saline solution and the HTS mixing, roasting.
7. according to the method for claim 1, it is characterized in that said oxidant is hydrogen peroxide, TBHP, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid, Perpropionic Acid.
8. according to the process of claim 1 wherein, the mol ratio of cyclohexanone and oxidant is 1: 2～15, and the mass ratio of solvent and catalyst is 2～150: 1, and the mass ratio of cyclohexanone and catalyst is 0.5～150: 1.
9. according to the method for claim 1, it is characterized in that reaction temperature is 40～120 ℃, reaction pressure is 0.1～2.5MPa.
10. according to the method for claim 1, it is characterized in that said solvent is selected from water, alcohol, ketone, acid, nitrile and/or their mixture.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103373978A (en) * | 2012-04-27 | 2013-10-30 | 中国石油化工股份有限公司 | Reaction method for preparing corresponding lactone, hydroxy acid and dicarboxylic acid through cyclic ketone oxidation |
| CN107266344A (en) * | 2017-07-17 | 2017-10-20 | 湘潭大学 | A kind of preparation method of cyclohexanone peroxide |
| CN109836561A (en) * | 2019-01-30 | 2019-06-04 | 青岛科技大学 | A kind of synthetic method of 6 hydroxycaproic acid oligomer and its resulting oligomer |
| CN114438522A (en) * | 2022-02-15 | 2022-05-06 | 万华化学集团股份有限公司 | Method for preparing epsilon-caprolactone from cyclohexanone |
| 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) |
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| CN101307045A (en) * | 2008-07-11 | 2008-11-19 | 湖南大学 | Method for preparing caprolactone from cyclohexanone by catalytic oxidation |
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| CN101307045A (en) * | 2008-07-11 | 2008-11-19 | 湖南大学 | Method for preparing caprolactone from cyclohexanone by catalytic oxidation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103373978A (en) * | 2012-04-27 | 2013-10-30 | 中国石油化工股份有限公司 | Reaction method for preparing corresponding lactone, hydroxy acid and dicarboxylic acid through cyclic ketone oxidation |
| CN103373978B (en) * | 2012-04-27 | 2015-03-18 | 中国石油化工股份有限公司 | Reaction method for preparing corresponding lactone, hydroxy acid and dicarboxylic acid through cyclic ketone oxidation |
| CN107266344A (en) * | 2017-07-17 | 2017-10-20 | 湘潭大学 | A kind of preparation method of cyclohexanone peroxide |
| CN107266344B (en) * | 2017-07-17 | 2021-09-14 | 湘潭大学 | Preparation method of cyclohexanone peroxide |
| CN109836561A (en) * | 2019-01-30 | 2019-06-04 | 青岛科技大学 | A kind of synthetic method of 6 hydroxycaproic acid oligomer and its resulting oligomer |
| CN114438522A (en) * | 2022-02-15 | 2022-05-06 | 万华化学集团股份有限公司 | Method for preparing epsilon-caprolactone from cyclohexanone |
| 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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