CN101412704A - Preparation of epsilon-caprolactone - Google Patents
Preparation of epsilon-caprolactone Download PDFInfo
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- CN101412704A CN101412704A CNA2008101553497A CN200810155349A CN101412704A CN 101412704 A CN101412704 A CN 101412704A CN A2008101553497 A CNA2008101553497 A CN A2008101553497A CN 200810155349 A CN200810155349 A CN 200810155349A CN 101412704 A CN101412704 A CN 101412704A
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- caprolactone
- aldehyde
- pimelinketone
- reaction
- solution
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- 238000002360 preparation method Methods 0.000 title abstract description 16
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title abstract description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 74
- 150000001299 aldehydes Chemical class 0.000 claims description 19
- 238000002604 ultrasonography Methods 0.000 claims description 16
- -1 phenyl aldehyde Chemical class 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- GISVICWQYMUPJF-UHFFFAOYSA-N 2,4-Dimethylbenzaldehyde Chemical compound CC1=CC=C(C=O)C(C)=C1 GISVICWQYMUPJF-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 12
- 150000004965 peroxy acids Chemical class 0.000 description 12
- 230000009466 transformation Effects 0.000 description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- FFFIRKXTFQCCKJ-UHFFFAOYSA-N 2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1 FFFIRKXTFQCCKJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- KNZSPKGFNVVCLS-UHFFFAOYSA-N 1,3,5-trimethylcyclohexa-2,4-diene-1-carbaldehyde Chemical compound CC1=CC(C)=CC(C)(C=O)C1 KNZSPKGFNVVCLS-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BMHBMLLQKJESDS-UHFFFAOYSA-N benzene;formaldehyde Chemical class O=C.C1=CC=CC=C1 BMHBMLLQKJESDS-UHFFFAOYSA-N 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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Abstract
The invention relates to a method for preparing epsilon-caprolactone, which comprises the following steps: adding aldehyde, cyclohexanone and an organic solvent into a sonochemical reactor; generating peroxoic acid by using oxygen to oxidize the aldehyde in organic solution, and oxidizing the cyclohexanone to prepare the epsilon-caprolactone by the peroxoic acid. The method for preparing the epsilon-caprolactone not only has simple synthesis process, but also shortens the preparation time by using the sonochemical reactor, realizes the selective oxidation under a mild condition, obtains the target product epsilon-caprolactone which has high yield, high selectivity, and high conversion rate, and reduces by-products of a material which is difficult to purify and separate in the product. At the same time, relatively-cheap and environment-friendly molecular oxygen is used as an oxidant to reduce the production cost so that the method is a green chemical reaction process for environment protection.
Description
Technical field
The present invention relates to prepare the 6-caprolactone technology by the oxidation pimelinketone, more precisely is that ultrasonic technique is incorporated into the aldehyde generation peroxy acid in oxygen (or air) the oxidation organic solvent, the method that peroxy acid oxidation pimelinketone prepares 6-caprolactone.
Background technology
Because 6-caprolactone is a kind of important organic synthesis intermediate, is widely used as the new polyester monomer, can carry out modification to various resins, to improve its glossiness, the transparency and non-stick property etc.People are to the synthetic extensive studies of carrying out of 6-caprolactone.
The research method that has earlier has following several:
In the technology that formerly has, known a kind of method for preparing 6-caprolactone is to carry out (Baeyer-Villiger) reaction by pimelinketone and peroxy acid.Used peroxy acid has Peracetic Acid, Perpropionic Acid etc. usually.
The thick 6-caprolactone product that obtains about the above-mentioned method for preparing 6-caprolactone once proposed multiple technologies to be separated, for example: in an internal-response volume is 2 liters flow reactor, with the flow of the 60g/hr pimelinketone of making a gift to someone, and send into the ethyl acetate solution of 30% peracetic acid (flow of pure peracid is 51.4g/hr with the flow of 170.5g/hr, 1.1 times of pimelinketone molar weight), under 50 ℃ temperature of reaction, carry out successive reaction.Analyze resulting crude product mixture, find wherein to comprise 28.78% 6-caprolactone, 0.52% unreacted pimelinketone, 1.31% unreacted peracetic acid, the hexanodioic acid that 0.59% side reaction produces, the polymerisate of 0.3% caprolactone, 21.16% acetate, 47.34% ethyl acetate.The thick 6-caprolactone that reaction obtains is sent in first distillation tower, collect the first distillation tower side component, the side component is sent in second distillation tower, give reaction system with liquid at the bottom of second tower as feedstock recycle, first base product liquid is sent in the 3rd distillation tower, and liquid of top of the tower is the 6-caprolactone (Chinese patent publication number CN 1496985A) of purification.Though this method is simple, cost is low, and operational condition is required harshness, exists the production safety problem, and the subsequent separation process of product is difficult.
In existing technology, second kind of method for preparing 6-caprolactone is to obtain peroxy acid by a kind of acid of hydrogen peroxide oxidation, and peroxy acid and pimelinketone reaction make 6-caprolactone.Acid used among this preparation method has propionic acid, acetate etc. usually.In reaction process, to add some dewatering agents such as anhydrous MgSO usually
4, entrainer such as alkyl chloride hydro carbons; Usually in preparation process, also to add some ortho-boric acids or metaboric acid etc.For example: Li Hongdao adopts propionic acid under the condition of catalyst-free be medium, and anhydrous MgSO4 is a dewatering agent, the H with 30%
2O
2The oxidation pimelinketone, obtained yield and be 79.9% 6-caprolactone (Li Hongdao. the study on the synthesis of 6-caprolactone [J] .1 Jiangsu Petrochemical Engineering College journal, 2002,14 (2): 11-13).This preparation method generates the material of low boiling component such as hydroxycaproic acid and high boiling material usually as 1, and the oligomer of 4-caprolactone etc. are so there is more impurity in reaction product.Therefore this method is can not be satisfactory.
Therefore, for obtaining a kind of method that industrial-scale production prepares 6-caprolactone that is able to.A kind of like this preparation method of strong request promptly produces the less by product of purifying of being unfavorable in the method, maybe can suppress the generation of by product, and industrial operation is simple, convenience, safety, production cost are low.
Compared to preceding two kinds of methods, the method that air (or oxygen) oxidation pimelinketone prepares 6-caprolactone is a kind of reaction process of pollution-free green environmental protection, and working method is simple, convenient, production cost is low.
Patent US 6,063,938 has in recent years introduced a kind of 80% pimelinketone that contains, 20% 2,4-dimethylbenzaldehyde, and the 1ppm cobalt naphthenate, temperature is inserted the 12L autoclave in the time of 35 ℃, and the pressure of reactor is 25kg/cm
2.G.Contain 6-caprolactone 12.3%, 2 in the reaction product, 4-mesitylenic acid 18.1%, 2,4-dimethylbenzaldehyde 2.7%, pimelinketone 66.1%, other by products 0.8%.US 6,472, and 540 have introduced a kind of 80% pimelinketone that contains, and 20%2, the 4-dimethylbenzaldehyde, the 1ppm cobalt naphthenate, temperature is inserted the 6L autoclave in the time of 35 ℃, and the pressure of reactor is 25kg/cm
2.G.Contain 6-caprolactone 7.92%, 2 in the reaction product, 4-mesitylenic acid 12.75%, 2,4-dimethylbenzaldehyde 7.58%, pimelinketone 70.60%, other by product 0.97%.Above technology is the method that air (or oxygen) oxidation pimelinketone prepares 6-caprolactone, and the productive rate of the 6-caprolactone that obtains is high relatively; But still exist not enough: require to add catalyzer, productive rate is low, transformation efficiency is low, severe reaction conditions, reaction pressure height, have the production safety problem, has therefore limited the possibility of scale operation.
Baeyer-Villiger Oxidation of Ketones Using Molecular Oxygen and Benzaldehydein the Absence of Metal Catalysts (J.Org.Chem, 1994,59,11) introduced in the literary composition in the time of 40 ℃, catalyst-free, phenyl aldehyde aerating oxygen in carbon tetrachloride solvent, add pimelinketone behind the aerating oxygen 30min, continued aerating oxygen 5 hours.The productive rate 82% of the 6-caprolactone that obtains.This method exists shortcomings such as transformation efficiency is low, productive rate is low, long reaction time, carbon tetrachloride solvent strong toxicity, price height, volatility height.
Summary of the invention
The objective of the invention is long for the preparation time that improves the existing method existence that prepare 6-caprolactone, operating process is dangerous, transformation efficiency is low, productive rate is low, the high deficiency of production cost and a kind of preparation method of 6-caprolactone is provided.
Technical scheme of the present invention is: a kind of method for preparing 6-caprolactone, and its concrete steps are as follows:
A. adding organic solvent and aldehyde react in the sonochemistry reactor, wherein by 5-40 moles of organic solvents of every mole of aldehyde, and 45-120 ℃ of control reaction temperature; Aldehyde in the aerating oxygen oxidation organic solution, open the cryogenic condensation device of sonochemistry reactor and-30-20 ℃ simultaneously, control ultrasonic frequency 10kHz-150kHz, behind ultrasound wave irradiation 1-60min, mol ratio in aldehyde and pimelinketone is that 1:0.2-1:1 ratio adds pimelinketone, continues aerating oxygen, control reaction temperature, ultrasound wave irradiation reaction 0.5-10 hours obtains the 6-caprolactone crude product;
B. use saturated Na
2SO
3Solution, saturated NaHCO
3Solution and deionized water be 6-caprolactone crude product washing, to the pH of washings be 6-8, isolate organic phase, organic phase is carried out underpressure distillation, obtain the pure product of 6-caprolactone.
Above-mentioned organic phase is carried out underpressure distillation, generally collect component 98-100 ℃ the time under 166Pa, what obtain is the pure product of 6-caprolactone.Organic phase is carried out the vacuum distillation process recovered solvent can be as reaction solvent next time.
The consumption of preferred above-mentioned pimelinketone is that every mole of aldehyde is with 0.3-0.8 mole.Above-mentioned ultrasonic frequency is 10.4kHz-80kHz, and ultrasonic voltage is 20v-350v.Preferred above-mentioned temperature of reaction is 50-100 ℃; Continue aerating oxygen and ultrasound wave irradiation reaction times at 2.5-5.5 hours.
Above-mentioned organic solvent is 1, the 2-ethylene dichloride, and tetracol phenixin, straight chain chloroparaffin, the consumption of organic solvent are that every mole of aldehyde adds 8-38 moles of organic solvents.Above-mentioned aldehyde is phenyl aldehyde, 2, and 4-dimethylbenzaldehyde, 1 formaldehyde, chlorinated benzene formaldehyde or isovaleric aldehyde.
The pressure of above-mentioned aerating oxygen is 0.05-1.15Mpa, and oxygen gas flow rate is 100-1000mL/min.
The aldehyde of the present invention in both can aerating oxygen oxidation organic solution, the aldehyde in also can bubbling air oxidation organic solution.
Process flow sheet of the present invention as shown in Figure 1; It comprises a ultrasound-enhanced preparation peroxy acid process, and a ultrasound-enhanced peroxy acid oxidation pimelinketone prepares the process (step for preparing thick 6-caprolactone solution) of 6-caprolactone and the process of the thick 6-caprolactone of purifying.
Aldehyde, pimelinketone, organic solvent should be a kind of impurity that is difficult in the 6-caprolactone purification and separation process that neither contains, and also do not contain its precursor compound, and preferably purity is up to the above compound of 90% (weight).
The device of wanting required for the present invention comprises conventional sonochemistry reactor, cryogenic condensation device, heating unit and tripping device etc.
Beneficial effect:
The present invention provides a kind ofly can obtain high yield, high yield, highly selective, high conversion, production cost is low, preparation time is short, environmental protection, working method are simple, convenience, safety, the method for preparing 6-caprolactone that the solvent evaporates degree is low; Preparation produces in the production process is difficult to purify, isolating material by product is less.
1, the present invention is in the phonochemical reaction device, and oxygen (or air) oxidation pimelinketone prepares 6-caprolactone.Because the present invention has realized the selective oxidation under the mild conditions; And the oxygenate oxygen (or air) that provides is a kind of energy of cleaning, realized green chemical reaction process.
2, the method that the present invention is under the ultrasound wave irradiation catalyst-free condition, the short period of time obtains high yield, high yield, highly selective, high conversion 6-caprolactone, the productive rate 90-98% of 6-caprolactone, the by product that this invention simultaneously obtains is less, be easy to later separation work, there be not pressure height, the unsafe problem of production operation process of producing in this invention, be one pollution-free, the preparation process of environmental protection.
Description of drawings
Fig. 1 is a process flow sheet of the present invention; 1-sonochemistry reactor; 2-tripping device; 3-constant temperature water bath apparatus; 4-cryogenic condensation device, A-pimelinketone, aldehyde, organic solvent charging; B-oxygen; C-thick 6-caprolactone solution; D-6-caprolactone; E-organic solvent (recovery), F-water of condensation.
Embodiment
Further specify characteristics of the present invention below by embodiment, but the protection domain of this patent is not subjected to the restriction of embodiment.
Embodiment 1
Add 355mmol 1,2-ethylene dichloride and 30mmol phenyl aldehyde are to ultrasonic irradiation apparatus; Feed the oxygen of pressure 1Mpa, flow velocity 300ml/min; Opening the constant temperature water bath apparatus control reaction temperature is 80 ℃; Opening phonochemical reaction device and cryogenic condensation device control condensing temperature is (15 ℃), adds pimelinketone 15mmol behind the ultrasound wave irradiation 15min, continues ultrasound wave irradiation 3h, obtains thick 6-caprolactone product.Use saturated Na
2SO
3, saturated NaHCO
3With phenylformic acid in the thick 6-caprolactone solution of deionized water flush away, washing soln is formed with the gas chromatograph assay products to pH to 6.
The amount of the peroxy acid that produces in this experimentation is identified by iodimetry,iodometry.
This result of experiment detects by gas-chromatography, and the content (volume) that obtains thick 6-caprolactone solution by stratographic analysis is as follows:
6-caprolactone: 4.14%
Phenyl aldehyde: 0.35%
Pimelinketone: 0.09%
Phenylformic acid: 8.15%
1,2-ethylene dichloride: 87%
Other: 0.27%
The transformation efficiency of pimelinketone: 98%
The productive rate of 6-caprolactone: 94%
The selectivity of 6-caprolactone: 95.9%
Benzoic selectivity: 96%
Embodiment 2 thick 6-caprolactone purified solution:
Add 355mmol tetracol phenixin and 30mmol chlorinated benzene formaldehyde solution to ultrasonic irradiation apparatus; Feed pressure 0.5Mpa, the oxygen of flow velocity 300ml/min; Open 70 ℃ of constent temperature heater control reactions; Opening phonochemical reaction device and cryogenic condensation device condensing temperature is (20 ℃), adds the 10mmol pimelinketone behind the ultrasound wave irradiation 15min, continues ultrasound wave irradiation 3.5h, obtains thick 6-caprolactone product.Use saturated Na
2SO
3, saturated NaHCO
3After phenylformic acid in the thick 6-caprolactone solution of solution and deionized water flush away, washing soln are 8 to pH, form with the gas chromatograph assay products.
The amount of the peroxy acid that produces in this experimentation is measured by iodimetry,iodometry.
This result of experiment detects by gas-chromatography, and the content (volume) that obtains thick 6-caprolactone solution by stratographic analysis is as follows:
6-caprolactone: 2.7%
Phenyl aldehyde: 0.9%
Pimelinketone: 0.09%
Phenylformic acid: 6.8%
1,2-ethylene dichloride: 88.2%
Other: 1.5%
The transformation efficiency of pimelinketone: 97%
The productive rate of 6-caprolactone: 93%
The selectivity of 6-caprolactone: 95%
Benzoic selectivity: 95%
Phenyl aldehyde transformation efficiency: 90%
Embodiment 3
Add 474mmol 1,2-ethylene dichloride and 30mmol 1,3,5-trimethylbenzaldehyde solution feeds the oxygen of pressure 1.15Mpa, flow velocity 400ml/min to ultrasonic irradiation apparatus, 70 ℃ of control reactions, opening phonochemical reaction device and condensing works condensing temperature is (15 ℃), add the 15mmol pimelinketone behind the ultrasound wave irradiation 10min, continue ultrasonic spoke 4h, obtain thick 6-caprolactone product.Use saturated Na
2SO
3, saturated NaHCO
3Phenylformic acid in solution, the thick 6-caprolactone solution of deionized water flush away is washed and is dripped after solution is 7 to pH, forms with the gas chromatograph assay products.
The amount of the peroxy acid that produces in this experimentation is identified by iodimetry,iodometry.
This result of experiment detects by gas-chromatography, and the content (volume) that obtains thick 6-caprolactone solution by stratographic analysis is as follows:
6-caprolactone: 3.4%
Phenyl aldehyde: 1.2%
Pimelinketone: 0.06%
Phenylformic acid: 5.3%
1,2-ethylene dichloride: 89.9%
Other: 0.14%
The transformation efficiency of pimelinketone: 98%
The productive rate of 6-caprolactone: 94%
The selectivity of 6-caprolactone: 97.8%
Benzoic selectivity: 94%
Phenyl aldehyde transformation efficiency: 82%
Embodiment 4
Add 532mmol tetracol phenixin and 30mmol isovaleric aldehyde solution to ultrasonic irradiation apparatus, feed the oxygen of pressure 1Mpa, flow velocity 600ml/min, 60 ℃ of control reactions, opening phonochemical reaction device and condensing works condensing temperature is (15 ℃), add the 15mmol pimelinketone behind the ultrasound wave irradiation 10min, continue ultrasound wave irradiation 5.5h, obtain thick 6-caprolactone product.Use saturated Na
2SO
3, saturated and NaHCO
3With phenylformic acid in the thick 6-caprolactone solution of deionized water solution flush away, wash and drip after solution is 8 to pH, form with the gas chromatograph assay products.
This result of experiment detects by gas-chromatography, and the content (volume) that obtains thick 6-caprolactone solution by stratographic analysis is as follows:
6-caprolactone: 2.65%
Phenyl aldehyde: 1.3%
Pimelinketone: 0.2%
Phenylformic acid: 4.75%
1,2-ethylene dichloride: 90.9%
Other: 0.2%
The transformation efficiency of pimelinketone: 94%
The productive rate of 6-caprolactone: 90%
The selectivity of 6-caprolactone: 95.7%
The transformation efficiency of phenyl aldehyde: 76%
Benzoic selectivity: 89.6%
Embodiment 5 thick 6-caprolactone purified solution:
Use saturated Na
2SO
3Solution, saturated NaHCO
3The thick 6-caprolactone solution that the thick the foregoing description 4 of solution deionized water rinsing makes to its pH8, is isolated organic phase, and organic phase is carried out underpressure distillation, and the component when collecting under the 166Pa 98-100 ℃ obtains the pure product of 6-caprolactone.The low-temperature mixed thing of collecting can cycle applications in reaction for the second time, can effectively improve the utilization ratio of solvent, promote the carrying out of reaction simultaneously.
As mentioned above, preparation method of the present invention is a kind of process of 6-caprolactone that is used to prepare high yield of reaction conditions gentleness, simultaneously can the good restraining production of by-products, help simplifying purification process, be a kind of cleaning, environmental protection, the preparation method that reaction cost is low.The transformation efficiency of pimelinketone is up to 92-98% in the reaction process, and the productive rate of 6-caprolactone is up to 90-98%, and the selectivity of 6-caprolactone reaches 95.9%.Solvent in the reaction process of the present invention can be reused by reclaiming, thereby has reduced production cost, has improved economic benefit.Preparation method provided by the invention is simple, convenient, safety, atmospheric pollution are little, the low commercial process that is suitable for of production cost.
Claims (7)
1. method for preparing 6-caprolactone, its concrete steps are as follows:
A. adding organic solvent and aldehyde react in the sonochemistry reactor, wherein add 5-40 moles of organic solvents, 45-120 ℃ of control reaction temperature by every mole of aldehyde; Aldehyde in the aerating oxygen oxidation organic solution, open the cryogenic condensation device of sonochemistry reactor and-30-20 ℃ simultaneously, control ultrasonic frequency 10kHz-150kHz, behind ultrasound wave irradiation 1-60min, mol ratio in aldehyde and pimelinketone is that 1:0.2-1:1 ratio adds pimelinketone, continues aerating oxygen, control reaction temperature, continue ultrasound wave irradiation reaction 0.5-10 hours, obtain the 6-caprolactone crude product;
B. use saturated Na
2SO
3Solution, saturated NaHCO
3Solution and deionized water be 6-caprolactone crude product washing, to the pH of washings be 6-8, isolate organic phase, organic phase is carried out underpressure distillation, obtain the pure product of 6-caprolactone.
2. method according to claim 1 is characterized in that the described consumption of stating pimelinketone is that every mole of aldehyde is with 0.3-0.8 mole.
3. method according to claim 1 is characterized in that above-mentioned ultrasonic frequency is controlled at 10.4kHz-80kHz, and ultrasonic voltage is at 20v-350v.
4. method according to claim 1 is characterized in that above-mentioned temperature of reaction is 50-100 ℃; Continue aerating oxygen and ultrasound wave irradiation reaction times at 2.5-5.5 hours.
5. method according to claim 1 is characterized in that above-mentioned organic solvent is 1, and 2-ethylene dichloride, tetracol phenixin or straight chain chloroparaffin, the consumption of organic solvent are that every mole of aldehyde is 8-38 moles of organic solvents.
6. method according to claim 1 is characterized in that above-mentioned aldehyde is phenyl aldehyde, 2,4-dimethylbenzaldehyde, 1 formaldehyde, chlorinated benzene formaldehyde or isovaleric aldehyde.
7. method according to claim 1, the pressure that it is characterized in that aerating oxygen is 0.05-1.15Mpa, oxygen gas flow rate is 100-1000mL/min.
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| CNA2008101553497A CN101412704A (en) | 2008-10-27 | 2008-10-27 | Preparation of epsilon-caprolactone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408404A (en) * | 2011-11-21 | 2012-04-11 | 上海应用技术学院 | Method for preparing epsilon-caprolactone by oxidizing cyclohexanone through molecular oxygen |
| CN108003130A (en) * | 2017-12-22 | 2018-05-08 | 黎明化工研究设计院有限责任公司 | The integrated apparatus and its application method of a kind of 6-caprolactone synthesis and concentration |
| CN110016128A (en) * | 2019-05-06 | 2019-07-16 | 湖南东为化工新材料有限公司 | A kind of reuse method of 6-caprolactone by-product |
-
2008
- 2008-10-27 CN CNA2008101553497A patent/CN101412704A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408404A (en) * | 2011-11-21 | 2012-04-11 | 上海应用技术学院 | Method for preparing epsilon-caprolactone by oxidizing cyclohexanone through molecular oxygen |
| CN102408404B (en) * | 2011-11-21 | 2013-05-01 | 上海应用技术学院 | Method for preparing epsilon-caprolactone by oxidizing cyclohexanone through molecular oxygen |
| CN108003130A (en) * | 2017-12-22 | 2018-05-08 | 黎明化工研究设计院有限责任公司 | The integrated apparatus and its application method of a kind of 6-caprolactone synthesis and concentration |
| CN110016128A (en) * | 2019-05-06 | 2019-07-16 | 湖南东为化工新材料有限公司 | A kind of reuse method of 6-caprolactone by-product |
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Application publication date: 20090422 |