CN102367246A - Preparation method of epsilon-caprolactone - Google Patents
Preparation method of epsilon-caprolactone Download PDFInfo
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- CN102367246A CN102367246A CN2010101261176A CN201010126117A CN102367246A CN 102367246 A CN102367246 A CN 102367246A CN 2010101261176 A CN2010101261176 A CN 2010101261176A CN 201010126117 A CN201010126117 A CN 201010126117A CN 102367246 A CN102367246 A CN 102367246A
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- caprolactone
- pimelinketone
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- peracetic acid
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Abstract
The invention discloses a preparation method of epsilon-caprolactone. The method includes reacting specially-prepared anhydrous peroxyacetic acid with cyclohexanone at a temperature of 30-80DEG C. No solvent, catalyst and stabilizing agent are needed to be added additionally in the reaction process, thus being in favor of the separation and purification of epsilon-caprolactone. The epsilon-caprolactone prepared by the method of the invention has a molar yield over 91% compared with peroxyacetic acid and a molar yield over 92% compared with cyclohexanone.
Description
Technical field
The present invention relates to a kind of method for preparing 6-caprolactone.
Background technology
6-caprolactone is a kind of important organic synthesis intermediate.6-caprolactone can be used for the polycaprolactone of synthetic different purposes; Polycaprolactone is the macromolecular material of one type of fully biodegradable, and it has unique biological intermiscibility, biological degradability and good penetration property, material, environmental protection and medical aspect obtained using widely.6-caprolactone also can with various resin copolymerization or blending and modifying, to improve product glossiness, the transparency and non-stick property etc., this series products can be used as the sustained release body and the wrapping material of plastic sheeting for farm use, tackiness agent, fertilizer.6-caprolactone also can be used as a kind of strong solvent, and the resin of some indissolubles is shown good solvency power.
Because of the synthetic difficult problem that has aspects such as raw materials quality, product stability and production security of 6-caprolactone, its synthetic technology requirement is high, difficulty is big, has only external several company to produce at present.In recent years, with the continuous expansion of 6-caprolactone purposes, its market requirement also strengthens gradually.Therefore, the study on the synthesis of 6-caprolactone has huge economic outlook.
Usually, prepare 6-caprolactone through the oxidation pimelinketone.The 6-caprolactone of following reaction formula prepares process and is: the reaction of acetic acid and ydrogen peroxide 50 forms peracetic acid soln in the presence of azeotropic solvent and strong acid catalyst; This peracetic acid soln is got rid of moisture content continuously through component distillation, and anhydrous peroxyacetic acid that obtains and pimelinketone reaction form 6-caprolactone solution.6-caprolactone solution distills through first distillation tower, and cat head distillates light constituents such as organic solvent and acetic acid; The heavy constituent that contain 6-caprolactone get into second column, obtain purified 6-caprolactone from cat head rectifying, discharge high boiling substances such as hexanodioic acid, polycaprolactone and strong acid catalyst at the bottom of the tower.
V.M.Vishnyakov etc. show that to the chemical kinetics research of pimelinketone and Peracetic Acid the fs of reaction is dimolecular reaction (Journal of applied chemistry, the USSR that two kinds of raw materials transform synchronously; Vol.49; NO.9, p.2035,1976).Yet, when preparing 6-caprolactone in early days, excessive from the security consideration pimelinketone; But the weakness that becomes this technology is reclaimed in the excessive then distillation of pimelinketone.Adopt excessive percarboxylic acids among the U.S. Pat 4994583A that announced in 1991 afterwards, promptly the mol ratio of pimelinketone and percarboxylic acids is between 0.75-0.9; Under the premise that security is guaranteed, let the pimelinketone complete reaction of trying one's best.Its decomposition loss can not ignore when percarboxylic acids was reclaimed in this technology distillation, and caused unnecessary wastage of material.In sum, the reaction of pimelinketone and Peracetic Acid, any raw material excessive or to lack all be feasible, but reactant is according to waiting mole number to add and transforming when thorough the most economical.
The reaction of pimelinketone and percarboxylic acids, the content of strong acid, water and ydrogen peroxide 50 all has direct relation with the 6-caprolactone yield in the raw material.In the presence of these materials; 6-caprolactone can be because of its hydrolysis, autohemagglutination or the oligomeric materials such as ε-hydroxycaproic acid, ε-Acyloxyhexanoic acid, hexanodioic acid and polycaprolactone that generate, thereby reduce the yield and the difficulty that increases the 6-caprolactone separation and purification of 6-caprolactone.Therefore, want high-level efficiency and prepare purified 6-caprolactone, the content of these materials in the essential control raw material.
Summary of the invention
The object of the present invention is to provide a kind of high-level efficiency to prepare the method for 6-caprolactone.
Technical solution of the present invention is:
A kind of method that is used to prepare 6-caprolactone, it comprises uses peracetic acid soln and pimelinketone reaction.Wherein peracetic acid soln is according to the described method preparation of patent 201010018162.X, promptly is shown below and uses sufficient aceticanhydride and ydrogen peroxide 50 to reach the reaction of moisture of wherein bringing into, prepares the acetic acid soln of Peracetic Acid; Wherein Peracetic Acid content is 20-46%, and water-content is not higher than 0.5%, and hydrogen peroxide content is not higher than 0.2%; This peracetic acid soln and pimelinketone reaction in same reactor drum, by the Peracetic Acid of every mole of pimelinketone supply 0.8-1.3 mole, above-mentioned pimelinketone and the reaction of above-mentioned peracetic acid soln generate 6-caprolactone.After reaction finishes, the transformation efficiency of percarboxylic acids and pimelinketone can reach simultaneously 99% reach more than.The 6-caprolactone solution that is dissolved in the acetate uses the traditional method fractionation by distillation, prepares purified 6-caprolactone product, and product content is not less than 99.5%.The 6-caprolactone product that so prepares is higher than 91% corresponding to the percarboxylic acids molar yield, is higher than 92% with respect to the molar yield of pimelinketone.This is more satisfactory product yield.
(CH
3CO)
2O+H
2O
2→CH
3COOOH+CH
3COOH
(CH
3CO)
2O+H
2O→2CH
3COOH
In the preparation 6-caprolactone process, the preparation anhydrous peroxyacetic acid if the use component distillation dewaters, the industry amplification of this process receives the material selectional restriction of distillation plant, and receives the restriction of expensive safety measures, and will eliminate moisture content simultaneously needs very long distillation time.The present invention prepares in the process of anhydrous peroxyacetic acid and has avoided component distillation to dewater, and has shortened the reaction times, reduced the cost of equipment input and has improved the security of operation.
In traditional 6-caprolactone production process, add the organic solvent dissolution percarboxylic acids mostly so that its can with the good homogeneous phase of the miscible formation of pimelinketone.Organic solvent such as acetone, benzene, propylene dichloride, ethylene dichloride, pyridine, ETHYLE ACETATE and acetonitrile etc. commonly used.Exist because of the percarboxylic acids solution of preparing has water among the present invention, percarboxylic acids may be dissolved in the acetic acid of reaction generation, thereby does not need to insert in addition organic solvent again, and this technology is favourable to reducing the separation power consumption.
The stablizer of percarboxylic acids commonly used has phosphoric acid salt, SULPHOSUCCINIC ACID ESTER, VPP, pyridine dicarboxylic acid, picoline etc.But under this temperature that process of the present invention is implemented, Peracetic Acid can't be decomposed in a large number and process is had a negative impact, thereby need not add stablizer and stablize peracetic acid soln.
Peracetic Acid and pimelinketone mol ratio are preferably 0.9-1.1 among the present invention; The transformation efficiency of Peracetic Acid and pimelinketone can surpass 99% simultaneously under this proportioning; I.e. reaction is complete basically, thereby the present invention has reduced the expense of separation and purification 6-caprolactone when raw material makes full use of.
Peracetic Acid and pimelinketone temperature of reaction preferable range are 40-65 ℃ among the present invention.The selection in reaction times will depend on temperature of reaction and material concentration.In general, to reach 99% optimal time be 3-7 hour to the Peracetic Acid transformation efficiency.
Do not use strong acid catalyst in the reaction process of the present invention; And water content is not higher than 0.5% in the peracetic acid soln, and hydrogen peroxide content is not higher than 0.2%, thereby byproduct of reaction is few; High boiling product quality as obtaining in the distillation purifying 6-caprolactone process is few, has guaranteed the yield of 6-caprolactone.
The present invention has following advantage:
Can under fully energy-conservation prerequisite, prepare purified 6-caprolactone safely, and 6-caprolactone is higher than 91% with respect to the yield of Peracetic Acid, is higher than 92%, be suitable for suitability for industrialized production with respect to the yield of pimelinketone.
Embodiment
Embodiment 1:
Adding concentration is 70% ydrogen peroxide 50 121g in having the 1000ml reactor drum of heating, stirring, TM, reflux condensing tube; Heating in water bath also keeps feed temperature constant in 40-45 ℃; Splash into aceticanhydride 492g; The dropping time was controlled at 1-1.5 hour, dripped off the back with uniform temp reaction 1.5 hours.Detect that Peracetic Acid content is 26.3% in the solution, hydrogen peroxide content is 0.07%, and water content is 0.24%; Reactor drum and solution temperature are increased to 50 ℃, splash into pimelinketone 205g, the dropping time was controlled at 1-1.5 hour, and dropping temperature is controlled at 50-55 ℃, dripped off the back with uniform temp reaction 3 hours; Obtain containing the acetum of 6-caprolactone.The transformation efficiency of this process Peracetic Acid and pimelinketone is respectively 99.5% and 99.2%.It is 99.6% 6-caprolactone 221.5g that this 6-caprolactone solution obtains content through traditional rectifying purge process; Be 6-caprolactone corresponding to the molar yield of Peracetic Acid being 91.5%, is 92.9% corresponding to the molar yield of pimelinketone.
Embodiment 2:
Adding concentration is 70% ydrogen peroxide 50 121g in having the 1000ml reactor drum of heating, stirring, TM, reflux condensing tube; Heating in water bath also keeps feed temperature constant in 40-45 ℃; Splash into aceticanhydride 492g; The dropping time was controlled at 1-1.5 hour, dripped off the back with uniform temp reaction 0.5 hour.Detect that Peracetic Acid content is 25.8% in the solution, hydrogen peroxide content is 0.12%, and water content is 0.38%; Splash into pimelinketone 205g under the equal temperature, the dropping time was controlled at 1-1.5 hour, dripped off the back with uniform temp reaction 5 hours; Obtain containing the acetum of 6-caprolactone.The transformation efficiency of this process Peracetic Acid and pimelinketone is respectively 99.3% and 99.1%.It is 99.7% 6-caprolactone 216.8g that this 6-caprolactone solution obtains content through traditional rectifying purge process; Be 6-caprolactone corresponding to the molar yield of Peracetic Acid being 91.3%, is 90.9% corresponding to the molar yield of pimelinketone.
Reference examples 1:
Adding concentration is 70% ydrogen peroxide 50 121g and sulfuric acid catalyst 0.2g in having the 1000ml reactor drum of heating, stirring, TM, reflux condensing tube; Heating in water bath also keeps feed temperature constant in 40-45 ℃; Splash into aceticanhydride 492g; The dropping time was controlled at 1-1.5 hour, dripped off the back with uniform temp reaction 0.5 hour.Detect that Peracetic Acid content is 28.1% in the solution, hydrogen peroxide content is 0.02%, and water content is 0.07%; Reactor drum and solution temperature are increased to 50 ℃, splash into pimelinketone 215g, the dropping time was controlled at 1-1.5 hour, and dropping temperature is controlled at 50-55 ℃, dripped off the back with uniform temp reaction 3 hours; Obtain containing the solution of 6-caprolactone.The transformation efficiency of this process Peracetic Acid and pimelinketone is respectively 98.6% and 99.2%.It is 99.2% 6-caprolactone 120.4g that this 6-caprolactone solution obtains content through traditional rectifying purge process; Be 6-caprolactone corresponding to the molar yield of Peracetic Acid being 46.6%, is 48.2% corresponding to the molar yield of pimelinketone.In the presence of strong acid, most of 6-caprolactone monomer has formed polymkeric substance and has influenced yield.
Reference examples 2:
Adding concentration is 70% ydrogen peroxide 50 132g in having the 1000ml reactor drum of heating, stirring, TM, reflux condensing tube; Heating in water bath also keeps feed temperature constant in 40-45 ℃; Splash into aceticanhydride 492g; The dropping time was controlled at 1-1.5 hour, dripped off the back with uniform temp reaction 0.5 hour.Detect that Peracetic Acid content is 24.6% in the solution, hydrogen peroxide content is 0.85%, and water content is 1.57%; Reactor drum and solution temperature are increased to 50 ℃, splash into pimelinketone 180g, the dropping time was controlled at 1-1.5 hour, and dropping temperature is controlled at 50-55 ℃, dripped off the back with uniform temp reaction 3 hours; Obtain containing 6-caprolactone solution.The transformation efficiency of this process Peracetic Acid and pimelinketone is respectively 99.0% and 98.7%.It is 99.5% 6-caprolactone 176.7g that this 6-caprolactone solution obtains content through traditional rectifying purge process; Be 6-caprolactone corresponding to the molar yield of Peracetic Acid being 76.7%, is 76.0% corresponding to the molar yield of pimelinketone.
Claims (8)
1. method for preparing 6-caprolactone is characterized in that: it comprises that using special anhydrous peroxyacetic acid solution and pimelinketone is 30-80 ℃ of reaction down in temperature; Reaction process does not need plus solvent, catalyzer and stablizer, helps the separation and purification of 6-caprolactone.
2. by the described a kind of method for preparing 6-caprolactone of claim 1, it is characterized in that: special anhydrous peroxyacetic acid solution makes with the hydrogen peroxide oxidation aceticanhydride, and the Peracetic Acid mass content is 20-46%.
3. by the described a kind of method for preparing 6-caprolactone of claim 1, it is characterized in that: water content is not higher than 0.5%, mass percent in the special anhydrous peroxyacetic acid solution.
4. by the described a kind of method for preparing 6-caprolactone of claim 1, it is characterized in that: hydrogen peroxide content is not higher than 0.2%, mass percent in the special anhydrous peroxyacetic acid solution.
5. by the described a kind of method for preparing 6-caprolactone of claim 1, it is characterized in that: Peracetic Acid and pimelinketone mol ratio are 0.8-1.3.
6. by the described a kind of method for preparing 6-caprolactone of claim 5, it is characterized in that: Peracetic Acid and pimelinketone mol ratio are preferably 0.9-1.1.
7. by the described a kind of method for preparing 6-caprolactone of claim 1, it is characterized in that: temperature of reaction is preferably 40-65 ℃.
8. by the described a kind of method for preparing 6-caprolactone of claim 1, it is characterized in that: reaction pressure is a normal pressure.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539770A (en) * | 2013-10-08 | 2014-01-29 | 常州大学 | Continuous reaction technological method for preparing epsilon-caprolactone, and microchannel reaction equipment |
| CN104447672A (en) * | 2014-07-24 | 2015-03-25 | 江苏红太阳新材料有限公司 | Method for synthesizing epsilon-caprolactone by using active carbon immobilized heteropoly acid |
| CN105646436A (en) * | 2014-11-10 | 2016-06-08 | 中国石油化工股份有限公司 | Method for increasing yield of caprolactone |
| CN109789341A (en) * | 2016-09-28 | 2019-05-21 | 佩什托普公司 | Processing by caprolactone produce in the device and method of product stream that generate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1496985A (en) * | 2002-10-22 | 2004-05-19 | 大赛璐化学工业株式会社 | Preparation method of e-caprolactone |
-
2010
- 2010-03-11 CN CN2010101261176A patent/CN102367246A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1496985A (en) * | 2002-10-22 | 2004-05-19 | 大赛璐化学工业株式会社 | Preparation method of e-caprolactone |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539770A (en) * | 2013-10-08 | 2014-01-29 | 常州大学 | Continuous reaction technological method for preparing epsilon-caprolactone, and microchannel reaction equipment |
| CN103539770B (en) * | 2013-10-08 | 2016-06-08 | 常州大学 | A kind of continuous reaction process method and microchannel reaction equipment preparing 6-caprolactone |
| CN104447672A (en) * | 2014-07-24 | 2015-03-25 | 江苏红太阳新材料有限公司 | Method for synthesizing epsilon-caprolactone by using active carbon immobilized heteropoly acid |
| CN105646436A (en) * | 2014-11-10 | 2016-06-08 | 中国石油化工股份有限公司 | Method for increasing yield of caprolactone |
| CN105646436B (en) * | 2014-11-10 | 2019-01-22 | 中国石油化工股份有限公司 | A method of improving caprolactone yield |
| CN109789341A (en) * | 2016-09-28 | 2019-05-21 | 佩什托普公司 | Processing by caprolactone produce in the device and method of product stream that generate |
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Application publication date: 20120307 |