CN105646436B - A method of improving caprolactone yield - Google Patents
A method of improving caprolactone yield Download PDFInfo
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- CN105646436B CN105646436B CN201410645459.7A CN201410645459A CN105646436B CN 105646436 B CN105646436 B CN 105646436B CN 201410645459 A CN201410645459 A CN 201410645459A CN 105646436 B CN105646436 B CN 105646436B
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- anhydride
- caprolactone
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- acid
- neck flask
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 22
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 12
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 9
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 4
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims abstract description 3
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims abstract description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims abstract description 3
- PKHMTIRCAFTBDS-UHFFFAOYSA-N hexanoyl hexanoate Chemical compound CCCCCC(=O)OC(=O)CCCCC PKHMTIRCAFTBDS-UHFFFAOYSA-N 0.000 claims abstract description 3
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 13
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- -1 propionic andydride Chemical compound 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 10
- 239000000498 cooling water Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of methods for improving caprolactone yield, the last stage reaction addition acid anhydrides substance for generating caprolactone is reacted with peracid in cyclohexanone, such as acetic anhydride, propionic andydride, butyric anhydride, valeric anhydride, caproic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, phthalic anhydride etc., to improve the yield of caprolactone.Method of the invention is simple, and easy to implement, is suitble to industrial applications, the production cost of caprolactone can be greatly lowered, bring huge economic benefit.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for improving the yield of caprolactone.
Background
Epsilon-caprolactone (epsilon-CL) is an important organic synthesis intermediate, for example, can be used for synthesizing polycaprolactone and polycaprolactone polyol, and can also be copolymerized with other esters or modified by blending, and polycaprolactone and modified polymers thereof have good biocompatibility, nontoxicity, biodegradability and good drug permeability, so that the epsilon-caprolactone (epsilon-CL) can be better applied to degradable plastics and biomedicine. Polycaprolactone polyol is one of starting materials of high-grade polyurethane materials, caprolactone is a temperature sensitive substance and can easily self-polymerize into 2-10 molecular oligomers at high temperature, and in the production process of epsilon-caprolactone, the temperature of a rectification process is high, epsilon-caprolactone can generate self-polymerization to a certain degree, so that the waste amount is increased, the production cost is increased, and the generated high-boiling-point waste is sludge-like fluid at normal temperature and becomes solid after being placed for a period of time, so that the treatment difficulty is high, and the method is a delicate environment-friendly problem. The problems cannot be well solved by adopting an azeotropic distillation mode at present.
Disclosure of Invention
The invention aims to provide a method for improving the yield of caprolactone, which is simple, efficient and convenient to implement, and greatly reduces the cost.
The invention discloses a method for improving the yield of caprolactone, which is characterized in that an anhydride substance is added at the final stage of the reaction of cyclohexanone and peracid for preparing caprolactone, wherein the anhydride substance is selected from one or more of acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride or phthalic anhydride; the addition amount of the anhydride substances is 0.5-10 t% of the mass of the whole reaction system.
The quality of the whole reaction system refers to the quality of raw materials and products in the whole cyclohexanone and peracid reaction system. The end of the reaction means that the reaction is more than 90% completed or the reaction is finished.
The addition amount of the acid anhydride substances is preferably 0.5-8% of the mass of the whole reaction system.
The addition amount of the acid anhydride substances is more preferably 1-5% of the mass of the whole reaction system.
The addition amount of the acid anhydride substances is more preferably 2.5-5% of the mass of the whole reaction system.
The acid anhydride is preferably acetic anhydride, propionic anhydride or succinic anhydride.
The preferable scheme is as follows:
the addition amount of the anhydride substances is 1-2.5% of the mass of the whole reaction system; the anhydride is acetic anhydride.
Or,
the addition amount of the anhydride substances is 2.5-5% of the mass of the whole reaction system; the acid anhydride substance is succinic anhydride.
It was found that the yield of caprolactone could be further improved by the above-mentioned preference.
The temperature for the reaction of cyclohexanone and peracid is 40-80 ℃.
The peracid is exemplified by peracetic acid, propionic acid peroxide, perbenzoic acid, etc.
The invention has the advantages of
Aiming at the defect of low yield of the caprolactone prepared by the prior art, the invention provides a method for improving the yield of the caprolactone. Specifically, the acid anhydride substances are added at the final stage of the reaction for preparing the caprolactone by reacting the cyclohexanone and the peracid, and the yield of the caprolactone can be greatly improved and the autopolymerization amount of the caprolactone can be effectively reduced by controlling the synergistic cooperation of the addition amount of the acid anhydride substances. Particularly, the effect of improving the yield of caprolactone which is greatly superior to that of the prior art can be obtained by selecting specific anhydride substances and controlling the content of the anhydride substances. The method is simple, easy to implement, suitable for industrial application, and capable of greatly reducing the production cost of caprolactone and bringing great economic benefits.
Detailed Description
The following examples further illustrate the invention without limiting it.
Example 1
Reacting anhydrous peroxypropionic acid with cyclohexanone at 40-80 deg.C for 1-10 hr to obtain caprolactone-containing mixture.
Putting 200g of the mixture containing caprolactone into a 500mL glass three-neck flask, adding 2g of acetic anhydride, sealing the three-neck flask, putting the three-neck flask on a heating oil bath, connecting a gas phase condenser, starting cooling water and stirring, reacting at constant temperature of 120 ℃ for 5 hours, distilling at 1.0-1.5kPa, cooling the gas phase, stopping distilling after no distillate flows out, discharging vacuum, weighing 9.0g of residual liquid (mainly, low polymer of caprolactone, the same below) in the three-neck flask, and obtaining the caprolactone yield of 82.0%.
Example 2
Putting 200g of the mixture containing caprolactone into a 500mL glass three-neck flask, adding 5g of acetic anhydride, sealing the three-neck flask, putting the three-neck flask on a heating oil bath, connecting a gas phase condenser, starting cooling water and stirring, reacting at constant temperature of 120 ℃ for 5 hours, distilling at 1.0-1.5kPa, cooling the gas phase, stopping distilling after no distillate flows out, discharging vacuum, weighing 8.9g of residue in the three-neck flask, and obtaining the caprolactone yield of 82.2%.
Example 3
Putting 200g of the mixture containing caprolactone into a 500mL glass three-neck flask, adding 10g of succinic anhydride, sealing the three-neck flask, putting the three-neck flask on a heating oil bath, connecting a gas phase condenser, starting cooling water and stirring, reacting at constant temperature of 120 ℃ for 5 hours, distilling at 1.0-1.5kPa, cooling the gas phase, stopping distilling after no distillate flows out, unloading the vacuum, weighing 8.9g of residue in the three-neck flask, and obtaining the caprolactone yield of 82.2%.
Example 4
Putting 200g of the mixture containing caprolactone into a 500mL glass three-necked bottle, adding 1g of propionic anhydride, sealing the three-necked bottle, putting the three-necked bottle on a heating oil bath, connecting a gas phase condenser, starting cooling water and stirring, reacting at constant temperature of 120 ℃ for 5 hours, distilling at 1.0-1.5kPa, cooling the gas phase, stopping distilling after no distillate flows out, unloading the vacuum, weighing the residual liquid in the three-necked bottle to be 9.8g, and obtaining the caprolactone yield of 80.4%.
Example 5
200g of the mixture containing caprolactone is put into a 500mL glass three-neck flask, 5g of phthalic anhydride is added, the three-neck flask is sealed and put on a heating oil bath, a gas phase condenser is connected, cooling water and stirring are started, the constant temperature reaction is carried out for 5 hours at 120 ℃, then the distillation is carried out under 1.0-1.5kPa, the gas phase is cooled, the distillation is stopped after no distillate flows out, the vacuum is discharged, the residual liquid amount in the three-neck flask is weighed to be 10.8g, and the caprolactone yield is 78.4%.
Example 6
Putting 200g of the mixture containing caprolactone into a 500mL glass three-necked bottle, adding 0.5g of acetic anhydride and 3g of propionic anhydride, sealing the three-necked bottle, putting the three-necked bottle on a heating oil bath, connecting a gas phase condenser, starting cooling water and stirring, reacting at constant temperature of 120 ℃ for 5 hours, distilling at 1.0-1.5kPa, cooling the gas phase, stopping distilling after no distillate flows out, discharging vacuum, weighing the residue in the three-necked bottle to be 10.0g, and obtaining caprolactone yield of 80.0%.
Comparative example 1
Putting 200g of the mixture containing caprolactone into a 500mL glass three-neck flask, adding 0.1g of acetic anhydride, sealing the three-neck flask, putting the three-neck flask on a heating oil bath, connecting a gas phase condenser, starting cooling water and stirring, reacting at constant temperature of 120 ℃ for 5 hours, distilling at 1.0-1.5kPa, cooling the gas phase, stopping distilling after no distillate flows out, unloading the vacuum, weighing the residual liquid in the three-neck flask to be 16.6g, and obtaining the caprolactone yield of 66.8%.
Comparative example 2
Putting 200g of the mixture containing caprolactone in a 500mL glass three-neck flask, sealing the three-neck flask without adding an acid anhydride substance, putting the three-neck flask on a heating oil bath, connecting a gas phase condenser, starting cooling water and stirring, reacting at constant temperature of 120 ℃ for 5 hours, distilling at 1.0-1.5kPa, cooling the gas phase, stopping distilling after no distillate flows out, unloading the vacuum, weighing the residual liquid in the three-neck flask to be 19.8g, and obtaining the caprolactone yield of 60.4%.
Comparative example 3
Putting 200g of the mixture containing caprolactone into a 500mL glass three-necked bottle, adding 20g of dried 4A molecular sieve, sealing the three-necked bottle, putting the three-necked bottle on a heating oil bath, connecting with a gas-phase condenser, starting cooling water and stirring, reacting at constant temperature of 120 ℃ for 5 hours, distilling at 1.0-1.5kPa, cooling the gas phase, stopping distilling after no distillate flows out, discharging vacuum, weighing the residual liquid in the three-necked bottle to be 17.8g, and obtaining the caprolactone yield of 64.4%.
Claims (5)
1. A method for improving the yield of caprolactone is characterized in that an anhydride substance is added at the last stage of the reaction for preparing caprolactone by reacting cyclohexanone and peracid, wherein the anhydride substance is selected from one or more of acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride or phthalic anhydride; the adding amount of the anhydride substances is 1-5% of the mass of the whole reaction system;
the peracid is peracetic acid, peroxopropionic acid or perbenzoic acid;
the end of the reaction is the end of the reaction.
2. The method of claim 1, wherein the anhydride species is acetic anhydride, propionic anhydride, or succinic anhydride.
3. The method according to claim 1, characterized in that the addition amount of the acid anhydride substances is 1-2.5% of the mass of the whole reaction system; the anhydride is acetic anhydride.
4. The method according to claim 1, characterized in that the addition amount of the acid anhydride substances is 2.5-5% of the mass of the whole reaction system; the acid anhydride substance is succinic anhydride.
5. The process according to claim 1, wherein the temperature of the cyclohexanone and peracid reaction is between 40 and 80 ℃.
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| CN201410645459.7A CN105646436B (en) | 2014-11-10 | 2014-11-10 | A method of improving caprolactone yield |
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| CN105646436B true CN105646436B (en) | 2019-01-22 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212055A (en) * | 2010-04-08 | 2011-10-12 | 湖南大学 | Method for preparing epsilon-caprolactone by virtue of catalytic oxidation of cyclohexanone |
| CN102367246A (en) * | 2010-03-11 | 2012-03-07 | 江苏清泉化学有限公司 | Preparation method of epsilon-caprolactone |
| CN102731465A (en) * | 2012-07-09 | 2012-10-17 | 武汉理工大学 | Method for synthesizing epsilon-caprolactone |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3478344B2 (en) * | 1992-11-25 | 2003-12-15 | 日本ゼオン株式会社 | Production method of lactones |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367246A (en) * | 2010-03-11 | 2012-03-07 | 江苏清泉化学有限公司 | Preparation method of epsilon-caprolactone |
| CN102212055A (en) * | 2010-04-08 | 2011-10-12 | 湖南大学 | Method for preparing epsilon-caprolactone by virtue of catalytic oxidation of cyclohexanone |
| CN102731465A (en) * | 2012-07-09 | 2012-10-17 | 武汉理工大学 | Method for synthesizing epsilon-caprolactone |
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