CN108191708B - Synthesis method of adipic acid dihydrazide - Google Patents
Synthesis method of adipic acid dihydrazide Download PDFInfo
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- CN108191708B CN108191708B CN201810089330.0A CN201810089330A CN108191708B CN 108191708 B CN108191708 B CN 108191708B CN 201810089330 A CN201810089330 A CN 201810089330A CN 108191708 B CN108191708 B CN 108191708B
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Abstract
The invention discloses a method for synthesizing adipic acid dihydrazide, which comprises the steps of taking dimethyl adipate, acetonitril and water as raw materials, adding a catalyst into a system at a certain temperature, reacting for a certain time, and then distilling, crystallizing, washing and drying a reaction product to obtain a white solid, namely the target product adipic acid dihydrazide. The method has simple synthetic route and high product yield; the produced by-products and impurities are less, the post-treatment process is simple, and the purity of the product is high; the synthesis process has no three wastes, is green and environment-friendly, has lower raw material cost and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing adipic acid dihydrazide.
Background
Adipic Dihydrazide (ADH), also known as dihydrazide, white crystalline powder and a double-functional group compound are important cross-linking agents, can perform a cross-linking effect with diacetone acrylamide in the post-cross-linking of aqueous emulsion and water-soluble polymers, and are applied to aqueous resins and the like; can be used as a protein drug carrier after being crosslinked with sodium hyaluronate and applied to the medical field; can also be used as indoor formaldehyde adsorbent and intermediate raw material.
At present, the methods for synthesizing adipic acid dihydrazide in the prior art are mainly divided into two methods, namely a one-step synthesis method and a two-step synthesis method. The one-step synthesis method adopts adipic acid and hydrazine hydrate to directly react to generate adipic acid dihydrazide: adipic acid and hydrazine hydrate are refluxed and reacted for a certain time under the heating condition, and then the adipic acid and the hydrazine hydrate are cooled, crystallized, filtered, washed, dried and recrystallized to obtain solid adipic acid dihydrazide. The method is simple and easy to operate, but the yield is low and is not more than 65%. The two-step synthesis method adopts esterification reaction and hydrazide reaction: the first esterification reaction synthesizes adipic acid dimethyl/ethyl ester, and the second hydrazide reaction generates adipic acid dihydrazide by the reaction of ester and hydrazine hydrate. In the first esterification reaction process, concentrated sulfuric acid is mostly used as a catalyst, and the problems of strong corrosivity, generation of a large amount of organic wastewater, serious environmental pollution, generation of byproducts and more impurities and the like exist. In addition, the two synthetic methods both need hydrazine hydrate which is an expensive raw material, have high production cost and are not suitable for industrial production.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a novel method for synthesizing adipic acid dihydrazide, which has the advantages of simple production process, high product purity and yield, simple post-treatment, low production cost and environmental protection.
In order to achieve the purpose, the invention adopts the following technical scheme, which comprises the following specific steps:
(1) adding dimethyl adipate and azino-acetonide into a reaction container, heating to 40-65 ℃, and continuously stirring until the dimethyl adipate and the azino-acetonide are completely mixed and dissolved to obtain a mixed solution;
(2) continuously heating the mixed solution obtained in the step (1) until the temperature of the mixed solution reaches 112-128 ℃, slowly adding water into the mixed solution, simultaneously adding a catalyst, and controlling the reaction temperature to react at 112-128 ℃ for 1-5h to obtain a reaction product; water is slowly added to ensure that the reaction is more sufficient, and the generation of byproducts is avoided;
(3) and (3) distilling, crystallizing, washing and drying the product obtained in the step (2) to obtain the solid adipic dihydrazide.
The catalyst in the step (2) is any one of 001 × 2 strong-acid styrene cation exchange resin, 001 × 3 strong-acid styrene cation exchange resin, 001 × 4 strong-acid styrene cation exchange resin, 003 × 7 strong-acid styrene cation exchange resin, D072 macroporous strong-acid styrene cation exchange resin and D061 macroporous strong-acid styrene cation exchange resin, preferably D072 macroporous strong-acid styrene cation exchange resin. The adoption of the cation exchange resin type catalyst can not only reduce the production cost, accelerate the reaction rate, shorten the reaction time, but also improve the yield and the purity of the product.
The dosage of the catalyst in the step (2) is 10-25 wt% of the total weight of the dimethyl adipate, the azino-acetone and the water.
The molar ratio of the dimethyl adipate to the azino acetonate in the step (2) is 1: 2.5-3.5, preferably 1: 2.5-3.
The molar ratio of the azinium acetonide to the water in the step (2) is 1:2-4, preferably 1: 2-3.
The heating temperature in the step (1) is preferably 45 to 60 ℃.
The reaction temperature in the step (2) is preferably 115-125 ℃.
The reaction time in the step (2) is preferably 3 to 4 hours.
In the step (3), any one of ethanol, propanol, butanol and diethyl ether is used for washing, and ethanol is preferred. The reaction product is washed by an organic solvent, so that the purity and the yield of the product can be improved.
The temperature condition of washing in the step (3) is 5-25 ℃, and the washing times are 3-5.
The drying in the step (3) is vacuum drying at 40-80 ℃, preferably at 50-70 ℃.
Compared with the prior art, the invention has the following advantages: (1) the adipic acid dihydrazide is synthesized by a one-step method, the synthesis route is simple, and the product yield is high; (2) the produced by-products and impurities are less, the post-treatment process is simple, and the purity of the product is high; (3) the synthesis process has no three wastes, is green and environment-friendly, has lower raw material cost and is suitable for industrial production.
Detailed Description
Example 1
Adding 17.4g (0.1mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 28g (0.25mol) of azino acetone, heating to 50 ℃, and stirring at a constant speed until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 120 ℃, slowly adding 9g (0.5mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 11g of catalyst D072 macroporous strong-acid styrene cation exchange resin, ensuring that the temperature of the system is reacted for about 3 hours at 120 ℃ until dimethyl adipate is completely reacted, and obtaining a reaction product adipic acid dihydrazide; distilling the unreacted acetonitril and water out completely, crystallizing the solid in the flask, cooling the system temperature to about 20 ℃, washing the solid with absolute ethyl alcohol for 3-5 times, putting the solid in a vacuum drying oven for drying at 60 ℃ for 5 hours to obtain 17.2g of white solid, namely the target product adipic dihydrazide, wherein the yield is 99%, and the purity is 99.6% by HPLC.
Example 2
Adding 17.4g (0.1mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 28g (0.25mol) of azino acetone, heating to 40 ℃, and stirring at a constant speed until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 128 ℃, slowly adding 9g (0.5mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 11g of a catalyst 001 x 2 strong-acid styrene cation exchange resin, ensuring that the temperature of the system reacts for about 3 hours at 128 ℃ until dimethyl adipate completely reacts, and obtaining a reaction product adipic acid dihydrazide; distilling the unreacted acetonitril and water out completely, crystallizing the solid in the flask, cooling the system temperature to about 25 ℃, washing the solid with propanol for 3-5 times, putting the solid in a vacuum drying oven for drying at 65 ℃ for 5 hours to obtain 17g of white solid, namely the target product adipic dihydrazide, wherein the yield is 98%, and the purity is 99.2% by HPLC.
Example 3
Adding 26.1g (0.15mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 50.4g (0.45mol) of azino acetone, heating to 50 ℃, and stirring at a constant speed until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 120 ℃, slowly adding 16.2g (0.9mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 18.5g of catalyst D072 macroporous strong-acid styrene cation exchange resin, ensuring that the temperature of the system is reacted for about 3 hours at 125 ℃ until dimethyl adipate completely reacts to obtain a reaction product adipic dihydrazide; distilling the unreacted acetonitril and water out completely, crystallizing the solid in the flask, cooling the system temperature to about 25 ℃, washing the solid with absolute ethyl alcohol for 3-5 times, putting the solid in a vacuum drying oven for drying at 60 ℃ for 5 hours to obtain 25.9g of white solid, namely the target product adipic dihydrazide, wherein the yield is 99.2%, and the purity is 99.5% by HPLC (high performance liquid chromatography).
Example 4
Adding 26.1g (0.15mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 50.4g (0.45mol) of azino acetone, heating to 50 ℃, and stirring at a constant speed until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 120 ℃, slowly adding 16.2g (0.9mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 18.5g of a catalyst 001 x 3 strong-acid styrene cation exchange resin, ensuring that the temperature of the system is reacted for about 4 hours at 115 ℃ until dimethyl adipate completely reacts to obtain a reaction product adipic acid dihydrazide; distilling the unreacted acetonitril and water out completely, crystallizing the solid in the flask, cooling the system temperature to about 20 ℃, washing the solid with ether for 3-5 times, putting the washed solid in a vacuum drying oven at 75 ℃ for 3h to obtain 25.7g of white solid, namely the target product adipic dihydrazide, wherein the yield is 98.5%, and the purity is 99% by HPLC.
Example 5
Adding 31.3g (0.18mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 52.4g (0.47mol) of azino acetone, heating to 50 ℃, and uniformly stirring until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 118 ℃, slowly adding 25.2g (1.4mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 21.8g of catalyst D061 macroporous strong-acid styrene cation exchange resin, ensuring that the temperature of the system is about 3.5 hours at 118 ℃ until dimethyl adipate completely reacts, thus obtaining a reaction product adipic acid dihydrazide; distilling the unreacted acetonitril and water out completely, crystallizing the solid in the flask, cooling the system temperature to about 20 ℃, washing the solid with absolute ethyl alcohol for 3-5 times, putting the washed solid in a vacuum drying oven at 65 ℃ for 5 hours to obtain 31.0g of white solid, namely the target product adipic dihydrazide, wherein the yield is 99%, and the purity is 99.4% by HPLC.
Example 6
Adding 17.4g (0.1mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 39.2g (0.35mol) of azino acetone, heating to 65 ℃, and uniformly stirring until the two are completely mixed and dissolved to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 128 ℃, slowly adding 25.2g (1.4mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 20.5g of catalyst D072 macroporous strong-acid styrene cation exchange resin, ensuring that the temperature of the system is reacted for about 5 hours at 128 ℃ until dimethyl adipate completely reacts, and obtaining a reaction product adipic dihydrazide; distilling the unreacted acetonitril and water, crystallizing the solid in the flask, cooling the system temperature to about 25 ℃, washing the solid with absolute ethyl alcohol for 3-5 times, and drying in a vacuum drying oven at 80 ℃ for 3 hours to obtain 16.9g of white solid, namely the target product adipic dihydrazide, wherein the yield is 97.1%, and the purity is 99% by HPLC.
Example 7
Adding 26.1g (0.15mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 50.4g (0.45mol) of azino acetone, heating to 50 ℃, and stirring at a constant speed until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 120 ℃, slowly adding 16.2g (0.9mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and ensuring that the temperature of the system reacts for about 3 hours at 125 ℃ until dimethyl adipate completely reacts to obtain a reaction product adipic dihydrazide; distilling the unreacted acetonitril and water out completely, crystallizing the solid in the flask, cooling the system temperature to about 25 ℃, washing the solid with absolute ethyl alcohol for 3-5 times, putting the solid in a vacuum drying oven for drying at 60 ℃ for 5 hours to obtain 22.8g of white solid, namely the target product adipic dihydrazide, wherein the yield is 87.4%, and the purity is 96.2% by HPLC (high performance liquid chromatography).
Claims (6)
1. The synthesis method of adipic acid dihydrazide is characterized by comprising the following specific steps of: adding 17.4g (0.1mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 28g (0.25mol) of azino acetone, heating to 50 ℃, and stirring at a constant speed until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 120 ℃, slowly adding 9g (0.5mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 11g of catalyst D072 macroporous strong-acid styrene cation exchange resin, ensuring that the temperature of the system is reacted for about 3 hours at 120 ℃ until dimethyl adipate is completely reacted, and obtaining a reaction product adipic acid dihydrazide; distilling the unreacted acetonitril and water out completely, crystallizing the solid in the flask, cooling the system temperature to about 20 ℃, washing the solid with absolute ethyl alcohol for 3-5 times, putting the solid in a vacuum drying oven for drying at 60 ℃ for 5 hours to obtain 17.2g of white solid, namely the target product adipic dihydrazide, wherein the yield is 99%, and the purity is 99.6% by HPLC.
2. The synthesis method of adipic acid dihydrazide is characterized by comprising the following specific steps of: adding 17.4g (0.1mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 28g (0.25mol) of azino acetone, heating to 40 ℃, and stirring at a constant speed until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 128 ℃, slowly adding 9g (0.5mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 11g of a catalyst 001 x 2 strong-acid styrene cation exchange resin, ensuring that the temperature of the system reacts for about 3 hours at 128 ℃ until dimethyl adipate completely reacts, and obtaining a reaction product adipic acid dihydrazide; distilling the unreacted acetonitril and water completely, crystallizing the solid in the flask, cooling the system temperature to about 25 ℃, washing the solid with propanol for 3-5 times, putting the solid in a vacuum drying oven for drying at 65 ℃ for 5 hours to obtain 17g of white solid, namely the target product adipic dihydrazide, wherein the yield is 98%, and the purity is 99.2% by HPLC.
3. The synthesis method of adipic acid dihydrazide is characterized by comprising the following specific steps of: adding 26.1g (0.15mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 50.4g (0.45mol) of azino acetone, heating to 50 ℃, and stirring at a constant speed until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 120 ℃, slowly adding 16.2g (0.9mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 18.5g of catalyst D072 macroporous strong-acid styrene cation exchange resin, ensuring that the temperature of the system is reacted for about 3 hours at 125 ℃ until dimethyl adipate completely reacts to obtain a reaction product adipic dihydrazide; distilling the unreacted acetonitril and water out completely, crystallizing the solid in the flask, cooling the system temperature to about 25 ℃, washing the solid with absolute ethyl alcohol for 3-5 times, putting the solid in a vacuum drying oven for drying at 60 ℃ for 5 hours to obtain 25.9g of white solid, namely the target product adipic dihydrazide, wherein the yield is 99.2%, and the purity is 99.5% by HPLC (high performance liquid chromatography).
4. The synthesis method of adipic acid dihydrazide is characterized by comprising the following specific steps of: adding 26.1g (0.15mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 50.4g (0.45mol) of azino acetone, heating to 50 ℃, and stirring at a constant speed until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 120 ℃, slowly adding 16.2g (0.9mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 18.5g of a catalyst 001 x 3 strong-acid styrene cation exchange resin, ensuring that the temperature of the system is reacted for about 4 hours at 115 ℃ until dimethyl adipate completely reacts to obtain a reaction product adipic acid dihydrazide; distilling the unreacted acetonitril and water, crystallizing the solid in the flask, cooling the system temperature to about 20 ℃, washing the solid with diethyl ether for 3-5 times, putting the washed solid in a vacuum drying oven at 75 ℃ for 3h to obtain 25.7g of white solid, namely the target product adipic dihydrazide, wherein the yield is 98.5%, and the purity is 99% by HPLC.
5. The synthesis method of adipic acid dihydrazide is characterized by comprising the following specific steps of: adding 31.3g (0.18mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 52.4g (0.47mol) of azino acetone, heating to 50 ℃, and uniformly stirring until the two are completely mixed to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 118 ℃, slowly adding 25.2g (1.4mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 21.8g of catalyst D061 macroporous strong-acid styrene cation exchange resin, ensuring that the temperature of the system is about 3.5 hours at 118 ℃ until dimethyl adipate completely reacts, thus obtaining a reaction product adipic acid dihydrazide; distilling the unreacted acetonitril and water out completely, crystallizing the solid in the flask, cooling the system temperature to about 20 ℃, washing the solid with absolute ethyl alcohol for 3-5 times, and drying in a vacuum drying oven at 65 ℃ for 5 hours to obtain 31.0g of white solid, namely the target product adipic dihydrazide, wherein the yield is 99%, and the purity is 99.4% by HPLC.
6. The synthesis method of adipic acid dihydrazide is characterized by comprising the following specific steps of: adding 17.4g (0.1mol) of dimethyl adipate into a four-neck flask with a stirring rod, a thermometer and a separating funnel, then adding 39.2g (0.35mol) of azino acetone, heating to 65 ℃, and uniformly stirring until the two are completely mixed and dissolved to obtain a mixed solution; continuing to heat the mixed solution, when the temperature of the mixed solution reaches 128 ℃, slowly adding 25.2g (1.4mol) of water into the mixed solution by a separating funnel at a dropping speed of 25-30 seconds per drop, and simultaneously adding 20.5g of catalyst D072 macroporous strong-acid styrene cation exchange resin, ensuring that the temperature of the system is reacted for about 5 hours at 128 ℃ until dimethyl adipate completely reacts, and obtaining a reaction product adipic dihydrazide; distilling the unreacted acetonitril and water, crystallizing the solid in the flask, cooling the system temperature to about 25 ℃, washing the solid with absolute ethyl alcohol for 3-5 times, and drying in a vacuum drying oven at 80 ℃ for 3 hours to obtain 16.9g of white solid, namely the target product adipic dihydrazide, wherein the yield is 97.1%, and the purity is 99% by HPLC.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810770A (en) * | 2006-02-21 | 2006-08-02 | 凌青云 | Prepn process of acyldhydrazino adipate with free hydrazine content lower than 10ppm |
| CN105541657A (en) * | 2015-12-24 | 2016-05-04 | 山东天一化学股份有限公司 | Method for preparing adipic acid dihydrazide |
| CN106117079A (en) * | 2016-06-28 | 2016-11-16 | 潍坊芝麻开门化工有限公司 | A kind of adipic dihydrazide preparation method |
| CN106865513A (en) * | 2017-02-14 | 2017-06-20 | 李亚杉 | A kind of preparation method of hydrazine hydrate |
| CN106967020A (en) * | 2017-05-19 | 2017-07-21 | 重庆丽澄环保科技有限公司 | A kind of synthetic method of 2 furoyl hydrazine |
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- 2018-01-30 CN CN201810089330.0A patent/CN108191708B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810770A (en) * | 2006-02-21 | 2006-08-02 | 凌青云 | Prepn process of acyldhydrazino adipate with free hydrazine content lower than 10ppm |
| CN105541657A (en) * | 2015-12-24 | 2016-05-04 | 山东天一化学股份有限公司 | Method for preparing adipic acid dihydrazide |
| CN106117079A (en) * | 2016-06-28 | 2016-11-16 | 潍坊芝麻开门化工有限公司 | A kind of adipic dihydrazide preparation method |
| CN106865513A (en) * | 2017-02-14 | 2017-06-20 | 李亚杉 | A kind of preparation method of hydrazine hydrate |
| CN106967020A (en) * | 2017-05-19 | 2017-07-21 | 重庆丽澄环保科技有限公司 | A kind of synthetic method of 2 furoyl hydrazine |
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