CN108484433A - A kind of synthetic method of adipic dihydrazide - Google Patents
A kind of synthetic method of adipic dihydrazide Download PDFInfo
- Publication number
- CN108484433A CN108484433A CN201810147634.8A CN201810147634A CN108484433A CN 108484433 A CN108484433 A CN 108484433A CN 201810147634 A CN201810147634 A CN 201810147634A CN 108484433 A CN108484433 A CN 108484433A
- Authority
- CN
- China
- Prior art keywords
- hydrazine hydrate
- reaction
- molecular sieve
- adipic dihydrazide
- adipic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/04—Preparation of hydrazides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of synthetic method of adipic dihydrazide, this method is to make catalyst with mordenite molecular sieve using adipic acid and hydrazine hydrate as raw material, carries out hydrazides at a certain temperature and adipic dihydrazide is obtained by the reaction.It keeps hydrazine hydrate excessive in the reaction system, and the water that reaction generates constantly is separated from reaction system, effectively promotes the progress of hydrazidesization reaction, shorten the reaction time, improve reaction yield.Compared with prior art, the method of the present invention is simple for process, reaction yield is high, the recyclable reuse of catalyst, eliminates esterification, shortens processing step, reduce production cost, acid waste water or salt-containing organic wastewater are not generated, reduces the discharge of waste, are a kind of environmental type production technologies.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of synthetic method of adipic dihydrazide.
Background technology
Adipic dihydrazide（ADH）, white crystalline solid is soluble easily in water, has symmetrical molecular structure, is double-functional group
Compound.ADH is a kind of good crosslinking agent, can be crosslinked with carbonyl, more typically has and is applied to doctor with cross-linking hyaluronic acid
Pharmacy is applied to water-base resin etc. with Diacetone Acrylamide crosslinking.As environmental legislation is to volatile organic matter in coating
Limitation be increasingly stringenter, in recent years, domestic and foreign scholars have carried out numerous studies to water paint, and Related product is quickly sent out
Exhibition, and in many application fields, substituted traditional solvent based coating in whole or in part it is contemplated that with
The raising of people's quality of life and technical progress of industry, the production cost of water paint can constantly reduce, and development prospect is very
It is wide.
Currently, there are mainly two types of the synthetic methods of adipic dihydrazide, i.e. one-step method and two-step method.One-step method is to use oneself
Diacid and hydrazine hydrate directly carry out hydrazidesization reaction and generate ADH：By adipic acid and hydrazine hydrate back flow reaction one in a heated condition
The section time, then crystallisation by cooling, obtains solid ADH after being filtered, washed, drying and recrystallize, and the method is simple, is easy to grasp
Make, but yield is relatively low, is no more than 65%；Two-step method refers to esterification and hydrazinolysisization reaction：First step esterification obtains oneself two
Sour two methyl/ethyl esters, the reaction of second step hydrazinolysis generate ADH by ester and hydration hydrazine reaction.Although two-step method is being received compared with one-step method
It increases in rate, but needs that adipic acid and methanol/ethanol are first carried out esterification, this just increases reaction step, increases
Production cost further, since esterification makees catalyst using the concentrated sulfuric acid will produce a large amount of acidic organic wastewaters, in alkali
With in processed waste water salt content and COD contents it is all very high, wastewater treatment difficulty is big, processing cost is high, due to waste arrange
It is high-volume big, easily cause environmental pollution.
Invention content
In order to overcome disadvantages mentioned above of the existing technology, the present invention provides it is a kind of it is simple for process, reaction yield is high, raw
Produce the adipic dihydrazide new synthetic method that at low cost, waste discharge is few, environmentally protective.
The technical solution adopted by the present invention is：Using adipic acid and hydrazine hydrate as raw material, it is catalyzed with mordenite molecular sieve
Agent carries out hydrazides and adipic dihydrazide is obtained by the reaction at a certain temperature.Keep hydrazine hydrate excessive in the reaction system, and will
The water that reaction generates constantly is separated from reaction system（To promote reaction balance to be moved to positive direction, the shortening reaction time,
Improve reaction yield）, excessive hydrazine hydrate is steamed by recycling using vacuum distillation after reaction, remaining solid matter is with pure
It is filtered after water dissolution, with appropriate pure water to recycle mordenite molecular sieve catalyst, filtrate concentrates filter cake through being evaporated under reduced pressure
Adipic dihydrazide crude product is obtained after removing moisture, then washed with absolute ethyl alcohol, obtain adipic dihydrazide finished product after drying.On
The grain size for stating hydrazidesization reaction mordenite molecular sieve used is 1~2mm, which repeats after regeneration treatment
It uses.
The specific processing step of the method for the present invention is as follows：Adipic acid, hydrazine hydrate and mordenite molecular sieve are put into and carried
In the reaction kettle of rectifying column, open stirring, be heated to reflux, after steam enters rectifying column, 98 DEG C of tower top temperature~
100 DEG C of extraction vapor, react 4~6 hours, react and terminate after rectifying tower top evaporated condensation water flows out, adopt at a reflux temperature
Remaining hydrazine hydrate is steamed into recycling with vacuum distillation, appropriate pure water is added by the solid in reaction kettle in hydrazine hydrate after all steaming
Substance fully dissolves, and mordenite molecular sieve catalyst is then recovered by filtration, and the appropriate pure water of filter cake steams filtrate decompression
Hair concentration obtains adipic dihydrazide crude product after removing moisture, then is washed with absolute ethyl alcohol, obtains adipic dihydrazide after drying
Finished product.
In above-mentioned steps, the mass ratio of adipic acid and hydrazine hydrate is 1: 1~1.5, and the dosage of mordenite molecular sieve is for oneself
The content of the 10%~20% of diacid quality, hydrazine hydrate is 80%~100%.
Compared with prior art, beneficial effects of the present invention are as follows：The present invention is using adipic acid and hydrazine hydrate as raw material, with silk
Geolyte sieve peg-raking catalyst, one-step synthesis method adipic dihydrazide is simple for process, and reaction yield is high（It is collected with adipic acid
Rate is 95% or more）, the recyclable reuse of catalyst eliminates esterification, shortens processing step, reduce and be produced into
This, does not generate acid waste water or salt-containing organic wastewater, reduces the discharge of waste, be a kind of environmental type production technology.
Specific implementation mode
Embodiment 1
By adipic acid 150g, content be 80% hydrazine hydrate 200g and mordenite molecular sieve 15g be put into stirring, thermometer,
In the four-hole boiling flask of rectifying column, stirring is opened, reflux is heated to, after steam enters rectifying column, in 98 DEG C of column top temperature
~100 DEG C of extraction vapor, react 4~6 hours at a reflux temperature, and reaction was completed after rectifying capital evaporated condensation water flows out,
Remaining hydrazine hydrate in flask is steamed into recycling with vacuum distillation, appropriate pure water is added in hydrazine hydrate after all steaming will be in flask
Solid matter fully dissolves, and then pours out solution, recycling mordenite molecular sieve catalyst is filtered by vacuum, filter cake is used appropriate pure
Water washing, filtrate is transferred to reduction vaporization concentration removing moisture in cucurbit and obtains adipic dihydrazide crude product, then uses absolute ethyl alcohol
Adipic dihydrazide finished product 170.4g is obtained after washing, drying.
Embodiment 2
By adipic acid 150g, content be 90% hydrazine hydrate 210g and mordenite molecular sieve 22g be put into stirring, thermometer,
In the four-hole boiling flask of rectifying column, stirring is opened, reflux is heated to, after steam enters rectifying column, in 98 DEG C of column top temperature
~100 DEG C of extraction vapor, react 4~6 hours at a reflux temperature, and reaction was completed after rectifying capital evaporated condensation water flows out,
Remaining hydrazine hydrate in flask is steamed into recycling with vacuum distillation, appropriate pure water is added in hydrazine hydrate after all steaming will be in flask
Solid matter fully dissolves, and then pours out solution, recycling mordenite molecular sieve catalyst is filtered by vacuum, filter cake is used appropriate pure
Water washing, filtrate is transferred to reduction vaporization concentration removing moisture in cucurbit and obtains adipic dihydrazide crude product, then uses absolute ethyl alcohol
Adipic dihydrazide finished product 172.7g is obtained after washing, drying.
Embodiment 3
By adipic acid 150g, content be 98% hydrazine hydrate 228g and mordenite molecular sieve 30g be put into stirring, thermometer,
In the four-hole boiling flask of rectifying column, stirring is opened, reflux is heated to, after steam enters rectifying column, in 98 DEG C of column top temperature
~100 DEG C of extraction vapor, react 4~6 hours at a reflux temperature, and reaction was completed after rectifying capital evaporated condensation water flows out,
Remaining hydrazine hydrate in flask is steamed into recycling with vacuum distillation, appropriate pure water is added in hydrazine hydrate after all steaming will be in flask
Solid matter fully dissolves, and then pours out solution, recycling mordenite molecular sieve catalyst is filtered by vacuum, filter cake is used appropriate pure
Water washing, filtrate is transferred to reduction vaporization concentration removing moisture in cucurbit and obtains adipic dihydrazide crude product, then uses absolute ethyl alcohol
Adipic dihydrazide finished product 174.4g is obtained after washing, drying.
Claims (1)
1. a kind of synthetic method of adipic dihydrazide, it is characterised in that include the following steps：By adipic acid, hydrazine hydrate and mercerising
Zeolite molecular sieve is put into the reaction kettle with rectifying column, is opened stirring, reflux is heated to, when steam enters rectifying column
Afterwards, it in 98 DEG C~100 DEG C extraction vapor of tower top temperature, reacts 4~6 hours at a reflux temperature, when rectifying tower top frozen-free
It reacts and terminates after water outflow, remaining hydrazine hydrate is steamed by recycling using vacuum distillation, hydrazine hydrate is added appropriate after all steaming
Pure water fully dissolves the solid matter in reaction kettle, mordenite molecular sieve catalyst is then recovered by filtration, filter cake is in right amount
Filtrate decompression is concentrated by evaporation after removing moisture and obtains adipic dihydrazide crude product, then washed with absolute ethyl alcohol, is dry by pure water
Adipic dihydrazide finished product is obtained after dry；In above-mentioned steps, the mass ratio of adipic acid and hydrazine hydrate is 1: 1~1.5, modenite
The dosage of molecular sieve is the 10%~20% of adipic acid quality, and the grain size of mordenite molecular sieve is 1~2mm, the content of hydrazine hydrate
It is 80%~100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810147634.8A CN108484433A (en) | 2018-02-13 | 2018-02-13 | A kind of synthetic method of adipic dihydrazide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810147634.8A CN108484433A (en) | 2018-02-13 | 2018-02-13 | A kind of synthetic method of adipic dihydrazide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108484433A true CN108484433A (en) | 2018-09-04 |
Family
ID=63340449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810147634.8A Withdrawn CN108484433A (en) | 2018-02-13 | 2018-02-13 | A kind of synthetic method of adipic dihydrazide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484433A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862333A (en) * | 2019-11-29 | 2020-03-06 | 万华化学集团股份有限公司 | Mixed dibasic acid dihydrazide and preparation method and application thereof |
-
2018
- 2018-02-13 CN CN201810147634.8A patent/CN108484433A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862333A (en) * | 2019-11-29 | 2020-03-06 | 万华化学集团股份有限公司 | Mixed dibasic acid dihydrazide and preparation method and application thereof |
| CN110862333B (en) * | 2019-11-29 | 2022-11-08 | 万华化学集团股份有限公司 | Mixed dibasic acid dihydrazide and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107628930A (en) | A kind of heat pump separation of extractive distillation methanol, the energy saving technique of isopropyl alcohol and water | |
| CN103951544B (en) | Method for separating ethyl acetate and ethanol azeotrope by differential pressure rectification | |
| CN107344786A (en) | A kind of ultra-violet absorber UV 531 produces the method for comprehensive utilization of waste water | |
| CN104140420A (en) | Synthesis process of thiothiamine | |
| CN107056646A (en) | A kind of synthetic method of adipic dihydrazide | |
| CN108484433A (en) | A kind of synthetic method of adipic dihydrazide | |
| CN108358813A (en) | A kind of method of two hydrazides of synthesizing adipic acid | |
| CN108218741A (en) | A kind of preparation method of adipic dihydrazide | |
| CN107963980A (en) | The synthetic method of adipic dihydrazide | |
| CN102180790B (en) | Method for removing water from ethyl acetate and butanone mixed solvent | |
| CN103145796B (en) | Synthesis process of neotame | |
| CN108299228A (en) | The preparation method of adipic dihydrazide | |
| CN108558698A (en) | A method of preparing adipic dihydrazide | |
| RU2524778C1 (en) | Method of producing betulin | |
| CN102382044A (en) | Purification method for 2,3-dimethylpyridine | |
| WO2020216115A1 (en) | Method and apparatus for continuous post-treatment of benzotriazole synthetic fluid | |
| CN108409596A (en) | The synthetic method of 3,4,5- trimethoxybenzoyl hydrazines | |
| CN108250100A (en) | A kind of synthetic method of acethydrazide | |
| CN109456172B (en) | Method for purifying dodecanedioic acid in water phase | |
| CN108329231A (en) | The preparation method of 3,4,5- trimethoxybenzoyl hydrazines | |
| CN108409597A (en) | A method of synthesis 3,4,5- trimethoxybenzoyl hydrazines | |
| CN108178734A (en) | A kind of synthetic method of 3,4,5- trimethoxybenzoyls hydrazine | |
| CN108299231A (en) | A kind of synthetic method of salicylyl hydrazine | |
| CN108299229A (en) | A kind of preparation method of 3,4,5- trimethoxybenzoyls hydrazine | |
| CN108299230A (en) | The synthetic method of salicylyl hydrazine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180904 |