CN108218741A - A kind of preparation method of adipic dihydrazide - Google Patents
A kind of preparation method of adipic dihydrazide Download PDFInfo
- Publication number
- CN108218741A CN108218741A CN201810149162.XA CN201810149162A CN108218741A CN 108218741 A CN108218741 A CN 108218741A CN 201810149162 A CN201810149162 A CN 201810149162A CN 108218741 A CN108218741 A CN 108218741A
- Authority
- CN
- China
- Prior art keywords
- hydrazine hydrate
- reaction
- adipic
- adipic dihydrazide
- type solid
- 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- Withdrawn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 preparation method of adipic dihydrazide, this method is using adipic acid and hydrazine hydrate as raw material, with HY type solid acid sieve peg-raking catalysts, 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 for reacting generation is constantly separated from reaction system, effectively promote the progress of hydrazidesization reaction, shorten the reaction time, improve reaction yield.Compared with prior art, the method for the present invention is simple for process, and reaction yield is high, the recyclable reuse of catalyst, esterification is eliminated, shortens processing step, reduces production cost, acid waste water and salt-containing organic wastewater are not generated, waste discharge is few, is a kind of environmental type production technology.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of preparation 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 it is more and more 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.
At present, there are mainly two types of the preparation methods of adipic dihydrazide, i.e. one-step method and two-step method.One-step method is using oneself
Diacid and hydrazine hydrate directly carry out hydrazidesization reaction generation ADH：By adipic acid and hydrazine hydrate back flow reaction one in a heated condition
Section time, then crystallisation by cooling, filtered, washing are dried and obtain solid ADH after recrystallizing, and the method is simple, is easy to grasp
Make, but yield is relatively low, no more than 65%；Two-step method refers to esterification and hydrazinolysisization reaction：First step esterification be by oneself two
Dimethyl adipate is obtained by the reaction in acid and methanol under concentrated sulfuric acid catalyst effect, and second step hydrazinolysis is reacted by dimethyl adipate
With hydration hydrazine reaction generation ADH.Although two-step method increases compared with one-step method on yield, need first by adipic acid with
Methanol carries out esterification, this just increases reaction step, increases production cost, further, since esterification uses dense sulphur
Acid as catalyst can generate a large amount of acidic organic wastewaters, with the salt content in alkali neutralization processed waste water and COD contents all very
Height, wastewater treatment difficulty is big, processing cost is high, since waste discharge amount is big, easily causes environmental pollution.
Invention content
In order to overcome disadvantages mentioned above of the existing technology, the present invention provides one kind is simple for process, reaction yield is high, raw
Produce the adipic dihydrazide novel preparation 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, urged with HY type solid acid molecular sieves
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
The water for reacting generation is constantly separated from reaction system（Reaction balance to be promoted to be moved to positive direction, when shortening reaction
Between, improve reaction yield）, excessive hydrazine hydrate is steamed by recycling, remaining solid matter using vacuum distillation after reaction
It is filtered after being dissolved with pure water, filter cake with appropriate pure water to recycle HY type solid acid molecular sieve catalysts, through decompression steam by filtrate
Hair concentration remove moisture after obtain adipic dihydrazide crude product, then washed with absolute ethyl alcohol, dry after obtain adipic dihydrazide
Finished product.The grain size of HY type solid acid molecular sieves used in the reaction of above-mentioned hydrazidesization is 1~2mm, the molecular sieve catalyst through regeneration at
It is reusable after reason.
The specific processing step of the method for the present invention is as follows：Adipic acid, hydrazine hydrate and HY type solid acid molecular sieves are put into band
Have in the reaction kettle of rectifying column, open stirring, be heated to reflux, after steam enters rectifying column, in 95 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 at a reflux temperature,
Remaining hydrazine hydrate is steamed by recycling using vacuum distillation, hydrazine hydrate adds in appropriate pure water after all being steamed will be in reaction kettle
Solid matter fully dissolves, and HY type solid acid molecular sieve catalysts, the appropriate pure water of filter cake, by filtrate is then recovered by filtration
Be evaporated under reduced pressure concentration remove moisture after obtain adipic dihydrazide crude product, then washed with absolute ethyl alcohol, dry after obtain adipic acid
Two hydrazides finished products.
In above-mentioned steps, the mass ratio of adipic acid and hydrazine hydrate is for the dosage of 1: 1~1.5, HY type solid acid molecular sieves
The 10%~20% of adipic acid quality, the content of hydrazine hydrate is 80%~100%.
Compared with prior art, beneficial effects of the present invention are as follows：The present invention uses HY using adipic acid and hydrazine hydrate as raw material
Type solid acid sieve peg-raking catalyst, one-step method prepares adipic dihydrazide, simple for process, and reaction yield is high（In terms of adipic acid
Yield is more than 95%）, the recyclable reuse of catalyst eliminates esterification, shortens processing step, reduce production
Cost does not generate acid waste water and salt-containing organic wastewater, reduces the discharge of waste, is a kind of environmental type production work
Skill.
Specific embodiment
Embodiment 1
Adipic acid 150g, the hydrazine hydrate 200g and HY type solid acid molecular sieve 15g that content is 80% are put into stirring, temperature
It counts, in the four-hole boiling flask of rectifying column, opens stirring, reflux is heated to, after steam enters rectifying column, in column top temperature 95
DEG C~100 DEG C of extraction vapor, it reacts 4~6 hours, terminates after rectifying capital evaporated condensation water flows out anti-at a reflux temperature
Should, hydrazine hydrate remaining in flask is steamed into recycling with vacuum distillation, hydrazine hydrate adds in appropriate pure water after all being steamed will burn
Solid matter in bottle fully dissolves, and then pours out solution, recycling HY type solid acid molecular sieve catalysts, filter cake is filtered by vacuum
With appropriate pure water, filtrate is transferred to reduction vaporization concentration removing moisture in cucurbit and obtains adipic dihydrazide crude product, then use
Adipic dihydrazide finished product 170.9g is obtained after absolute ethyl alcohol washing, drying.
Embodiment 2
Adipic acid 150g, the hydrazine hydrate 210g and HY type solid acid molecular sieve 22g that content is 90% are put into stirring, temperature
It counts, in the four-hole boiling flask of rectifying column, opens stirring, reflux is heated to, after steam enters rectifying column, in column top temperature 95
DEG C~100 DEG C of extraction vapor, it reacts 4~6 hours, terminates after rectifying capital evaporated condensation water flows out anti-at a reflux temperature
Should, hydrazine hydrate remaining in flask is steamed into recycling with vacuum distillation, hydrazine hydrate adds in appropriate pure water after all being steamed will burn
Solid matter in bottle fully dissolves, and then pours out solution, recycling HY type solid acid molecular sieve catalysts, filter cake is filtered by vacuum
With appropriate pure water, filtrate is transferred to reduction vaporization concentration removing moisture in cucurbit and obtains adipic dihydrazide crude product, then use
Adipic dihydrazide finished product 172.4g is obtained after absolute ethyl alcohol washing, drying.
Embodiment 3
Adipic acid 150g, the hydrazine hydrate 228g and HY type solid acid molecular sieve 30g that content is 98% are put into stirring, temperature
It counts, in the four-hole boiling flask of rectifying column, opens stirring, reflux is heated to, after steam enters rectifying column, in column top temperature 95
DEG C~100 DEG C of extraction vapor, it reacts 4~6 hours, terminates after rectifying capital evaporated condensation water flows out anti-at a reflux temperature
Should, hydrazine hydrate remaining in flask is steamed into recycling with vacuum distillation, hydrazine hydrate adds in appropriate pure water after all being steamed will burn
Solid matter in bottle fully dissolves, and then pours out solution, recycling HY type solid acid molecular sieve catalysts, filter cake is filtered by vacuum
With appropriate pure water, filtrate is transferred to reduction vaporization concentration removing moisture in cucurbit and obtains adipic dihydrazide crude product, then use
Adipic dihydrazide finished product 173.5g is obtained after absolute ethyl alcohol washing, drying.
Claims (1)
1. a kind of preparation method of adipic dihydrazide, it is characterised in that include the following steps：By adipic acid, hydrazine hydrate and HY types
Solid acid 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 95 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 adds in suitable after all being steamed
Amount pure water fully dissolves the solid matter in reaction kettle, and HY type solid acid molecular sieve catalysts are then recovered by filtration, and filter cake is used
Filtrate decompression is concentrated by evaporation after removing moisture and obtains adipic dihydrazide crude product, then washed with absolute ethyl alcohol by appropriate pure water
Wash, dry after obtain adipic dihydrazide finished product；In above-mentioned steps, the mass ratio of adipic acid and hydrazine hydrate is 1: 1~1.5, HY
The dosage of type solid acid molecular sieve is that the grain size of 10%~20%, the HY type solid acid molecular sieves of adipic acid quality is 1~2mm, water
The content for closing hydrazine is 80%~100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810149162.XA CN108218741A (en) | 2018-02-13 | 2018-02-13 | A kind of preparation method of adipic dihydrazide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810149162.XA CN108218741A (en) | 2018-02-13 | 2018-02-13 | A kind of preparation method of adipic dihydrazide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108218741A true CN108218741A (en) | 2018-06-29 |
Family
ID=62661800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810149162.XA Withdrawn CN108218741A (en) | 2018-02-13 | 2018-02-13 | A kind of preparation method of adipic dihydrazide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108218741A (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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107056646A (en) * | 2017-03-24 | 2017-08-18 | 李亚杉 | A kind of synthetic method of adipic dihydrazide |
-
2018
- 2018-02-13 CN CN201810149162.XA patent/CN108218741A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107056646A (en) * | 2017-03-24 | 2017-08-18 | 李亚杉 | A kind of synthetic method of adipic dihydrazide |
Non-Patent Citations (1)
| Title |
|---|
| 韩兴刚，冯朋鑫: "《苏里格气田天然气集输新技术》", 31 August 2015, 石油工业出版社 * |
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 |
|---|---|---|
| HUANG et al. | Recycling and reuse of ionic liquid in homogeneous cellulose acetylation | |
| CN102344220B (en) | Method for treating metronidazole waste water | |
| CN101318901A (en) | Novel synthesis process for dimethyl fumarate | |
| CN108218741A (en) | A kind of preparation method of adipic dihydrazide | |
| 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 | |
| CN107963980A (en) | The synthetic method of adipic dihydrazide | |
| CN110818573B (en) | Preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane | |
| CN103145796B (en) | Synthesis process of neotame | |
| CN102180790B (en) | Method for removing water from ethyl acetate and butanone mixed solvent | |
| RU2524778C1 (en) | Method of producing betulin | |
| CN108299228A (en) | The preparation method of adipic dihydrazide | |
| CN108558698A (en) | A method of preparing adipic dihydrazide | |
| CN112694409B (en) | Method and device for recycling triethylamine in wastewater | |
| CN108250100A (en) | A kind of synthetic method of acethydrazide | |
| CN110818548A (en) | Method for preparing benzylidene acetone | |
| CN112645815A (en) | Preparation method for catalytically synthesizing methyl cinnamate based on eutectic solvent | |
| CN108409596A (en) | The synthetic method of 3,4,5- trimethoxybenzoyl hydrazines | |
| CN108329231A (en) | The preparation method of 3,4,5- trimethoxybenzoyl hydrazines | |
| CN108299231A (en) | A kind of synthetic method of salicylyl hydrazine | |
| CN110590677A (en) | Synthesis method of tinidazole | |
| CN108409597A (en) | A method of synthesis 3,4,5- trimethoxybenzoyl hydrazines | |
| CN108299229A (en) | A kind of preparation method of 3,4,5- trimethoxybenzoyls hydrazine | |
| CN108191705A (en) | A kind of method for preparing acethydrazide |
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: 20180629 |