CN109748815A - A kind of synthetic method of adipic dihydrazide - Google Patents
A kind of synthetic method of adipic dihydrazide Download PDFInfo
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- CN109748815A CN109748815A CN201910058770.4A CN201910058770A CN109748815A CN 109748815 A CN109748815 A CN 109748815A CN 201910058770 A CN201910058770 A CN 201910058770A CN 109748815 A CN109748815 A CN 109748815A
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Abstract
The present invention provides a kind of synthetic methods of adipic dihydrazide, using two hydrazides of two-step method synthesizing adipic acid, esterification occurs under the catalysis of potassium acid sulfate and the concentrated sulfuric acid using the mixture of adipic acid and methanol and ethyl alcohol and has synthesized dimethyl adipate/ethyl ester, then by dimethyl adipate/ethyl ester and hydrazine hydrate hydrazides, adipic dihydrazide is obtained, the conversion ratio of obtained adipic dihydrazide finished product is 98 ~ 99%, method of the invention greatly improves esterification yield, catalytic activity, keep catalyst recycling easier, it is more to reuse number, it is economical and practical to be convenient for industrialized production.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of synthetic method of adipic dihydrazide.
Background technique
Adipic dihydrazide (ADH), white crystalline solid have symmetrical molecular structure, are double-functional group compounds.
ADH good crosslinking agent, can be crosslinked with carbonyl, more typically have and be applied to medicine and pharmacology with cross-linking hyaluronic acid, with diacetone third
Acrylamide crosslinking is applied to water-base resin etc..As limitation of the environmental legislation to volatile organic matter in coating is more and more tighter
Lattice, in recent years, domestic and foreign scholars have conducted extensive research Related product to water paint and are rapidly developed, and answer in many
With in field, traditional solvent based coating is substituted in whole or in part.It is contemplated that with people's quality of life
It improves and technical progress of industry, the production cost of water paint can be reduced constantly, development prospect is boundless.
As the monomer of ketone hydrazine crosslinking, the synthesis and application of Diacetone Acrylamide, domestic and international pertinent literature report is more
The study on the synthesis of ADH is relatively fewer.The method that document report adipic acid directly reacts synthesis ADH with hydrazine hydrate, but yield
It is lower.The 80's had document to describe two-step method synthesis ADH, two methyl/ethyl ester of first step synthesizing adipic acid, second step by ester and
It is hydrated hydrazine reaction and generates ADH.In first step esterification, the concentrated sulfuric acid is mostly used to make catalyst greatly, there are corrosivity by force, ring
The problems such as border harm is big, side reaction is miscellaneous.Environmentally friendly catalyst such as solid acid, heteropoly acid and metallic compound etc., although
It receives more and more attention, but the drawbacks such as generally existing higher cost, synthesis technology be cumbersome, conveniently in laboratory scale
Research and development need to solve in production application there are many more problem.The reaction of second step hydrazidesization, has document using raw material
Crystallisation by cooling after heated reflux a period of time filters out the washed method for being dried to obtain ADH product of solid.
Chinese patent CN201510983675.7 discloses a kind of preparation method of adipic dihydrazide, and steps are as follows: (1)
Adipic acid and the storng-acid cation exchange resin as catalyst are added in methanol, then heat reaction system to the shape that flows back
State carries out esterification at reflux；After esterification, under the conditions of 5 ~ 40 DEG C of temperature, first into reaction system
Ammonium hydroxide is added, hydrazine hydrate is then added, reaction system is made to carry out hydrazine generation reaction at 5 ~ 40 DEG C of temperature；Hydrazine generation after reaction,
Catalyst is filtered out, product after reaction is made；(2) after product removes methanol after distillation reaction, adipic dihydrazide crude product is obtained；Oneself
Dihydrazi crude product washed, dried after to get to adipic dihydrazide.The invention uses storng-acid cation exchange resin
It is at high cost complicated for operation as catalyst, be not suitable for industrialization large-scale production.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the present invention provides a kind of simple production process, product are pure
It spends and high income, the adipic dihydrazide new synthetic method that post-processing is simple, production cost is low, environmentally protective.
A kind of synthetic method of adipic dihydrazide, two hydrazides of two-step method synthesizing adipic acid use adipic acid and first first
Alcohol esterification reaction has synthesized dimethyl adipate, then by dimethyl adipate and hydrazine hydrate hydrazides, has obtained adipic acid two
Hydrazides, it is characterised in that: the esterification is urging reactant using the mixture of adipic acid and methanol and ethyl alcohol as reactant
The mixture of Dimethyl Adipate Catalyzed and diethylene adipate under the catalysis of agent；The hydrazidesization reaction synthesizes oneself obtained
The mixture of acid dimethyl and diethylene adipate is reacted with the hydrazine hydrate that mass fraction is 80%, obtains two acyl of diacid
Hydrazine product.
Further, the ratio between amount of substance of mixture of the adipic acid and methanol and ethyl alcohol is 3.4 ~ 4.5:1, described
The ratio between amount of substance of methanol and ethyl alcohol is 0.5 ~ 1.5:1 in the mixture of methanol and ethyl alcohol, and the methanol quality score is
100%, the mass fraction of the ethyl alcohol is 75 ~ 80%, and the reaction time of the esterification is 0.25 ~ 2h, reaction temperature is 40 ~
50℃。
Further, the ratio between the amount of substance of mixture and hydrazine hydrate of the dimethyl adipate and diethylene adipate
For 1:1.5 ~ 2.5, the reaction time of the hydrazidesization reaction is 1 ~ 2h, and reaction temperature is 20 ~ 40 DEG C.
Further, in the catalyst choice p-methyl benzenesulfonic acid, potassium acid sulfate, the concentrated sulfuric acid and lewis acid zinc chloride
It is one or several kinds of.
Further, the mixture of the catalyst choice potassium acid sulfate and the concentrated sulfuric acid.
Further, the ratio between amount of substance of the potassium acid sulfate and the concentrated sulfuric acid is 1:4.
Further, the ratio between amount of substance of the catalyst and adipic acid is 0.3 ~ 0.5:1.
Beneficial effects of the present invention:
1. the mixing that methanol of the present invention and alcohol mixture synthesize own dicarboxylic acid dimethyl ester and diethylene adipate as reactant
Object, it is therefore an objective to utilize ethyl alcohol, water binary azeotrope, can with benzene,
The entrainment reagents such as toluene, hexamethylene form the property of ternary azeotrope, during the reaction, pass through entrainment reagent constantly band ester output
Change the water generated, so that reaction balance be made to move right, greatly improves esterification yield.
2. catalyst sulfuric acid hydrogen potassium and the concentrated sulfuric acid that the present invention uses improve catalytic activity, keep catalyst recycling easier,
It is more to reuse number.
Specific embodiment
Further illustrate that technical solution of the present invention, these embodiments are intended merely to show this hair in detail below by embodiment
Bright technical concept and its exploitativeness, is not limiting the scope of the invention, is made using the technology of the present invention design
Equivalence replacement and it is flexible still within protection scope of the present invention.
Embodiment 1
A kind of synthetic method of adipic dihydrazide, specific steps are as follows:
(1) it injects into 500mL beaker in the mixed solution of 100% methanol (0.5mol) and 75% ethyl alcohol (0.5mol), then will
Adipic acid (3.5mol) is added in the mixed solution of methanol and ethyl alcohol, and potassium acid sulfate (0.1mol) and potassium sulfate is then added
The mixture of (0.4mol) carries out catalysis reaction, heating reaction system to reflux state, 45 DEG C of esters under reflux state and stirring
Change reaction 0.25h.
(2) after reaction time of esterification, cooling system is to 25 DEG C, and under stirring, mass fraction is first added dropwise into system is
80% hydrazine hydrate (5.25mol) is stirred for after dripping and carries out hydrazineization reaction 1.5h, hydrazineization reaction under the conditions of 25 DEG C of temperature
After, catalyst is filtered out, product after reaction is just made, catalyst can reuse after processing.
(3) then the material that reaction obtains filtered in closed centrifuge, washed once with methanol, after centrifugation
The exhaust gas in centrifuge is subjected to stripping with nitrogen before putting material, for stripping exhaust gas through level-one deep cooling recovered material, fixed gas is logical
It crosses pipeline and drains into active carbon adsorber.
(4) centrifuge mother liquor main component is methanol and ethyl alcohol, contains the complete hydrazine hydrate of a small amount of unreacted, adipic acid diformazan
Ester/ethyl ester enters methanol/ethanol rectification working process and recycles methanol/ethanol after collection.Hydrazine hydrate and methanol/ethanol azeotropic, steam together
It is collected out through -10 DEG C of deep coolings of the condensation of level-one room temperature and level-one and enters toluene tank, methanol rectification kettle remnants waste water relies on existing dirt
Water treatment station processing.
(5) wet product being prepared manually is added to vacuum double-cone dryer, obtains ADH solid after drying.It is dry
Exhaust gas collects methanol after -10 DEG C of subzero treatments of level-one, and fixed gas enters active carbon adsorber, adipic acid two by vacuum system
The molar yield of hydrazides reaction is 98%, molar yield 92%.
Embodiment 2
A kind of synthetic method of adipic dihydrazide, specific steps are as follows:
(1) it injects into 500mL beaker in the mixed solution of 100% methanol (0.75mol) and 75% ethyl alcohol (0.5mol), then will
Adipic acid (4.25mol) is added in the mixed solution of methanol and ethyl alcohol, and potassium acid sulfate (0.1mol) and potassium sulfate is then added
The mixture of (0.4mol) carries out catalysis reaction, heating reaction system to reflux state, 40 DEG C of esters under reflux state and stirring
Change reaction 1.5h.
(2) after reaction time of esterification, cooling system is to 20 DEG C, and under stirring, mass fraction is first added dropwise into system is
80% hydrazine hydrate (4.25mol) is stirred for after dripping and carries out hydrazineization reaction 1h, hydrazineization reaction knot under the conditions of 20 DEG C of temperature
Shu Hou filters out catalyst, and product after reaction is just made, and catalyst can reuse after processing.
(3) then the material that reaction obtains filtered in closed centrifuge, washed once with methanol, after centrifugation
The exhaust gas in centrifuge is subjected to stripping with nitrogen before putting material, for stripping exhaust gas through level-one deep cooling recovered material, fixed gas is logical
It crosses pipeline and drains into active carbon adsorber.
(4) centrifuge mother liquor main component is methanol and ethyl alcohol, contains the complete hydrazine hydrate of a small amount of unreacted, adipic acid diformazan
Ester/ethyl ester enters methanol/ethanol rectification working process and recycles methanol/ethanol after collection.Hydrazine hydrate and methanol/ethanol azeotropic, steam together
It is collected out through -10 DEG C of deep coolings of the condensation of level-one room temperature and level-one and enters toluene tank, methanol rectification kettle remnants waste water relies on existing dirt
Water treatment station processing.
(5) wet product being prepared manually is added to vacuum double-cone dryer, obtains ADH solid after drying.It is dry
Exhaust gas collects methanol after -10 DEG C of subzero treatments of level-one, and fixed gas enters active carbon adsorber, adipic acid two by vacuum system
The molar yield of hydrazides reaction is 99%, molar yield 95%.
Embodiment 3
A kind of synthetic method of adipic dihydrazide, specific steps are as follows:
(1) it injects into 500mL beaker in the mixed solution of 100% methanol (0.5mol) and 80% ethyl alcohol (0.25mol), then will
Adipic acid (3.5mol) is added in the mixed solution of methanol and ethyl alcohol, and potassium acid sulfate (0.1mol) and potassium sulfate is then added
The mixture of (0.4mol) carries out catalysis reaction, heating reaction system to reflux state, 50 DEG C of esters under reflux state and stirring
Change reaction 2h.
(2) after reaction time of esterification, cooling system is to 30 DEG C, and under stirring, mass fraction is first added dropwise into system is
80% hydrazine hydrate (3.375mol) is stirred for after dripping and carries out hydrazineization reaction 2hh, hydrazineization reaction under the conditions of 30 DEG C of temperature
After, catalyst is filtered out, product after reaction is just made, catalyst can reuse after processing.
(3) then the material that reaction obtains filtered in closed centrifuge, washed once with methanol, after centrifugation
The exhaust gas in centrifuge is subjected to stripping with nitrogen before putting material, for stripping exhaust gas through level-one deep cooling recovered material, fixed gas is logical
It crosses pipeline and drains into active carbon adsorber.
(4) centrifuge mother liquor main component is methanol and ethyl alcohol, contains the complete hydrazine hydrate of a small amount of unreacted, adipic acid diformazan
Ester/ethyl ester enters methanol/ethanol rectification working process and recycles methanol/ethanol after collection.Hydrazine hydrate and methanol/ethanol azeotropic, steam together
It is collected out through -10 DEG C of deep coolings of the condensation of level-one room temperature and level-one and enters toluene tank, methanol rectification kettle remnants waste water relies on existing dirt
Water treatment station processing.
(5) wet product being prepared manually is added to vacuum double-cone dryer, obtains ADH solid after drying.It is dry
Exhaust gas collects methanol after -10 DEG C of subzero treatments of level-one, and fixed gas enters active carbon adsorber, adipic acid two by vacuum system
The molar yield of hydrazides reaction is 99%, molar yield 95%.
It should be understood by those skilled in the art that the present invention is not limited to the above embodiments, above-described embodiment and explanation
It is merely illustrated the principles of the invention described in book, without departing from the spirit and scope of the present invention, the present invention also has
Various changes and modifications, these changes and improvements all fall within the protetion scope of the claimed invention.
Claims (7)
1. a kind of synthetic method of adipic dihydrazide, using two hydrazides of two-step method synthesizing adipic acid, first using adipic acid and
Methanol esterification reaction has synthesized dimethyl adipate, then by dimethyl adipate and hydrazine hydrate hydrazides, has obtained adipic acid
Two hydrazides, it is characterised in that: the esterification exists reactant using the mixture of adipic acid and methanol and ethyl alcohol as reactant
The mixture of Dimethyl Adipate Catalyzed and diethylene adipate under the catalysis of catalyst；What the hydrazidesization reaction synthesis obtained
The mixture of dimethyl adipate and diethylene adipate is reacted with the hydrazine hydrate that mass fraction is 80%, obtains diacid two
Hydrazides product.
2. a kind of synthetic method of adipic dihydrazide according to claim 1, it is characterised in that: the adipic acid and first
The ratio between amount of substance of mixture of pure and mild ethyl alcohol is 3.4 ~ 4.5:1, methanol and ethyl alcohol in the mixture of the methanol and ethyl alcohol
The ratio between the amount of substance be 0.5 ~ 1.5:1, the methanol quality score is 100%, and the mass fraction of the ethyl alcohol is 75 ~ 80%,
The reaction time of the esterification is 0.25 ~ 2h, and reaction temperature is 40 ~ 50 DEG C.
3. a kind of synthetic method of adipic dihydrazide according to claim 1, it is characterised in that: the adipic acid diformazan
The ratio between amount of substance of mixture and hydrazine hydrate of ester and diethylene adipate is 1:1.5 ~ 2.5, and the hydrazidesization reacts anti-
It is 1 ~ 2h between seasonable, reaction temperature is 20 ~ 40 DEG C.
4. a kind of synthetic method of adipic dihydrazide according to claim 1, it is characterised in that: the catalyst choice
One of p-methyl benzenesulfonic acid, potassium acid sulfate, the concentrated sulfuric acid and lewis acid zinc chloride are several.
5. according to claim 1 with a kind of synthetic method of adipic dihydrazide described in 4, it is characterised in that: the catalyst
Select the mixture of potassium acid sulfate and the concentrated sulfuric acid.
6. a kind of synthetic method of adipic dihydrazide according to claim 5, it is characterised in that: the potassium acid sulfate and
The ratio between amount of substance of the concentrated sulfuric acid is 1:4.
7. a kind of synthetic method of adipic dihydrazide according to claim 1, it is characterised in that: the catalyst and oneself
The ratio between amount of substance of diacid is 0.3 ~ 0.5:1.
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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 |
| CN114957036A (en) * | 2022-06-13 | 2022-08-30 | 亚士创能新材料(滁州)有限公司 | Synthesis method of dibasic acid dihydrazide |
-
2019
- 2019-01-22 CN CN201910058770.4A patent/CN109748815A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 杨俊阁等: "己二酸二酰肼的合成工艺研究", 《化学工业与工程》 * |
Cited By (3)
| 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 |
| CN114957036A (en) * | 2022-06-13 | 2022-08-30 | 亚士创能新材料(滁州)有限公司 | Synthesis method of dibasic acid dihydrazide |
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