CN114957036A - Synthesis method of dibasic acid dihydrazide - Google Patents
Synthesis method of dibasic acid dihydrazide Download PDFInfo
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- CN114957036A CN114957036A CN202210678288.2A CN202210678288A CN114957036A CN 114957036 A CN114957036 A CN 114957036A CN 202210678288 A CN202210678288 A CN 202210678288A CN 114957036 A CN114957036 A CN 114957036A
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Abstract
The invention provides a method for synthesizing dibasic acid dihydrazide, which comprises the following steps: (1) reacting a dibasic ester compound with hydrazine hydrate to obtain dibasic acid monohydrazide; (2) and (2) reacting the dibasic acid monohydrazide obtained in the step (1) with hydrazine hydrate to obtain the dibasic acid dihydrazide. According to the invention, the dibasic ester compound and hydrazine hydrate are synthesized into the dibasic acid dihydrazide in two steps, so that the yield of the dibasic acid dihydrazide can be improved, the consumption of the hydrazine hydrate can be reduced, the cost is reduced, the environmental pollution is reduced, and meanwhile, the product quality is stable and the production is controllable.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a synthetic method of dibasic acid dihydrazide.
Background
Dibasic acid dihydrazides are important and representative compounds among hydrazide derivatives of hydrazine, and are widely used as raw materials for various polymers. In addition, the dibasic acid dihydrazide can be used as an epoxy resin curing agent and is widely applied to the fields of powder coating, adhesives, encapsulation and plastic package of electronic components and the like. Meanwhile, the dibasic acid dihydrazide is used as a crosslinking monomer, has wide application in emulsion synthesis, and can endow the emulsion with good performance. Along with the development of powder coatings, the application of dibasic acid dihydrazide is more and more extensive.
At present, the synthesis method of the dibasic acid dihydrazide is few reports, mainly adopts the traditional one-pot method type process, generally adopts the method that dibasic acid dimethyl ester or dibasic acid diethyl ester is mixed with excessive hydrazine hydrate, the heat preservation reaction is carried out for 3 to 5 hours at a certain temperature, and then the dibasic acid dihydrazide is obtained after cooling, filtering and drying. For example, a method for preparing sebacic dihydrazide is disclosed in the literature (preparation, use and analysis of gesper. sebacic dihydrazide, journal of chemical industry, 1992, 4, 24-26), and comprises: hydrazine hydrate and dimethyl sebacate are prepared by a one-step method according to the molar ratio of (4-8) to 1, and the yield of the dihydrazide sebacate is 85-91%. The preparation method requires a large amount of hydrazine hydrate and has a low yield.
A common drawback in the prior art is that the reaction rate tends to decrease as methanol or ethanol is produced during the reaction. In order to increase the reaction rate, the hydrazine hydrate is required to be excessive, so that a large amount of hydrazine hydrate is consumed, and the large amount of residual hydrazine hydrate causes environmental pollution due to the high toxicity of the hydrazine hydrate. Meanwhile, the production process of the traditional one-pot method is adopted, so that the efficiency is low, the product quality is unstable, and the side reactions are more.
Therefore, the development of a synthetic method for producing controllable dibasic acid dihydrazide, which has high production efficiency, low cost, no use of a large amount of hydrazine hydrate, environmental protection, stable product and needs to be solved urgently in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for synthesizing the binary acid dihydrazide, wherein the method for synthesizing the binary acid dihydrazide adopts a two-step method, so that the yield and the purity of the binary acid dihydrazide are improved, the use of a large amount of hydrazine hydrate is avoided, the pollution is reduced, and the cost is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for synthesizing dibasic acid dihydrazide, comprising the following steps:
(1) reacting a dibasic ester compound with hydrazine hydrate to obtain dibasic acid monohydrazide;
(2) and (2) reacting the dibasic acid monohydrazide obtained in the step (1) with hydrazine hydrate to obtain the dibasic acid dihydrazide.
According to the invention, a two-step method is adopted, firstly, a dibasic ester compound reacts with a certain amount of hydrazine hydrate to obtain dibasic acid mono-hydrazide, and then the dibasic acid mono-hydrazide continuously reacts with the hydrazine hydrate to obtain the dibasic acid dihydrazide, so that the yield of the dibasic acid dihydrazide can be improved, the consumption of the hydrazine hydrate can be reduced, the cost is reduced, and the environmental pollution is reduced.
In the invention, the dibasic acid monohydrazide refers to a compound which is obtained by reaction and contains a hydrazide group at one end.
Preferably, the dibasic ester compound comprises a dibasic ester compound of C3-C10, such as a dibasic ester compound of C3, C4, C5, C6, C7, C8, C9 or C10, exemplary include, but are not limited to, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, dipropyl glutarate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dimethyl pimelate, diethyl pimelate, dipropyl pimelate, dibutyl pimelate, dipentyl pimelate, dimethyl suberate, diethyl suberate, dipropyl suberate, dibutyl suberate, dihexyl suberate, dimethyl azelate, diethyl azelate, dipropyl azelate, dibutyl azelate, dimethyl sebacate, diethyl sebacate, dipropyl sebacate, or dibutyl sebacate.
In the present invention, the dibasic ester compound of C3-C10 means that the number of carbon atoms of dibasic acid used for preparing the dibasic ester compound is C3-C10, and the number of carbon atoms of the alcohol compound used for preparing the dibasic ester compound of C3-C10 is not limited.
Preferably, the dibasic ester compound comprises any one of dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, dimethyl adipate, diethyl adipate, dimethyl pimelate, diethyl pimelate, dimethyl suberate, diethyl suberate, dimethyl azelate, diethyl azelate, dimethyl sebacate or diethyl sebacate.
Preferably, the molar ratio of the diester compound to hydrazine hydrate in the step (1) is 1 (0.9-1.1), and may be, for example, 1:0.92, 1:0.94, 1:0.96, 1:0.98, 1:1, 1:1.02, 1:1.04, 1:1.06, 1:1.08, and the like.
In the invention, because the reaction rate is high, the molar ratio of the dibasic ester compound to the hydrazine hydrate is controlled to be 1 (0.9-1.1), so that the dibasic acid monohydrazide can be efficiently formed, and the generation of byproducts is inhibited; meanwhile, the second step of reaction is padded, so that the reaction selectivity is improved, and the reaction is carried out in the direction of generating the dibasic acid dihydrazide. The molar ratio of the dibasic ester compound to the hydrazine hydrate is more than 1:0.9, and the reaction is incomplete; less than 1:1.1, side reactions increase and reaction efficiency is low.
Preferably, the reaction of step (1) is carried out in the presence of a catalyst.
Preferably, the catalyst comprises zinc chloride.
In the present invention, the zinc chloride is in the form of a rod and/or a granule.
According to the invention, when the molar ratio of the dibasic ester compound to the hydrazine hydrate is 1 (0.9-1.1), and the catalyst is zinc chloride, the reaction efficiency is high; the use of other catalysts increases the probability of side reactions.
Preferably, the reaction of step (1) is carried out in a solvent.
Preferably, the solvent comprises methanol.
The mass ratio of the dibasic ester compound to methanol is preferably 1 (1.5-2.5), and may be, for example, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, and the like.
Preferably, the diester compound in step (1) further comprises a step of preheating before the reaction.
Preferably, the preheating temperature is 60 to 65 ℃, for example, 61 ℃, 62 ℃, 63 ℃, 64 ℃ and the like.
Preferably, the hydrazine hydrate in the step (1) further comprises a preheating step before the reaction.
Preferably, the temperature of the hydrazine hydrate preheating is 70-75 ℃, for example, 71 ℃, 72 ℃, 73 ℃, 74 ℃ and the like.
Preferably, the reaction temperature in the step (1) is 70 to 75 ℃, for example, 71 ℃, 72 ℃, 73 ℃, 74 ℃ and the like.
Preferably, the molar ratio of the dibasic acid monohydrazide to the hydrazine hydrate in the step (2) is 1 (1.6-1.8), and may be, for example, 1:1.62, 1:1.64, 1:1.66, 1:1.68, 1:1.7, 1:1.72, 1:1.74, 1:1.76, 1:1.78, and the like.
In the second step of reaction, the reaction rate is slowed, so that the consumption of hydrazine hydrate is increased, and when the molar ratio of the dibasic acid monohydrazide to the hydrazine hydrate is 1 (1.6-1.8), the reaction can be ensured to be complete, the occurrence of side reactions can be reduced, and the selectivity of the hydrazine hydrate and the yield of the dibasic acid dihydrazide are improved; the molar ratio of the dibasic acid monohydrazide to the hydrazine hydrate is more than 1:1.6, and the reaction is incomplete; less than 1:1.8, increases hydrazine hydrate by-products and has low reaction efficiency.
Preferably, the reaction of step (2) is carried out in a catalyst.
Preferably, the catalyst in step (2) comprises ferric chloride.
In the present invention, the form of the ferric trichloride is rod-like and/or granular.
In the invention, when the molar ratio of the dibasic acid monohydrazide to the hydrazine hydrate is 1 (1.6-1.8), and the catalyst is ferric trichloride, the reaction efficiency is high; the use of other catalysts increases the probability of side reactions.
Preferably, the hydrazine hydrate in the step (2) further comprises a step of preheating before the reaction.
Preferably, the temperature for preheating the hydrazine hydrate in the step (2) is 70-75 ℃, for example, 71 ℃, 72 ℃, 73 ℃, 74 ℃ and the like.
Preferably, the reaction temperature in the step (2) is 75 to 80 ℃, and for example, 76 ℃, 77 ℃, 78 ℃, 79 ℃ and the like can be adopted.
Preferably, the reaction in step (2) further comprises a centrifugation and/or drying step after completion.
Preferably, the drying temperature is 40 to 50 ℃, for example, 42 ℃, 44 ℃, 46 ℃, 48 ℃ and the like.
Preferably, the drying pressure is-0.08 to-0.1 MPa, and may be-0.082 MPa, -0.085MPa, -0.09MPa, -0.095MPa, or the like.
Preferably, the method for synthesizing the dibasic acid dihydrazide comprises a continuous synthesis method.
According to the invention, the continuous synthesis method is characterized in that the whole process is carried out continuously, reaction raw materials are continuously fed into a first fixed bed reaction tower through a delivery pump for reaction, the obtained dibasic acid monohydrazide is continuously fed into a second fixed bed reaction tower for reaction, and the dibasic acid dihydrazide is finally obtained.
Preferably, the continuous synthesis apparatus comprises a fixed bed continuous reaction apparatus.
Preferably, the fixed bed continuous reaction apparatus includes a first fixed bed reaction tower and a second fixed bed reaction tower connected in series.
Preferably, the first fixed bed reaction column and the second fixed bed reaction column are each independently packed with a catalyst.
In the invention, the dosage of the catalyst in the first fixed bed reaction tower is determined by the mass space velocity of the dibasic ester compound solution; the mass space velocity of the dibasic ester compound solution relative to the catalyst in the first fixed bed reaction tower is 10-12 kg/h.kg, for example, 10.2kg/h.kg, 10.4kg/h.kg, 10.6kg/h.kg, 10.8kg/h.kg, 11kg/h.kg, 11.2kg/h.kg, 11.4kg/h.kg, 11.6kg/h.kg, 11.8kg/h.kg and the like.
In the invention, the dosage of the catalyst in the second fixed bed reaction tower is determined by the mass space velocity of the dibasic acid monohydrazide; the mass space velocity of the dibasic acid monohydrazide relative to the catalyst in the second fixed bed reaction tower is 8-10 kg/h.kg, for example, 8.2kg/h.kg, 8.4kg/h.kg, 8.6kg/h.kg, 8.8kg/h.kg, 9kg/h.kg, 9.2kg/h.kg, 9.4kg/h.kg, 9.6kg/h.kg, 9.8kg/h.kg and the like.
Preferably, a first reaction buffer tank is arranged between the first fixed bed reaction tower and the second fixed bed reaction tower.
Preferably, the feed inlet of the first reaction buffer tank is connected with the first fixed bed reaction tower.
Preferably, the discharge port of the first reaction buffer tank is connected with the second fixed bed reaction tower through a first delivery pump.
Preferably, a first reflux condenser is arranged at the top of the first fixed bed reaction tower.
Preferably, a second reflux condenser is arranged at the top of the second fixed bed reaction tower.
In the invention, the vaporized solvent returns to the fixed bed reaction tower after being condensed and refluxed by the reflux cooler in the reaction process.
Preferably, the fixed bed continuous reaction apparatus further comprises a feeding apparatus.
Preferably, the feeding device comprises a dibasic ester compound feeding device and a hydrazine hydrate feeding device.
Preferably, the dibasic ester compound feeding device comprises a dissolving kettle, a second delivery pump and a first preheater which are connected in sequence.
Preferably, the discharge port of the first preheater is connected with the first fixed bed reaction tower.
Preferably, a stirring device is arranged in the dissolving kettle.
Preferably, the hydrazine hydrate feeding device comprises a first hydrazine hydrate feeding device and a second hydrazine hydrate feeding device.
Preferably, the first hydrazine hydrate feeding device comprises a first hydrazine hydrate preheater and a first hydrazine hydrate delivery pump which are connected in sequence.
Preferably, the discharge port of the first hydrazine hydrate preheater is connected with the first fixed bed reaction tower.
Preferably, the second hydrazine hydrate feeding device comprises a second hydrazine hydrate preheater and a second hydrazine hydrate delivery pump.
Preferably, the discharge port of the second hydrazine hydrate preheater is connected with the second fixed bed reaction tower.
Preferably, the fixed bed continuous reaction apparatus further comprises a centrifugal tank.
Preferably, a second reaction buffer tank and a third delivery pump which are connected in sequence are arranged between the centrifugal kettle and the second fixed bed reaction tower.
Preferably, the feed inlet of the second reaction buffer tank is connected with the second fixed bed reaction tower.
Preferably, a stirring device is arranged in the centrifugal kettle.
According to the invention, the obtained dibasic acid dihydrazide enters a centrifugal kettle, is stirred and cooled, the temperature in the centrifugal kettle is controlled to be 5-10 ℃, and simultaneously, the dibasic acid dihydrazide is continuously fed into a centrifugal machine for solid-liquid separation.
As a preferred technical scheme of the invention, the synthesis method comprises the following steps:
(1) conveying the dibasic ester compound and hydrazine hydrate to a first fixed bed reaction tower through a feeding device, and reacting at 70-75 ℃ to obtain dibasic acid monohydrazide;
(2) and (2) conveying the dibasic acid monohydrazide obtained in the step (1) to a second fixed bed reaction tower to react with hydrazine hydrate at the temperature of 75-80 ℃ to obtain the dibasic acid dihydrazide.
In the present invention, the synthesis process is carried out continuously throughout.
In the invention, when the reaction temperature of the step (1) and the step (2) is too low, the reaction rate is slow, and the reaction is incomplete; when the temperature is too high, side reactions are more.
In the invention, the time required from dissolution in the dissolution kettle to completion of the whole process by centrifugation in the centrifugal kettle is 2-3 h, for example, 2h, 2.5h, 3h and the like.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for synthesizing the binary acid dihydrazide, provided by the invention, through adopting a two-step method, the purity and yield of the binary acid dihydrazide can be improved, excessive hydrazine hydrate introduction can be avoided, the pollution of the hydrazine hydrate is reduced, the cost is low, the production efficiency is high, the stability of a product can be improved, and the production is controllable; the yield of the dibasic acid dihydrazide is more than or equal to 94.2 percent, and the molar consumption of the hydrazine hydrate is less than 3 times of that of the dibasic ester compound raw material.
Drawings
FIG. 1 is a schematic diagram of a fixed bed continuous reaction apparatus used in the method for synthesizing dibasic acid dihydrazide provided in embodiments 1 to 14 of the present invention;
the method comprises the following steps of 1-a first fixed bed reaction tower, 2-a second fixed bed reaction tower, 3-a first reaction buffer tank, 4-a first delivery pump, 5-a dissolution kettle, 6-a second delivery pump, 7-a first preheater, 8-a stirring device, 9-a first hydrazine hydrate preheater, 10-a first hydrazine hydrate delivery pump, 11-a second hydrazine hydrate preheater, 12-a second hydrazine hydrate delivery pump, 13-a second reaction buffer tank, 14-a third delivery pump, 15-a centrifugal kettle, 16-a first reflux condenser and 17-a second reflux condenser.
FIG. 2 is an infrared spectrum of a dibasic acid dihydrazide provided in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the invention, hydrazine hydrate used in all examples and comparative examples is 80% by mass of hydrazine hydrate, and the molar ratio of the dibasic ester compound to the hydrazine hydrate and the molar ratio of the dibasic acid monohydrazide to the hydrazine hydrate are both the molar ratio to the effective hydrazine hydrate.
Example 1
The present embodiment provides a method for synthesizing dibasic acid dihydrazide, wherein a schematic diagram of a fixed bed continuous reaction apparatus adopted in the method is shown in fig. 1, and the method specifically comprises the following steps:
(1) feeding methanol and dimethyl sebacate into a dissolving kettle through a dimethyl sebacate feeding hole and a methanol feeding pump, and stirring to obtain a methanol solution of the dimethyl sebacate; preheating the methanol solution of dimethyl sebacate by a first preheater by using a second delivery pump at 65 ℃, then delivering the preheated methanol solution into a first fixed bed reaction tower containing zinc chloride, simultaneously preheating hydrazine hydrate by a first hydrazine hydrate preheater by using a first hydrazine hydrate delivery pump at 75 ℃, and then delivering the preheated hydrazine hydrate into the first fixed bed reaction tower, wherein the dimethyl sebacate and the hydrazine hydrate react in the first fixed bed reaction tower under the catalysis of the zinc chloride at 75 ℃ to obtain dibasic acid monohydrazide; in the reaction process, vaporized methanol is condensed and refluxed by a first reflux cooler above a first fixed bed reaction tower and then returns to the first fixed bed reaction tower, the mass ratio of dimethyl sebacate to methanol is 1:2, the molar ratio of dimethyl sebacate to hydrazine hydrate is 1:0.93, and the mass space velocity of the methanol solution of dimethyl sebacate relative to zinc chloride is 11 kg/h.kg.
(2) Allowing the dibasic acid monohydrazide obtained in the step (1) to flow out of a first fixed bed reaction tower and enter a first reaction buffer tank, conveying the dibasic acid monohydrazide into a second fixed bed reaction tower containing a ferric trichloride catalyst by using a first conveying pump, preheating hydrazine hydrate by using a second hydrazine hydrate preheater at 75 ℃ by using a second hydrazine hydrate conveying pump, and conveying the hydrazine hydrate into a second fixed bed reaction tower, wherein the dibasic acid monohydrazide and the hydrazine hydrate react in the second fixed bed reaction tower at 80 ℃ under the catalysis of ferric trichloride to obtain a dibasic acid dihydrazide solution; in the reaction process, the vaporized methanol is condensed and refluxed by a second reflux cooler and returns to a second fixed bed reaction tower, the obtained binary acid dihydrazide solution flows out of the second fixed bed reaction tower, enters a centrifugal kettle through a second reaction buffer tank by using a third conveying pump, is stirred and cooled, the temperature in the kettle is controlled to be 5-10 ℃, simultaneously, the binary acid dihydrazide solution is continuously transferred to a centrifugal machine for solid-liquid separation, and is dried in vacuum at the temperature of 45 ℃ and the pressure of-0.09 MPa to obtain the binary acid dihydrazide solid; the molar ratio of the dibasic acid monohydrazide to the hydrazine hydrate is 1:1.8, and the mass space velocity of the dibasic acid monohydrazide reaction liquid relative to ferric trichloride is 9 kg/h.kg.
The structure of the dibasic acid dihydrazide provided in example 1 was characterized by using Shimadzu IRPrestige-21 Fourier infrared spectrometer, and the results are shown in FIG. 2.
Example 2
This example provides a method for synthesizing dibasic acid dihydrazide, which is different from example 1 only in that the dimethyl sebacate in step (1) is replaced by diethyl sebacate, the molar ratio of the diethyl sebacate to hydrazine hydrate is 1:1, and the mass space velocity of the methanol solution of the diethyl sebacate relative to the zinc chloride is 10 kg/h.kg; the reaction temperature of diethyl sebacate and hydrazine hydrate in a fixed bed reaction tower 1 is 70 ℃; in the step (2), the molar ratio of the dibasic acid monohydrazide to the hydrazine hydrate is 1:1.6, and the mass space velocity of the dibasic acid monohydrazide relative to the ferric trichloride is 10 kg/h.kg; the reaction temperature of the dibasic acid monohydrazide and the hydrazine hydrate in the fixed bed reaction tower 2 is 75 ℃, and other raw materials, the using amount, the synthetic method and the process flow are the same as those of the example 1.
Example 3
This example provides a method for synthesizing dibasic acid dihydrazide, which differs from example 1 only in that in step (1), the dimethyl sebacate is replaced by dimethyl adipate, the molar ratio of the dimethyl adipate to hydrazine hydrate is 1:1.1, and the mass space velocity of the methanol solution of the dimethyl adipate relative to the zinc chloride is 12 kg/h.kg; in the step (2), the molar ratio of the dibasic acid monohydrazide to the hydrazine hydrate is 1:1.7, the mass space velocity of the dibasic acid monohydrazide relative to the ferric trichloride is 8kg/h.kg, and other raw materials, the using amount, the synthetic method and the process flow are the same as those in the example 1.
Example 4
This example provides a method for synthesizing a dibasic acid dihydrazide, which is different from example 1 only in that dimethyl sebacate is replaced by dimethyl suberate in step (1), and other raw materials, use amounts, synthesis methods and process flows are the same as those in example 1.
Example 5
This example provides a method for synthesizing dibasic acid dihydrazide, which is different from example 1 only in that dimethyl sebacate is replaced by diethyl succinate in step (1), and other raw materials, usage amounts, synthetic methods and process flows are the same as those in example 1.
Example 6
This example provides a method for synthesizing dibasic acid dihydrazide, which is different from example 1 only in that the molar ratio of dimethyl sebacate to hydrazine hydrate in step (1) is 1:2, and other raw materials, amounts, synthetic methods and process flows are the same as those in example 1.
Example 7
This example provides a method for synthesizing dibasic acid dihydrazide, which is different from example 1 only in that the molar ratio of dimethyl sebacate to hydrazine hydrate in step (1) is 1:3, and other raw materials, amounts, synthetic methods and process flows are the same as those in example 1.
Example 8
This example provides a method for synthesizing dibasic acid dihydrazide, which is different from example 1 only in that the molar ratio of the dibasic acid monohydrazide to hydrazine hydrate in step (2) is 1:2.5, and other raw materials, amounts, synthetic methods and process flows are the same as those of example 1.
Example 9
This example provides a method for synthesizing a dibasic acid dihydrazide, which is different from example 1 only in that the molar ratio of the dibasic acid monohydrazide to hydrazine hydrate in step (2) is 1:1.2, and other raw materials, amounts, synthetic methods and process flows are the same as those of example 1.
Example 10
This example provides a method for synthesizing dibasic acid dihydrazide, which is different from example 1 only in that the ferric chloride catalyst is replaced by zinc chloride in an equimolar amount in step (2), and other raw materials, amounts, synthetic methods and process flows are the same as those of example 1.
Example 11
This example provides a method for synthesizing a dibasic acid dihydrazide, which is different from example 1 only in that the zinc chloride catalyst is replaced by an equimolar amount of ferric chloride in step (1), and other raw materials, amounts, synthetic methods and process flows are the same as those of example 1.
Example 12
This example provides a method for synthesizing a dibasic acid dihydrazide, which is different from example 1 only in that zinc chloride catalyst is replaced by an equimolar amount of ferric chloride in step (1), a ferric chloride catalyst is replaced by an equimolar amount of zinc chloride in step (2), and other raw materials, amounts, synthesis methods and process flows are the same as those in example 1.
Example 13
This example provides a method for synthesizing dibasic acid dihydrazide, which is different from example 1 only in that the mass space velocity of the methanol solution of dimethyl sebacate relative to zinc chloride in step (1) is 8kg/h.kg, and other raw materials, usage amounts, synthetic method and process flow are the same as those in example 1.
Example 14
This example provides a method for synthesizing dibasic acid dihydrazide, which is different from example 1 only in that the mass space velocity of dibasic acid monohydrazide relative to ferric trichloride in step (2) is 6kg/h.kg, and other raw materials, usage amounts, synthetic method and process flow are the same as those in example 1.
Comparative example 1
This comparative example provides a method for synthesizing dibasic acid dihydrazide, which is different from example 1 only in that the continuous synthesis is carried out without using a fixed bed continuous reaction device, and the specific steps comprise:
(1) preheating dimethyl sebacate and methanol in a reaction bottle at 65 ℃, adding hydrazine hydrate and zinc chloride, condensing and refluxing, and reacting for 2.5 hours at 75 ℃ to obtain dibasic acid monohydrazide;
(2) adding hydrazine hydrate and ferric trichloride into the dibasic acid monohydrazide reaction liquid obtained in the step (1), reacting for 3.5h at the temperature of 80 ℃, centrifuging, and drying in vacuum to obtain the sebacic dihydrazide.
The raw material ratio and the catalyst dosage in the step (1) and the step (2) are the same as those in the example 1.
Comparative example 2
The comparative example provides a method for synthesizing dibasic acid dihydrazide, which comprises the following specific steps:
adding hydrazine hydrate and zinc chloride into a reaction bottle, heating to 75 ℃ under a stirring state, then dropwise adding a methanol solution of dimethyl sebacate for 1.5 hours, continuing to perform heat preservation reaction for 3 hours after dropwise adding is finished, then cooling to 5 ℃, filtering and drying to obtain the dibasic acid dihydrazide; the mass ratio of the dimethyl sebacate to the methanol is 1:2, the molar ratio of the dimethyl sebacate to the hydrazine hydrate is 1:3, and the molar ratio of the dimethyl sebacate to the zinc chloride is 192: 1.
Comparative example 3
This comparative example provides a method for synthesizing dibasic acid dihydrazide, which is different from comparative example 2 only in that the amount of hydrazine hydrate is increased so that the molar ratio of dimethyl sebacate to hydrazine hydrate is 1:4, and other raw materials, amounts and synthesis methods are the same as those of comparative example 2.
Comparative example 4
The comparative example provides a method for synthesizing dibasic acid dihydrazide, which is different from the comparative example 2 only in that the zinc chloride catalyst is replaced by potassium bisulfate with equal mass, and other raw materials, using amount and synthesizing method are the same as the comparative example 2.
Comparative example 5
This comparative example provides a method for synthesizing a dibasic acid dihydrazide, which is different from comparative example 3 only in that the zinc chloride catalyst is replaced by potassium bisulfate of equal mass, and other raw materials, amounts and synthesis methods are the same as those of comparative example 2.
Comparative example 6
This comparative example provides a method of synthesis of dibasic acid dihydrazide which differs from example 1 only in that step (2) is not performed in the method of synthesis, and the molar ratio of dimethyl sebacate to hydrazine hydrate in step (1) is 1: 2.73, the fixed bed reaction tower 1 is filled with zinc chloride and ferric trichloride, and other raw materials, the using amount and the synthetic method are the same as those of the embodiment 1.
Performance testing
Testing the purity of the dibasic acid dihydrazide provided in the examples 1-14 and the comparative examples 1-6 by using an Agilent 1200-LC liquid chromatograph, and calculating the yield of the dibasic acid dihydrazide;
yield is M 2 /M 1 *100％；
Wherein M is 2 Mass of the dibasic acid dihydrazide actually produced in a unit time, M 1 The mass of the dibasic acid dihydrazide theoretically produced by the feed mass of the dibasic ester compound in unit time.
The specific test results are shown in table 1:
TABLE 1
As can be seen from the above table, the method for synthesizing the dibasic acid dihydrazide provided by the invention adopts a two-step method, controls the ratio of raw materials and the selection of the catalyst in each step, and adopts a fixed bed continuous reaction device for continuous synthesis, so that the purity and yield of the dibasic acid dihydrazide can be improved, the excessive introduction of hydrazine hydrate can be avoided, the pollution of the hydrazine hydrate is reduced, the cost is low, the production efficiency is high, the stability of the product can be improved by adopting the fixed bed continuous reaction device, and the production can be controlled. As can be seen from examples 1 to 5, the dibasic acid dihydrazide obtained by the synthesis method provided by the present invention has a purity of 99.63 to 99.69% and a yield of 97.4 to 97.8%.
As can be seen from comparison between example 1 and examples 6 to 9, the raw materials in the step (1) and the step (2) are not in the specific mixture ratio, and the purity and yield of the dibasic acid dihydrazide are reduced; from examples 1 and 10 to 12, it is understood that the purity and yield of the dibasic acid dihydrazide are lowered when the specific catalyst is not selected in the step (1) and the step (2); as is clear from comparison of example 1 with examples 13 and 14, when the amount of the catalyst used in the step (1) or the step (2) is too large, the purity and yield of the dibasic acid dihydrazide are lowered.
As can be seen from comparison of example 1 with comparative example 1, when the continuous synthesis was not carried out using the fixed bed reaction apparatus, the purity of the dibasic acid dihydrazide was lowered and the yield was greatly lowered; as can be seen from the comparison between examples 1 to 5 and comparative examples 2 to 6, the use of one-step method for synthesizing the dibasic acid dihydrazide not only increases the amount of hydrazine hydrate, but also decreases the yield of the dibasic acid dihydrazide.
In conclusion, the method adopts a two-step method through a fixed bed continuous reaction device, improves the conversion rate of hydrazine hydrate and the purity and yield of the dibasic acid dihydrazide by controlling the proportion of raw materials in each step and the selection of the type and the dosage of the catalyst, avoids the need of a large amount of hydrazine hydrate in the traditional one-pot method for synthesizing the dibasic acid dihydrazide, reduces the cost and reduces the pollution; meanwhile, the continuous synthesis method is adopted, so that the stability of the product can be improved, and the production is controllable.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A synthetic method of dibasic acid dihydrazide is characterized by comprising the following steps:
(1) reacting a dibasic ester compound with hydrazine hydrate to obtain dibasic acid monohydrazide;
(2) and (2) reacting the dibasic acid monohydrazide obtained in the step (1) with hydrazine hydrate to obtain the dibasic acid dihydrazide.
2. The method for synthesizing dibasic acid dihydrazide according to claim 1, wherein the dibasic ester compound comprises dibasic ester compounds of C3-C10;
preferably, the dibasic ester compound comprises any one of dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, dimethyl adipate, diethyl adipate, dimethyl pimelate, diethyl pimelate, dimethyl suberate, diethyl suberate, dimethyl azelate, diethyl azelate, dimethyl sebacate or diethyl sebacate;
preferably, the molar ratio of the diester compound to the hydrazine hydrate in the step (1) is 1 (0.9-1.1);
preferably, the reaction of step (1) is carried out in the presence of a catalyst;
preferably, the catalyst comprises zinc chloride.
3. The method for synthesizing dibasic acid dihydrazide according to claim 1 or 2, wherein the reaction of step (1) is performed in a solvent;
preferably, the solvent comprises methanol;
preferably, the mass ratio of the dibasic ester compound to the methanol is 1 (1.5-2.5).
4. The method for synthesizing dibasic acid dihydrazide according to any one of claims 1 to 3, wherein the step (1) of preheating the dibasic ester compound before the reaction;
preferably, the preheating temperature is 60-65 ℃;
preferably, the hydrazine hydrate in the step (1) further comprises the step of preheating before the reaction;
preferably, the preheating temperature of the hydrazine hydrate is 70-75 ℃;
preferably, the temperature of the reaction in the step (1) is 70-75 ℃.
5. The method for synthesizing dibasic acid dihydrazide according to any one of claims 1 to 4, wherein the molar ratio of the dibasic acid monohydrazide to the hydrazine hydrate in the step (2) is 1 (1.6 to 1.8);
preferably, the reaction of step (2) is carried out in a catalyst;
preferably, the catalyst of step (2) comprises ferric chloride.
6. The method for synthesizing dibasic acid dihydrazide according to any one of claims 1 to 5, wherein the hydrazine hydrate in the step (2) further comprises a step of preheating before the reaction;
preferably, the preheating temperature of the hydrazine hydrate in the step (2) is 70-75 ℃;
preferably, the reaction temperature in the step (2) is 75-80 ℃;
preferably, the reaction in step (2) further comprises a centrifugation and/or drying step after completion.
7. The method for synthesizing a dibasic acid dihydrazide according to any one of claims 1 to 6, wherein the method for synthesizing a dibasic acid dihydrazide comprises a continuous synthesis method;
preferably, the apparatus of the continuous process comprises a fixed bed continuous reaction apparatus;
preferably, the fixed bed continuous reaction device comprises a first fixed bed reaction tower and a second fixed bed reaction tower which are connected in sequence.
8. The method for synthesizing dibasic acid dihydrazide according to claim 7, wherein the first fixed bed reaction tower and the second fixed bed reaction tower are each independently packed with a catalyst;
preferably, a first reaction buffer tank is arranged between the first fixed bed reaction tower and the second fixed bed reaction tower;
preferably, the feed inlet of the first reaction buffer tank is connected with the first fixed bed reaction tower;
preferably, the discharge port of the first reaction buffer tank is connected with the second fixed bed reaction tower through a first delivery pump.
9. The method for synthesizing dibasic acid dihydrazide according to claim 7 or 8, wherein the fixed bed continuous reaction device further comprises a feeding device;
preferably, the feeding device comprises a dibasic ester compound feeding device and a hydrazine hydrate feeding device;
preferably, the dibasic ester compound feeding device comprises a dissolving kettle, a second delivery pump and a first preheater which are connected in sequence;
preferably, the discharge port of the first preheater is connected with the first fixed bed reaction tower;
preferably, a stirring device is arranged in the dissolving kettle;
preferably, the hydrazine hydrate feeding device comprises a first hydrazine hydrate feeding device and a second hydrazine hydrate feeding device;
preferably, the first hydrazine hydrate feeding device comprises a first hydrazine hydrate preheater and a first hydrazine hydrate delivery pump which are connected in sequence;
preferably, the discharge hole of the first hydrazine hydrate preheater is connected with the first fixed bed reaction tower;
preferably, the second hydrazine hydrate feeding device comprises a second hydrazine hydrate preheater and a second hydrazine hydrate delivery pump;
preferably, the discharge port of the second hydrazine hydrate preheater is connected with the second fixed bed reaction tower;
preferably, the fixed bed continuous reaction device further comprises a centrifugal kettle;
preferably, a second reaction buffer tank and a third delivery pump which are connected in sequence are arranged between the centrifugal kettle and the second fixed bed reaction tower;
preferably, the feed inlet of the second reaction buffer tank is connected with the second fixed bed reaction tower.
10. The method for synthesizing the dibasic acid dihydrazide according to any one of claims 1 to 9, wherein the method comprises the following steps:
(1) conveying the dibasic ester compound and hydrazine hydrate to a first fixed bed reaction tower through a feeding device, and reacting at 70-75 ℃ to obtain dibasic acid monohydrazide;
(2) and (2) conveying the dibasic acid monohydrazide obtained in the step (1) to a second fixed bed reaction tower to react with hydrazine hydrate at the temperature of 75-80 ℃ to obtain the dibasic acid dihydrazide.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109574870A (en) * | 2018-12-25 | 2019-04-05 | 维思普新材料（苏州）有限公司 | A kind of continuous preparation method of hydrazides |
| CN109748815A (en) * | 2019-01-22 | 2019-05-14 | 江苏鑫露化工新材料有限公司 | A kind of synthetic method of adipic dihydrazide |
| 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 |
| CN114057601A (en) * | 2021-12-14 | 2022-02-18 | 重庆腾泽化学有限公司 | Preparation method of succinic dihydrazide |
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2022
- 2022-06-13 CN CN202210678288.2A patent/CN114957036A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109574870A (en) * | 2018-12-25 | 2019-04-05 | 维思普新材料（苏州）有限公司 | A kind of continuous preparation method of hydrazides |
| CN109748815A (en) * | 2019-01-22 | 2019-05-14 | 江苏鑫露化工新材料有限公司 | A kind of synthetic method of adipic dihydrazide |
| 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 |
| CN114057601A (en) * | 2021-12-14 | 2022-02-18 | 重庆腾泽化学有限公司 | Preparation method of succinic dihydrazide |
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