CN108440304B - Diallyl ammonium chloride and preparation method thereof - Google Patents
Diallyl ammonium chloride and preparation method thereof Download PDFInfo
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- CN108440304B CN108440304B CN201810320662.5A CN201810320662A CN108440304B CN 108440304 B CN108440304 B CN 108440304B CN 201810320662 A CN201810320662 A CN 201810320662A CN 108440304 B CN108440304 B CN 108440304B
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C—CHEMISTRY; METALLURGY
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/20—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
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Abstract
The invention provides high-purity diallyl ammonium chloride and a preparation method thereof. In the application, diallylamine is dissolved in a nonpolar organic solvent, so that the reaction concentration of diallylamine is controllable, and the nonpolar solvent can better transfer heat out, so that the temperature of a system is kept stable. The hydrogen chloride gas is introduced into the reactor, and the hydrogen chloride gas reacts with the diallylamine through the surface of the bubbles by utilizing the principle of surface reaction, so that the problem of severe reaction caused by directly adding the hydrochloric acid or the hydrogen chloride gas to the diallylamine is solved, and the safety is improved.
Description
Technical Field
The invention relates to the technical field of chemical preparation, in particular to diallyl ammonium chloride and a preparation method thereof.
Background
Currently, the diallylammonium chloride products in the market are mostly obtained by titrating diallylamine with about 30% of industrial hydrochloric acid, and the diallylammonium chloride products prepared by the method have the following defects:
(1) because the industrial hydrochloric acid contains about 70 percent of moisture, the obtained diallyl ammonium chloride product contains a large amount of moisture, and although part of manufacturers remove part of the water by a vacuum heating distillation method, an isolated system cannot develop towards a low-entropy state, namely cannot become ordered according to the principle of physical and chemical entropy increase, and the separation of two mixed substances into two pure substances is difficult. Both laboratories and industrial production prove that distillation of 60% diallyl ammonium chloride aqueous solution is difficult with the increase of the concentration of diallyl ammonium chloride, the concentration rate is gradually reduced, the energy consumption is large, generally industrial distillation can only obtain products with the concentration of about 70%, and the preparation of 90% products by the method is very difficult.
(2) The diallyl amine is directly titrated by hydrochloric acid, due to violent acid-base neutralization reaction, the heat release is large, diallyl ammonium chloride is easy to generate amino-group discoloration reaction at high temperature, and the discoloration of the product is serious, so that the quality of the obtained product is poor.
(3) The carbon-carbon double bond is opened under the condition of high heat or initiator to generate polymerization reaction in the state of aqueous solution, the reaction of titrating diallylamine by hydrochloric acid is carried out in the aqueous solution, and the heat released by the reaction is easy to initiate the micro polymerization of diallylammonium chloride monomers, thereby influencing the product quality.
(4) The direct introduction of hydrogen chloride gas into diallylamine can cause violent reaction, heat cannot be transferred out in time, and improper control can cause explosion hazard.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides diallyl ammonium chloride and a preparation method thereof, which reduce energy consumption and improve product quality.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing diallylammonium chloride, the method comprising the steps of:
s01: adding diallylamine and a nonpolar organic solvent into a reactor in a mass ratio of 1:1-60, and cooling to maintain the temperature of the system below 15 ℃.
High temperature makes diallyl ammonium chloride take place amino discoloration reaction easily, and this application is cooled down the reactor and is kept the temperature below 15 ℃, effectively reduces amino discoloration degree, and simultaneously, low temperature can effectual reduction carbon-carbon double bond polymerization's emergence, guarantees product quality.
S02: the molar ratio of hydrogen chloride to diallylamine is 1:1.2-1.3, hydrogen chloride gas is slowly introduced into the reactor, the temperature of the reactor is controlled below 15 ℃, and the reaction is carried out for 24-48 hours.
The hydrogen chloride gas is introduced into the reactor, and the hydrogen chloride gas is reacted with the diallylamine through the surface of the bubble by utilizing the principle of surface reaction, so that the reaction is mild, and the problem of violent reaction when the hydrochloric acid directly titrates the diallylamine is solved. In the present application, diallylamine is in excess relative to the amount of hydrogen chloride used, because hydrogen chloride is a gas, and is discharged into the atmosphere to pollute the environment, and if hydrogen chloride is in excess, the excess hydrogen chloride is absorbed by soda lime to waste the raw materials. The diallylamine can be dissolved in a nonpolar organic solvent, can be recycled, protects the environment and can reduce the cost.
In the application, the concentration of hydrogen chloride gas is unchanged, the concentration change of diallylamine is a unique variable, diallylamine is dissolved in a nonpolar organic solvent, a similar intermiscibility principle is adopted, the reaction concentration of diallylamine can be controlled by controlling the content of a diallylamine raw material, so that the intensity of reaction is controlled, diallylamine is not ionized in the nonpolar organic solvent, heat release cannot be diluted, and the safety of the reaction process is ensured. No water exists in the reaction process, the target product does not have the ionization phenomenon in the water solution, and the product quality is more stable.
S03: and (4) carrying out liquid-solid separation on the reaction obtained in the step S02, and drying the obtained solid for 3-5h under vacuum at the temperature of 80-100 ℃ to obtain a diallyl ammonium chloride product.
Diallyl ammonium chloride is a solid and insoluble in a nonpolar organic solvent, liquid-solid separation is carried out on the two materials after centrifugation to obtain a diallyl ammonium chloride solid, and a diallyl ammonium chloride product is obtained after drying to remove the surface solvent, wherein the drying time can be adjusted according to the conditions and is usually between 3 and 5 hours.
According to the method, high-purity raw materials are selected, the content of the diallylamine raw materials is more than 99.9%, the content of hydrogen chloride gas is more than 99.9%, a diallylammonium chloride product with high content can be obtained, the diallylammonium chloride solid is insoluble in a non-polar organic solvent, the impurity content of the finally obtained product is low, the product purity is higher and can reach more than 99%, and compared with low-concentration diallylammonium chloride, the storage and transportation amount can be properly reduced, so that the transportation and storage space is saved, the storage and transportation cost is reduced, the preparation process is simple, the time is saved, and the energy consumption is low.
The method provided by the application is also suitable for high-purity products such as diallylamine acetate, diallylamine citrate, diallylamine sulfate and the like.
Preferably, the reactor is a tubular reactor, and the tubular reactor adopts a multistage series connection mode to increase the reaction rate of the hydrogen chloride gas. The cooling mode is freezing brine cooling or circulating water cooling.
Preferably, in step S02, the unreacted exhaust gas is absorbed by the alkaline desiccant.
Preferably, the non-polar organic solvent is: high alkane compounds such as white oil, naphtha, etc. Good fluidity, high flash point and safety guarantee. The non-polar solvent can better transfer heat out, so that the temperature of the system is kept stable. And the diallyl ammonium chloride generated by the reaction has very high polarity, is insoluble in a nonpolar organic solvent, has higher density than the nonpolar organic solvent, is solid, is beneficial to the separation of the diallyl ammonium chloride and the nonpolar organic solvent, and the nonpolar organic solvent obtained after the separation can be recycled, thereby reducing the cost and the pollution to the environment.
Preferably, in step S02, a microbubble treatment technique is used when the hydrogen chloride gas is slowly introduced into the reactor. For example, hydrogen chloride gas is introduced into the reactor after passing through the micropores, so that the hydrogen chloride gas is dispersed into small bubbles as much as possible to contact and react with the surface of the diallylamine solution, the reaction area is increased, and the reaction rate is accelerated.
Titration of diallylamine by hydrochloric acid is a solution reaction, the hydrochloric acid is dissolved in diallylamine after titration of diallylamine, hydrogen chloride molecules and diallylamine molecules rapidly react, the reaction degree is severe, the reaction instantly releases heat, the local temperature is too high, an amino color change reaction is caused, and carbon-carbon double bond polymerization is initiated at high temperature, so that the product quality is seriously influenced. In the application, hydrogen chloride gas is adopted to react with diallylamine in a nonpolar organic solvent, hydrogen chloride molecules are a compound with strong polarity, the hydrogen chloride molecules are insoluble in the nonpolar organic solvent and can exist in a bubble form after entering the nonpolar organic solvent, the reaction is carried out on the interface of the bubbles and the diallylamine nonpolar organic solvent, the reaction is mild, and meanwhile, the intensity of the reaction can be effectively adjusted by controlling the concentration of diallylamine in the organic solvent.
In a second aspect, the invention provides a diallylammonium chloride product prepared by the above method.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
the invention provides diallyl ammonium chloride and a preparation method thereof, wherein diallyl amine is dissolved in a non-polar organic solvent according to a certain proportion, the temperature of the system is maintained below 15 ℃, hydrogen chloride gas is slowly introduced into the liquid, and a diallyl ammonium chloride product is obtained after a reacted diallyl ammonium chloride solid is dried to remove a surface solvent. In the reaction process, as the concentration of hydrogen chloride gas is unchanged and the concentration of diallylamine is changed into a unique variable, diallylamine is dissolved in a nonpolar organic solvent, a similar and compatible principle is adopted, and the reaction concentration of diallylamine can be controlled by controlling the content of the raw material of diallylamine, so that the intensity of the reaction is controlled, and the reaction safety is ensured. The finally obtained product diallyl ammonium chloride is an organic salt solid, the boiling point of the diallyl ammonium chloride is higher than 500 ℃, the boiling point of the diallyl amine is 112 ℃, the boiling point of the hydrogen chloride is-85 ℃, and the unreacted diallyl amine and the hydrogen chloride can be removed by vacuum drying at the temperature of about 80 ℃ to obtain a high-concentration product, and the energy consumption is low. Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Diallylammonium chloride is an important chemical substance which has the following uses:
(1) the method is applied to the preparation of crosslinking type formaldehyde-free fixing agents (diallyl ammonium chloride and dimethyl diallyl ammonium chloride copolymerization), crosslinking agents, pharmaceutical intermediates, intermediates of agricultural chemicals, dyes and coatings, organic synthesis and resin modifiers and the like, and can also be used for preparing amphoteric high molecular polymers and the like;
(2) the pesticide product is mainly used as a protective agent of some herbicides;
(3) diallyl amine serving as a functional monomer can be copolymerized with a styrene skeleton monomer and a cross-linking agent divinylbenzene to prepare a molecularly imprinted polymer of quercetin containing basic functional groups, and the molecularly imprinted polymer has good binding capacity and characteristic recognition performance on the quercetin;
(4) dimethyl diallyl ammonium chloride, diallyl ammonium chloride and acrylamide are used as main raw materials to synthesize the ternary polymerization formaldehyde-free color fixing agent.
Therefore, the method for preparing the diallyl ammonium chloride is of great significance, and the application provides the method for preparing the diallyl ammonium chloride based on the important significance.
The raw materials used in the examples of the present invention are all test materials that are conventional in the art and are commercially available.
Example 1
This example provides a method for preparing diallylammonium chloride, which comprises the following steps:
s01: adding 1:1 by mass of diallylamine and a nonpolar organic solvent (white oil) into a tubular reactor, and starting frozen brine to reduce the temperature to keep the system temperature below 15 ℃;
s02: preparing hydrogen chloride gas with the molar ratio of 1:1.2 to diallylamine, slowly introducing the prepared hydrogen chloride gas into a tubular reactor, controlling the temperature of the reactor to be below 15 ℃, reacting for 24 hours, and absorbing unreacted tail gas by using an alkali type drying agent;
s03: after the reaction is finished, carrying out liquid-solid separation on the product, and drying the obtained solid for 4h under vacuum at the temperature of 80 ℃ to obtain the diallyl ammonium chloride product.
Through detection, the concentration of the diallylammonium chloride product prepared in this example is 99.3%.
Example 2
This example provides a method for preparing diallylammonium chloride, which comprises the following steps:
s01: adding diallylamine and a nonpolar organic solvent (naphtha) into a tubular reactor in a mass ratio of 1:60, and starting circulating water to reduce the temperature to keep the system temperature below 10 ℃;
s02: preparing hydrogen chloride gas with the molar ratio of 1:1.3 to diallylamine, slowly introducing the prepared hydrogen chloride gas into a tubular reactor, controlling the temperature of the reactor to be below 15 ℃, reacting for 48 hours, and absorbing unreacted tail gas by using an alkali type drying agent;
s03: and after the reaction is finished, carrying out liquid-solid separation on the product, and drying the obtained solid for 5 hours in vacuum at the temperature of 100 ℃ to obtain the diallyl ammonium chloride product.
Through detection, the concentration of the diallylammonium chloride product prepared in this example is 99.2%.
Example 3
This example provides a method for preparing diallylammonium chloride, which comprises the following steps:
s01: adding diallylamine and a nonpolar organic solvent (white oil) in a mass ratio of 1:50 into a tubular reactor, and starting frozen brine to reduce the temperature to keep the system temperature below 15 ℃;
s02: preparing hydrogen chloride gas with the molar ratio of 1:1.2 to diallylamine, slowly introducing the prepared hydrogen chloride gas into a tubular reactor, controlling the temperature of the reactor to be below 15 ℃, reacting for 36 hours, and absorbing unreacted tail gas by using an alkali type drying agent;
s03: after the reaction is finished, carrying out liquid-solid separation on the product, and drying the obtained solid for 3.5h under vacuum at the temperature of 80 ℃ to obtain the diallyl ammonium chloride product.
Through detection, the concentration of the diallylammonium chloride product prepared in this example is 99.6%.
Example 4
This example provides a method for preparing diallylammonium chloride, which comprises the following steps:
s01: adding diallylamine and a nonpolar organic solvent (naphtha) into a tubular reactor in a mass ratio of 1:20, and starting frozen brine to reduce the temperature to keep the temperature of the system below 15 ℃;
s02: preparing hydrogen chloride gas with the molar ratio of 1:1.3 to diallylamine, slowly introducing the prepared hydrogen chloride gas into a tubular reactor, controlling the temperature of the reactor to be below 10 ℃, reacting for 48 hours, and absorbing unreacted tail gas by using an alkali type drying agent;
s03: after the reaction is finished, carrying out liquid-solid separation on the product, and drying the obtained solid for 4.5h at the temperature of 90 ℃ to obtain the diallyl ammonium chloride product.
Through detection, the concentration of the diallylammonium chloride product prepared in this example is 99.5%.
Of course, the above description is not limited to the above examples, and the undescribed technical features of the present invention can be implemented by or using the prior art, and will not be described herein again; the above embodiments are merely for illustrating the technical solutions of the present invention and not for limiting the present invention, and the present invention has been described in detail with reference to the preferred embodiments, and those skilled in the art should understand that changes, modifications, additions or substitutions which are made by those skilled in the art within the spirit of the present invention are also within the scope of the claims of the present invention.
Claims (1)
1. A preparation method of diallylammonium chloride is characterized by comprising the following steps:
s01: adding diallylamine and a nonpolar organic solvent in a mass ratio of 1:1-60 into a reactor, and cooling, wherein the reactor is a tubular reactor, the tubular reactor adopts a multistage series connection mode, the cooling mode is cooling by circulating water, the temperature of a system is kept below 15 ℃, and the nonpolar organic solvent is: white oil or naphtha;
s02: passing hydrogen chloride gas with the molar ratio of 1:1.2-1.3 of hydrogen chloride to diallylamine through the micropores, slowly introducing the hydrogen chloride gas into the reactor, controlling the temperature of the reactor below 15 ℃, and reacting for 24-48 hours; absorbing unreacted tail gas by using an alkaline drying agent through the through holes;
s03: and (4) carrying out liquid-solid separation on the reaction obtained in the step S02, and drying the obtained solid for 3-5h under vacuum at the temperature of 80-100 ℃ to obtain a diallyl ammonium chloride product.
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