CN108329214B - Allyl ammonium chloride and preparation method thereof - Google Patents
Allyl ammonium chloride and preparation method thereof Download PDFInfo
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- CN108329214B CN108329214B CN201810312470.XA CN201810312470A CN108329214B CN 108329214 B CN108329214 B CN 108329214B CN 201810312470 A CN201810312470 A CN 201810312470A CN 108329214 B CN108329214 B CN 108329214B
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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Abstract
The invention provides a high-purity allyl ammonium chloride and a preparation method thereof, wherein allyl amine is dissolved in a non-polar organic solvent according to a certain proportion, hydrogen chloride gas is slowly introduced into an organic solution for reaction under the condition of cooling, the reacted product is separated by a separating funnel, and then unreacted allyl amine and hydrogen chloride are removed by vacuum distillation, so that the high-content allyl ammonium chloride product is finally obtained. In the application, allylamine is dissolved in a nonpolar organic solvent, so that the reaction concentration of the allylamine 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 allylamine through the surface of the bubble by utilizing the principle of surface reaction, so that the problem of violent reaction when the hydrochloric acid or the hydrogen chloride gas is directly added into the allylamine is solved, and the safety is improved.
Description
Technical Field
The invention relates to the technical field of chemical preparation, in particular to allyl ammonium chloride and a preparation method thereof.
Background
Currently, the allyl ammonium chloride products existing in the market are mostly obtained by titrating allyl amine with about 30% of industrial hydrochloric acid, and the preparation of the allyl ammonium chloride products by adopting the method has the following defects:
(1) because the industrial hydrochloric acid contains about 70 percent of moisture, the obtained allyl ammonium chloride product contains a large amount of moisture, and although part of manufacturers remove part of the moisture by a vacuum heating distillation method, an isolated system cannot develop towards a low-entropy state or become orderly 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% allyl ammonium chloride aqueous solution is difficult with the increase of the concentration of allyl 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 allyl amine is directly titrated by hydrochloric acid, the heat release is large due to the violent acid-base neutralization reaction, the allyl ammonium chloride is easy to generate amino-group color change reaction at high temperature, and the color change 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 allyl amine 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 allyl ammonium chloride monomers, thereby influencing the product quality.
(4) The direct introduction of hydrogen chloride gas into allyl amine 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 allyl ammonium chloride and a preparation method thereof, which can 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 process for the preparation of allylammonium chloride, the process comprising the steps of:
s01: adding allyl amine and a nonpolar organic solvent into a reactor in a mass ratio of 1:1-100, and reducing the temperature to keep the temperature of the system below 10 ℃.
High temperature makes allyl ammonium chloride take place amino discoloration reaction easily, and this application is cooled down the reactor and is kept the temperature below 10 ℃, effectively reduces amino discoloration degree, and simultaneously, low temperature can effectually reduce carbon-carbon double bond polymerization's emergence, guarantees product quality.
S02: the mol ratio of hydrogen chloride to allyl amine is 1:1.1-1.3, hydrogen chloride gas is slowly introduced into a reactor, the temperature of the reactor is controlled below 10 ℃, and the reaction lasts 24-48 hours.
The hydrogen chloride gas is introduced into the reactor, and the hydrogen chloride gas reacts with the allylamine 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 allylamine is directly titrated by hydrochloric acid is solved. In the present application, allylamine is in excess relative to the amount of hydrogen chloride used, since 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 raw materials. And the allylamine can be dissolved in a nonpolar organic solvent, can be recycled, protects the environment and can reduce the cost at the same time.
In the application, the concentration of hydrogen chloride gas is unchanged, the concentration change of allylamine is a unique variable, allylamine is dissolved in a nonpolar organic solvent, the similarity intermiscibility principle is adopted, the reaction concentration of allylamine can be controlled by controlling the content of allylamine raw materials, so that the intensity of the reaction is controlled, allylamine 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) separating the reaction product obtained in the step S02 by using a separating funnel to obtain allyl ammonium chloride and a non-polar organic solvent.
The allyl ammonium chloride is a polar compound, is insoluble in a non-polar organic solvent, is easy to separate two materials after standing, and can be separated by using a separating funnel.
S04: and (4) distilling the allyl ammonium chloride obtained in the step S03 for 1-2h under the vacuum condition of 60-100 ℃ to obtain high-purity allyl ammonium chloride.
The allyl ammonium chloride product obtained by the method is an organic salt, the boiling point is higher than 500 ℃, the boiling point of allyl amine is 56 ℃, the boiling point of hydrogen chloride is-85 ℃, and the unreacted allyl amine and hydrogen chloride can be removed by vacuum distillation at the temperature of about 60 ℃, so that the problem of high energy consumption in the background technology is solved.
According to the method, high-purity raw materials are selected, the content of the allylamine raw materials is greater than 99.9%, the content of hydrogen chloride gas is greater than 99.9%, a high-content allylammonium chloride product can be obtained, the allylammonium chloride product 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 the storage and transportation amount of the allylammonium chloride product can be properly reduced compared with that of low-concentration allylammonium chloride, 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 lower.
The method provided by the application is also suitable for high-purity products such as allyl amine acetate, allyl amine citrate, allyl amine 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 allyl 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 deposited at the bottom of the reactor after the reaction, is beneficial to the layered separation of the allyl 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 environmental pollution.
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 allylamine solution, the reaction area is increased, and the reaction rate is accelerated.
The hydrochloric acid titrates the allylamine to be a solution reaction, the hydrochloric acid titrates the allylamine and then is dissolved in the allylamine, hydrogen chloride molecules and the allylamine molecules quickly 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 the high temperature initiates a carbon-carbon double bond polymerization reaction, so that the product quality is seriously influenced. In the application, hydrogen chloride gas is adopted to react with allylamine 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 allylamine nonpolar organic solution, the reaction is mild, and meanwhile, the intensity of the reaction can be effectively adjusted by controlling the concentration of the allylamine in the organic solvent.
In a second aspect, the present invention provides an allylic ammonium 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 allyl ammonium chloride and a preparation method thereof, wherein the method comprises the steps of dissolving allyl amine in a non-polar organic solvent according to a certain proportion, keeping the temperature of the system below 10 ℃, slowly introducing hydrogen chloride gas into the liquid, separating the reacted product through a separating funnel, and then removing unreacted allyl amine and hydrogen chloride through vacuum distillation to finally obtain the high-content allyl ammonium chloride product. In the reaction process, the concentration of the hydrogen chloride gas is unchanged, the concentration of the allylamine is changed into a unique variable, the allylamine is dissolved in a nonpolar organic solvent, the principle of similarity and intermiscibility is adopted, and the reaction concentration of the allylamine can be controlled by controlling the content of the allylamine raw material, so that the intensity of the reaction is controlled, and the reaction safety is ensured. The finally obtained product allyl ammonium chloride is an organic salt, the boiling point of the allyl ammonium chloride is higher than 500 ℃, the boiling point of the allyl amine is 56 ℃, the boiling point of the hydrogen chloride is-85 ℃, and the unreacted allyl amine and the hydrogen chloride can be removed by vacuum distillation at the temperature of about 60 ℃, so that a high-concentration product is obtained, 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.
Allyl ammonium chloride is an important chemical substance that has the following uses:
(1) the allyl ammonium chloride is a multipurpose organic intermediate, can be used as a corrosion inhibitor in steel pickling, for manufacturing resin, diuretic drugs and the like, can also react with aniline to generate quinoline, and can be used for preparing microcapsules, high-molecular fluorescent probes, carriers of high-molecular catalysts and the like;
(2) intermediates for the production of pharmaceuticals, agrochemicals, emulsion modifiers and plastics additives;
(3) it is applied to pharmaceutical intermediates (sevelamer intermediates), and intermediates of agrochemicals, dyes and paints, organic synthesis and resin modifiers, etc. Can also be used for preparing amphoteric high molecular polymers and the like;
(4) the allyl ammonium chloride monomer can be used for graft copolymerization modification of bacterial cellulose to prepare a substance with higher reaction activity, and has good development potential and application prospect;
(5) can be used for synthesizing polyallylamine type macromolecular dye;
(6) can be used for synthesizing polyallylamine silica gel composite materials;
(7) can be used for preparing allylamine antifungal compounds.
Therefore, the method for preparing the allyl ammonium chloride has important significance in selecting a safe and effective method, and the application provides the method for preparing the allyl ammonium chloride on the basis of the method.
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 allyl ammonium chloride, which is performed according to the following steps:
s01: adding allyl amine and a nonpolar organic solvent (white oil) in a mass ratio of 1:1 into a tubular reactor, and starting frozen brine to reduce the temperature to maintain the system temperature below 10 ℃;
s02: preparing hydrogen chloride gas with the molar ratio of 1:1.1 to allylamine, slowly introducing the prepared hydrogen chloride gas into a tubular reactor, controlling the temperature of the reactor to be below 10 ℃, reacting for 24 hours, and absorbing unreacted tail gas by using an alkali type drying agent;
s03: after the reaction is finished, discharging the materials through a valve at the bottom of the reactor, and separating the allyl ammonium chloride from the nonpolar organic solvent through a separating funnel;
s04: and (5) distilling the allyl ammonium chloride obtained in the step (S03) for 2h at the temperature of 60 ℃ in vacuum to obtain a high-purity allyl ammonium chloride product.
The concentration of the high-purity allyl ammonium chloride product prepared by the embodiment is 99.2% by adopting a drying solid content method.
Example 2
This example provides a method for preparing allyl ammonium chloride, which is performed according to the following steps:
s01: adding allyl amine and a nonpolar organic solvent (naphtha) in a mass ratio of 1:100 into a tubular reactor, and starting circulating water to reduce the temperature so as to maintain the temperature of the system below 10 ℃;
s02: preparing hydrogen chloride gas with the molar ratio of 1:1.3 to allylamine, 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, discharging the materials through a valve at the bottom of the reactor, and separating the allyl ammonium chloride from the nonpolar organic solvent through a separating funnel;
s04: and (4) distilling the allyl ammonium chloride obtained in the step (S03) for 1h at the temperature of 100 ℃ in vacuum to obtain a high-purity allyl ammonium chloride product.
The concentration of the high-purity allyl ammonium chloride product prepared by the embodiment is 99.5% by adopting a drying solid content method.
Example 3
This example provides a method for preparing allyl ammonium chloride, which is performed according to the following steps:
s01: adding allyl amine 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 maintain the system temperature below 10 ℃;
s02: preparing hydrogen chloride gas with the molar ratio of 1:1.2 to allyl amine, slowly introducing the prepared hydrogen chloride gas into a tubular reactor, controlling the temperature of the reactor to be below 10 ℃, reacting for 36 hours, and absorbing unreacted tail gas by an alkali type drying agent;
s03: after the reaction is finished, discharging the materials through a valve at the bottom of the reactor, and separating the allyl ammonium chloride from the nonpolar organic solvent through a separating funnel;
s04: and (5) distilling the allyl ammonium chloride obtained in the step (S03) for 1.5h at the temperature of 80 ℃ in vacuum to obtain a high-purity allyl ammonium chloride product.
The concentration of the high-purity allyl ammonium chloride product prepared by the embodiment is 99.3% by adopting a drying solid content method.
Example 4
This example provides a method for preparing allyl ammonium chloride, which is performed according to the following steps:
s01: adding allylamine and a non-polar 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 10 ℃;
s02: preparing hydrogen chloride gas with the molar ratio of 1:1.1 to allylamine, 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, discharging the materials through a valve at the bottom of the reactor, and separating the allyl ammonium chloride from the nonpolar organic solvent through a separating funnel;
s04: and (5) distilling the allyl ammonium chloride obtained in the step (S03) for 1.5h at the temperature of 60 ℃ in vacuum to obtain a high-purity allyl ammonium chloride product.
The concentration of the high-purity allyl ammonium chloride product prepared by the embodiment is 99.4% by adopting a drying solid content method.
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 allyl ammonium chloride is characterized by comprising the following steps:
s01: adding allyl amine and a nonpolar organic solvent in a mass ratio of 1:1-100 into a reactor, and cooling to maintain the temperature of the system below 10 ℃; the non-polar organic solvent is: white oil or naphtha; the reactor is a tubular reactor, the tubular reactor adopts a multistage series connection mode, and the cooling mode is freezing brine cooling or circulating water cooling;
s02: passing hydrogen chloride gas with the molar ratio of 1:1.1-1.3 of hydrogen chloride to allylamine through the micropores, slowly introducing the hydrogen chloride gas into the reactor, controlling the temperature of the reactor below 10 ℃, and reacting for 24-48 hours; absorbing unreacted tail gas by an alkaline drying agent;
s03: separating the reaction product obtained in the step S02 by using a separating funnel to obtain allyl ammonium chloride and a non-polar organic solvent;
s04: and (4) distilling the allyl ammonium chloride obtained in the step S03 for 1-2h under the vacuum condition of 60-100 ℃ to obtain high-purity allyl ammonium chloride.
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