CN108440304A - A kind of high-purity diallyl ammonium chloride and preparation method thereof - Google Patents
A kind of high-purity diallyl ammonium chloride and preparation method thereof Download PDFInfo
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- CN108440304A CN108440304A CN201810320662.5A CN201810320662A CN108440304A CN 108440304 A CN108440304 A CN 108440304A CN 201810320662 A CN201810320662 A CN 201810320662A CN 108440304 A CN108440304 A CN 108440304A
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- ammonium chloride
- diallyl ammonium
- diallylamine
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- hydrogen chloride
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C211/21—Monoamines
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Abstract
A kind of high-purity diallyl ammonium chloride of present invention offer and preparation method thereof, this method is to be dissolved in diallylamine in non-polar organic solvent according to a certain percentage, in the case of cooling, hydrogen chloride gas is slowly introducing in organic solution and is reacted, product after reaction passes through solid-liquor separation, then the drying surface of solids is easy to get to high-purity diallyl ammonium chloride product.Diallylamine is dissolved in non-polar organic solvent in the application, keeps diallylamine reaction density controllable, nonpolar solvent can also preferably transfer heat away from coming so that system temperature keeps stablizing.Hydrogen chloride gas is passed through reactor, using surface reactology principle, so that hydrogen chloride gas is passed through bubble surface and is reacted with diallylamine, solves the problems, such as that hydrochloric acid or hydrogen chloride gas are applied directly to diallylamine and react violent, improves safety.
Description
Technical field
The present invention relates to chemicals preparing technical field more particularly to a kind of high-purity diallyl ammonium chloride and its preparations
Method.
Background technology
Currently, existing diallyl ammonium chloride product is to titrate diene by 30% or so technical hydrochloric acid mostly in the market
Propyl amine obtains, and prepares diallyl ammonium chloride product in this way and has the following disadvantages：
(1) since technical hydrochloric acid contains 70% or so moisture, contain in the diallyl ammonium chloride product to make
There is large quantity of moisture, although part of the manufacturer removes part water by heating in vacuum distillating method, is increased according to physical chemistry entropy former
Reason, an isolated blob can not possibly will not become orderly towards the state development of low entropy, two kinds of compounding substances are separated into two kinds
Pure substance is a very difficult thing.Laboratory and industrialized production all prove, distill 60% diallyl ammonium chloride water
Solution, with the increase of diallyl ammonium chloride concentration, distillation becomes difficult, and concentration rate continuously decreases, and energy consumption is very big, generally
Industrialization distillation can only obtain a concentration of 70% or so product, be made up of the method 90% product it is extremely difficult.
(2) hydrochloric acid direct titration diallylamine is used, due to violent acid-base neutralization reaction, thermal discharge is big, and high temperature is easy
Make diallyl ammonium chloride that amino metachromasia occur, product discoloration is more serious, and there are quality problems for the product to make.
(3) carbon-carbon double bond is under aqueous solution state, and it is poly- to open generation for carbon-carbon double bond under the conditions of high fever or initiator
Reaction is closed, and the reaction of titration with hydrochloric acid diallylamine carries out in aqueous solution, the heat for reacting releasing is easy to cause diallyl
The micro- polymerization of ammonium chloride monomer, influences product quality.
(4) vigorous reaction can be caused by directly hydrogen chloride gas being passed through in diallylamine, and heat cannot pass out in time
Come, controls the improper danger that can set off an explosion.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of high-purity diallyl ammonium chloride and preparation method thereof, drops
Low energy consumption improves product quality.
The present invention is achieved through the following technical solutions：
In a first aspect, the present invention provides a kind of preparation method of high-purity diallyl ammonium chloride, the method includes such as
Lower step：
S01：It is 1 by mass ratio:The diallylamine and non-polar organic solvent of 1-60 is added into reactor, and drops
Temperature makes system temperature maintain 15 DEG C or less.
High temperature is easy to make diallyl ammonium chloride that amino metachromasia occurs, and the application cools down to reactor and by temperature
Maintain 15 DEG C hereinafter, effectively reduce amino discoloration, meanwhile, low temperature can effectively reduce carbon-carbon double bond polymerisation
Occur, ensures product quality.
S02：It is 1 by the molar ratio of hydrogen chloride and diallylamine:1.2-1.3 hydrogen chloride gas is slowly introducing to reaction
In device, control temperature of reactor is at 15 DEG C hereinafter, reacting 24-48 hours.
Hydrogen chloride gas is passed through reactor, using surface reactology principle, make hydrogen chloride gas pass through bubble surface with
Diallylamine is reacted, and keeps reaction mild, solves the problems, such as to react violent when hydrochloric acid direct titration diallylamine.This
In application, relative to the dosage of hydrogen chloride, diallylamine is excessive, because hydrogen chloride is gas, being discharged into air can pollute
Environment, if chlorination excess hydrogen, excessive hydrogen chloride can waste raw material by soda lime absorbent.And diallylamine can be dissolved in
It in non-polar organic solvent, can recycle, environmental protection while can reduce cost.
In the application, the concentration of hydrogen chloride gas is constant, and the concentration variation of diallylamine is unique variable, will
Diallylamine is dissolved in non-polar organic solvent, uses the similar principle that mixes, by controlling containing for diallylamine raw material
Amount, can control the reaction density of diallylamine, to control the severe degree of reaction, and diallylamine has in nonpolarity
Unionization in solvent will not dilute heat release, to ensure that the safety of reaction process.There is no the presence of water in reaction process,
Ionization phenomena in aqueous solution is not present in target product, and product quality is more stablized.
S03：The reaction that the step S02 is obtained carries out solid-liquor separation, by obtained solid under the conditions of 80-100 DEG C
Vacuum drying 3-5h obtains diallyl ammonium chloride product.
Diallyl ammonium chloride is a kind of solid, does not dissolve in non-polar organic solvent, and two kinds of materials are carried out liquid after centrifugation
Gu separation, you can diallyl ammonium chloride solid is obtained, diallyl ammonium chloride product is obtained after drying removal surface solvent,
Drying time can be adjusted according to circumstances, usually between 3-5h.
The application is by selecting high purity raw material, the content ＞ 99.9% of diallylamine raw material, hydrogen chloride gas
The diallyl ammonium chloride product of high level can be obtained in ＞ 99.9%, and since diallyl ammonium chloride solid is insoluble in non-
The impurity content of polar organic solvent, finally obtained product is low, and product purity higher can reach 99% or more, relative to low
The diallyl ammonium chloride of concentration can suitably reduce the amount of its storage and transport, to save the space of transport and storage, reduce
Carrying cost, and the preparation process of the application is simple, saves the time, energy consumption is relatively low.
Method provided by the present application is equally applicable to diallylamine acetate, diallylamine citrate, two allyls
The high purity products such as base amine sulfate.
Preferably, the reactor is shell and tube reactor, the shell and tube reactor uses plural serial stage mode, increases
Add hydrogen chloride gas reactivity.The cooling method is chilled brine cooling or circulating water cooling.
Preferably, in the step S02, unreacted tail gas through-hole alkalinity drier absorbs.
Preferably, the non-polar organic solvent is：High alkane derivative, such as white oil, naphtha.Mobility
Good, high-flash ensures safety.Nonpolar solvent can preferably transfer heat away from coming so that system temperature keeps stablizing.And
It is very big to react the diallyl ammonium chloride polarity generated, does not dissolve in non-polar organic solvent, density ratio non-polar organic solvent
Greatly, it is in solid, is conducive to the separation of diallyl ammonium chloride and non-polar organic solvent, the nonpolarity obtained after separation is organic molten
Agent can also recycle, and reduce cost, reduce the pollution to environment.
Preferably, in the step S02, handled using microbubble when hydrogen chloride gas is slowly introducing into reactor
Technology.For example, by hydrogen chloride gas by being passed through into reactor after micropore, make hydrogen chloride use up it is more be dispersed into minute bubbles with
Diallylamine solution surface haptoreaction increases response area, accelerates reaction rate.
Titration with hydrochloric acid diallylamine is solution reaction, and diallylamine can be dissolved into after titration with hydrochloric acid to diallylamine
In, chlorination hydrogen molecule reacts rapidly with diallyl amine molecule, and the extent of reaction is more violent, reacts abrupt release heat,
Local temperature is excessively high, and amino metachromasia and high temperature can be caused to cause carbon-carbon double bond polymerisation, seriously affect product matter
Amount.And using the diallylamine reaction in hydrogen chloride gas and non-polar organic solvent in the application, chlorination hydrogen molecule is one
Kind of the stronger compound of polarity, it does not dissolve in non-polar organic solvent, into non-polar organic solvent after can deposit in the form of bubbles
It is being reacted with diallylamine non-polar organic solutions interface in bubble, reaction is milder, at the same time it can also pass through
The concentration of diallylamine in organic solvent is controlled, reaction severe degree is effectively adjusted.
Second aspect, the present invention provide a kind of diallyl ammonium chloride product being prepared using the above method.
Technical solution provided in an embodiment of the present invention can include following advantageous effect：
A kind of high-purity diallyl ammonium chloride of present invention offer and preparation method thereof, the method is by diallylamine
It is dissolved in non-polar organic solvent according to a certain percentage, system temperature is made to maintain 15 DEG C hereinafter, hydrogen chloride gas is slowly led to
Enter in aforesaid liquid, after the diallyl ammonium chloride solid drying removal surface solvent after reaction, obtains high-purity diallyl
Ammonium chloride product.In reaction process, since the concentration of hydrogen chloride gas is constant, the concentration variation of diallylamine is unique
Variable, diallylamine is dissolved in non-polar organic solvent, uses the similar principle that mixes, passes through that control diallylamine former
The content of material can control the reaction density of diallylamine, to control the severe degree of reaction, ensure reaction safety.
Finally obtained product diallyl ammonium chloride is a kind of organic salt solid, and boiling point is higher than 500 degrees Celsius, diallylamine boiling point
112 DEG C, hydrogen chloride boiling point is -85 DEG C, and 80 DEG C or so Temperature Vacuum drying can remove unreacted diallylamine and chlorination
Hydrogen obtains the product of high concentration, and low energy consumption.
Specific implementation mode
In order to make those skilled in the art more fully understand the technical solution in the present invention, below to the embodiment of the present invention
In technical solution be clearly and completely described, it is clear that described embodiments are only a part of the embodiments of the present invention,
Instead of all the embodiments.Based on the embodiments of the present invention, those skilled in the art are not before making creative work
The every other embodiment obtained is put, should all be belonged to the scope of protection of the present invention.
Diallyl ammonium chloride is a kind of important chemical substance, with following purposes：
(1) being applied to making cross-linking type aldehyde-free colour stabilizer, (diallyl ammonium chloride is total with dimethyl diallyl ammonium chloride
It is poly-), the centre of crosslinking agent, pharmaceutical intermediate and agricultural chemicals, dyestuff and coating, organic synthesis and resin modifying agent etc.
Body can be also used for preparing amphoteric macromolecule polymer etc.；
(2) it is mainly used to cook the protective agent of some herbicides in terms of Pesticidal products；
(3) diallylamine can be prepared and contained with styrene skeleton monomer and the copolymerization of crosslinking agent divinylbenzene as function monomer
There is the molecularly imprinted polymer of the Quercetin of alkaline functional base, which has Quercetin combines energy well
Power and feature recognition performance；
(4) dimethyl diallyl ammonium chloride, diallyl ammonium chloride and acrylamide are main Material synthesis one kind
Ternary polymerization formaldehyde-free color fixing agent.
Therefore, safely and effectively method prepares diallyl ammonium chloride and is of great significance for selection, is based on this, the application carries
For a kind of preparation method of high-purity diallyl ammonium chloride.
Raw material used in the embodiment of the present invention are the test material of this field routine, can be purchased by commercial channel
It can buy.
Embodiment 1
The present embodiment provides a kind of preparation method of high-purity diallyl ammonium chloride, the method in accordance with the following steps into
Row：
S01：By mass ratio 1:1 diallylamine and non-polar organic solvent (white oil) are added in shell and tube reactor, are opened
Chilled brine cooling is opened, system temperature is made to maintain 15 DEG C or less；
S02：Prepare with the molar ratio of diallylamine to be 1:1.2 hydrogen chloride gas, by ready hydrogen chloride gas
It is slowly introducing in shell and tube reactor, temperature of reactor control is at 15 DEG C hereinafter, reacting for 24 hours, unreacted tail gas passes through alkali formula
Drier absorbs；
S03：After the completion of reaction, product is subjected to solid-liquor separation, by obtained solid under the conditions of 80 DEG C vacuum drying 4h,
Up to high-purity diallyl ammonium chloride product.
After testing, a concentration of the 99.3% of the high-purity diallyl ammonium chloride product that the present embodiment is prepared.
Embodiment 2
The present embodiment provides a kind of preparation method of high-purity diallyl ammonium chloride, the method in accordance with the following steps into
Row：
S01：By mass ratio 1:60 diallylamines and non-polar organic solvent (naphtha) are added in shell and tube reactor,
ON cycle water cools down, and system temperature is made to maintain 10 DEG C or less；
S02：Prepare with the molar ratio of diallylamine to be 1:1.3 hydrogen chloride gas, by ready hydrogen chloride gas
It is slowly introducing in shell and tube reactor, temperature of reactor control is at 15 DEG C hereinafter, reaction 48h, unreacted tail gas pass through alkali formula
Drier absorbs；
S03：After the completion of reaction, product is subjected to solid-liquor separation, by obtained solid under the conditions of 100 DEG C vacuum drying
5h is to get high-purity diallyl ammonium chloride product.
After testing, a concentration of the 99.2% of the high-purity diallyl ammonium chloride product that the present embodiment is prepared.
Embodiment 3
The present embodiment provides a kind of preparation method of high-purity diallyl ammonium chloride, the method in accordance with the following steps into
Row：
S01：By mass ratio 1:50 diallylamines and non-polar organic solvent (white oil) are added in shell and tube reactor, are opened
Chilled brine cooling is opened, system temperature is made to maintain 15 DEG C or less；
S02：Prepare with the molar ratio of diallylamine to be 1:1.2 hydrogen chloride gas, by ready hydrogen chloride gas
It is slowly introducing in shell and tube reactor, temperature of reactor control is at 15 DEG C hereinafter, reaction 36h, unreacted tail gas pass through alkali formula
Drier absorbs；
S03：After the completion of reaction, product is subjected to solid-liquor separation, by obtained solid under the conditions of 80 DEG C vacuum drying
3.5h is to get high-purity diallyl ammonium chloride product.
After testing, a concentration of the 99.6% of the high-purity diallyl ammonium chloride product that the present embodiment is prepared.
Embodiment 4
The present embodiment provides a kind of preparation method of high-purity diallyl ammonium chloride, the method in accordance with the following steps into
Row：
S01：By mass ratio 1:20 diallylamines and non-polar organic solvent (naphtha) are added in shell and tube reactor,
Chilled brine cooling is opened, system temperature is made to maintain 15 DEG C or less；
S02：Prepare with the molar ratio of diallylamine to be 1:1.3 hydrogen chloride gas, by ready hydrogen chloride gas
It is slowly introducing in shell and tube reactor, temperature of reactor control is at 10 DEG C hereinafter, reaction 48h, unreacted tail gas pass through alkali formula
Drier absorbs；
S03：After the completion of reaction, product is subjected to solid-liquor separation, obtained solid is dried into 4.5h under the conditions of 90 DEG C, i.e.,
Obtain high-purity diallyl ammonium chloride product.
After testing, a concentration of the 99.5% of the high-purity diallyl ammonium chloride product that the present embodiment is prepared.
Certainly, above description is also not limited to the example above, technical characteristic of the present invention without description can by or
It is realized using the prior art, details are not described herein；It is not to this that above example, which is only used to illustrate the technical scheme of the present invention,
The limitation of invention, describes the invention in detail with reference to preferred embodiment, and those skilled in the art should
Understand, the variations, modifications, additions or substitutions that those skilled in the art are made in the essential scope of the present invention
Without departure from spirit of the invention, it should also belong to the claims of the present invention.
Claims (6)
1. a kind of preparation method of high-purity diallyl ammonium chloride, which is characterized in that described method includes following steps：
S01：It is 1 by mass ratio:The diallylamine and non-polar organic solvent of 1-60 is added into reactor, and cools down, and makes
System temperature maintains 15 DEG C or less；
S02：It is 1 by the molar ratio of hydrogen chloride and diallylamine:1.2-1.3 hydrogen chloride gas be slowly introducing to reactor
In, control temperature of reactor is at 15 DEG C hereinafter, reacting 24-48 hours；
S03：The reaction that the step S02 is obtained carries out solid-liquor separation, by obtained solid under the conditions of 80-100 DEG C vacuum
3-5h is dried, diallyl ammonium chloride product is obtained.
2. a kind of preparation method of high-purity diallyl ammonium chloride according to claim 1, which is characterized in that described anti-
It is shell and tube reactor to answer device, and the shell and tube reactor uses plural serial stage mode, the cooling method to be dropped for chilled brine
Temperature or circulating water cooling.
3. a kind of preparation method of high-purity diallyl ammonium chloride according to claim 1, which is characterized in that the step
In rapid S02, unreacted tail gas through-hole alkalinity drier absorbs.
4. a kind of preparation method of high-purity diallyl ammonium chloride according to claim 1, which is characterized in that described non-
Polar organic solvent is：High alkane derivative.
5. a kind of preparation method of high-purity diallyl ammonium chloride according to claim 1, which is characterized in that the step
In rapid S02, by hydrogen chloride gas by being passed through in reactor after micropore.
6. diallyl ammonium chloride product prepared by a kind of any one of claim 1-5 the methods.
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| CN201810320662.5A CN108440304B (en) | 2018-04-09 | 2018-04-09 | Diallyl ammonium chloride and preparation method thereof |
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| CN201810320662.5A CN108440304B (en) | 2018-04-09 | 2018-04-09 | Diallyl ammonium chloride and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1296690A (en) * | 1968-12-20 | 1972-11-15 | ||
| CN1514159A (en) * | 2002-12-26 | 2004-07-21 | �ʾ����ʲ�ҵ��ʽ���� | Pipe joint |
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2018
- 2018-04-09 CN CN201810320662.5A patent/CN108440304B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1296690A (en) * | 1968-12-20 | 1972-11-15 | ||
| CN1514159A (en) * | 2002-12-26 | 2004-07-21 | �ʾ����ʲ�ҵ��ʽ���� | Pipe joint |
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