CN109320420A - A kind of synthetic method of chain alkyl methyl carbonate quaternary ammonium salt - Google Patents
A kind of synthetic method of chain alkyl methyl carbonate quaternary ammonium salt Download PDFInfo
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- CN109320420A CN109320420A CN201811371636.1A CN201811371636A CN109320420A CN 109320420 A CN109320420 A CN 109320420A CN 201811371636 A CN201811371636 A CN 201811371636A CN 109320420 A CN109320420 A CN 109320420A
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- Prior art keywords
- chain alkyl
- quaternary ammonium
- ammonium salt
- synthetic method
- dimethyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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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
Abstract
The invention discloses a kind of synthetic method of chain alkyl methyl carbonate quaternary ammonium salt, reaction equation is as follows:
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of synthesis side of chain alkyl methyl carbonate quaternary ammonium salt
Method.
Background technique
Long chain alkyl ammonium salt is a kind of important cationic surfactant, is widely used in daily-use chemical industry, weaving, print
The fields such as dye, building, plastic processing, petrochemical industry.According to statistics, the average growth rate per annum of whole world cationic surfactant is about
5.4%, the average growth rate per annum of Asia is about 8%, is more than the average annual increasing degree in the world, has good development potentiality with before
Scape.
Currently, synthesis quaternary cationic surfactant is often used the quaternizing agent of severe toxicity: halomethane and sulfuric acid
Dimethyl ester.Human body and environment are caused great harm, the acid generated in synthesis technology corrodes very serious, subsequent mistake to equipment
Cheng Zhongxu adds alkali to be neutralized, and generates a large amount of abraum salts；Remaining quaternizing agent also can cause to dive to user in downstream product
It is endangering.The best method for solving these deterrences is exactly to develop, using the harmless quaternizing agent of novel non-toxic, to substitute tradition
Poisonous and hazardous quaternizing agent such as uses green non-poisonous dimethyl carbonate as quaternizing agent.
1992 dimethyl carbonate (DMC) by European registration be nonpoisonous chemicla, contain methyl in molecule, can be used as first
Base reagent.The scholars such as Geng Tao synthesize trimethyl methyl carbonate quaternary ammonium (Geng Tao, Li Qiu little, Jiang Ya using DMC
Clean, Wang Wei, the synthesis and characterization of methyl carbonic acid ester quat, fine chemistry industry, 2010,27 (6), 537-540), and carbonic acid first
The acidity of ester is very weak, can react with most weak acid, and preparing counter ion is CH3COO-、HCOO-、HCO3 -Quaternary ammonium salt, e.g.,
Quaternary ammonium base needed for electroplating industry can prepare (Dong by the alkylcarbonic acid hydrogen ammonium that methyl carbonate ammonium hydrolyzes after being electrolysed
Son good, Geng Tao, Jiang Yajie, Ju Hongbin, the preparation process and performance of chain alkyl quaternary ammonium base, fine chemistry industry, 2015,32 (7),
746-750)；It is acted on strong acid, can be Cl with the anion for being entirely free of toxic quaternizing agent is prepared-、CH3SO4 -、Br-、
C2H5SO4 -Quaternary ammonium salt.
The technique is to be reacted using DMC and the chain alkyl dimethyl tertiary amine temperature reaction in methanol solution using pressure
Kettle increases reaction temperature to shorten the reaction time, and after reaction, vacuum distillation removal methanol obtains sticky white product, institute
Alkyl tertiary amine that can be complete containing methanol and unreacted in product is obtained, product purity is influenced.
Summary of the invention
It is an object of the invention to overcome prior art defect, a kind of synthesis of chain alkyl methyl carbonate quaternary ammonium salt is provided
Method.
Technical scheme is as follows:
A kind of synthetic method of chain alkyl methyl carbonate quaternary ammonium salt, reaction equation are as follows:
Wherein R is the alkyl of C12~18, and chain alkyl methyl carbonate quaternary ammonium salt is precipitated from dimethyl carbonate automatically, not
The chain alkyl dimethyl tertiary amine of reaction is dissolved in dimethyl carbonate, is separated with chain alkyl methyl carbonate quaternary ammonium salt, through solid
Liquid separation can be obtained chain alkyl methyl carbonate quaternary ammonium salt.
In a preferred embodiment of the invention, include the following steps:
(1) chain alkyl dimethyl tertiary amine is added in dimethyl carbonate, it is anti-in 145~155 DEG C under nitrogen protection
Answer 2.5~3.5h；
(2) by after the resulting material cooling of step (1), chain alkyl methyl carbonate quaternary ammonium salt is automatically from dimethyl carbonate
It is precipitated, is separated by solid-liquid separation to obtain the final product, unreacted chain alkyl dimethyl tertiary amine is dissolved in dimethyl carbonate.
It is further preferred that the step (1) are as follows: chain alkyl dimethyl tertiary amine is added in dimethyl carbonate,
In 150 DEG C of reaction 3h under nitrogen protection.
It is further preferred that described be separated by solid-liquid separation to filter or filtering.
In a preferred embodiment of the invention, the R is dodecyl, myristyl, cetyl or 18
Alkyl.
In a preferred embodiment of the invention, the chain alkyl dimethyl tertiary amine is in the dimethyl carbonate
Concentration be 10~25wt%.
The beneficial effects of the present invention are:
1, the reaction temperature of synthetic method of the invention is high, shortens the nearly half reaction time, and pressure is lower, more pacifies
Entirely.
2, the post-processing of synthetic method of the invention is simple, does not need distillation removal solvent, only need to be separated by solid-liquid separation and can obtain
To product.
3, the resulting product of synthetic method of the invention is free of dimethyl carbonate, unreacted chain alkyl dimethyl tertiary amine
It stays in filtrate, is nearly no detectable remaining tertiary amine in the product using gas chromatography confirmation.
4, synthetic method of the invention avoids using toxic methanol as reaction medium, using the carbonic acid diformazan of green
Ester both does reaction raw materials, also does reaction medium, safer.
5, in synthetic method of the invention, the long-chain alkyl tertiary amine in dimethyl carbonate is stayed in completely without processing, it can
To add chain alkyl dimethyl tertiary amine, the reaction was continued
Specific embodiment
Technical solution of the present invention is further explained and described below by way of specific embodiment.
Embodiment 1: the synthesis of trimethyl methyl carbonate quaternary ammonium salt
A certain amount of Dodecyl Dimethyl Amine is added to dimethyl carbonate (DMC), being configured to mass ratio is 10%-
25% solution, is placed in reaction kettle, under nitrogen protection in 150 DEG C of reaction 3h.Cooling, suction filtration obtains white crystal, yield
85% or more.Gained trimethyl methyl carbonate quaternary ammonium salt is characterized as below:1H NMR(CD3OD, 400MHz) δ:
0.92 (t, 3H), 1.32-1.42 (m, 18H), 1.80 (m, 2H), 3.14 (s, 9H), 3.32 (m, 2H), 3.37 (s, 3H).
Embodiment 2: the synthesis of tetradecyltrimethylammonium methyl carbonate quaternary ammonium salt
A certain amount of dodecyldimethylamine base tertiary amine is added to dimethyl carbonate (DMC), being configured to mass ratio is 10%-
25% solution, is placed in reaction kettle, under nitrogen protection in 150 DEG C of reaction 3h.Cooling, suction filtration obtains white crystal, yield
85% or more.Gained tetradecyltrimethylammonium methyl carbonate quaternary ammonium salt is characterized as below:1H NMR(CD3OD, 400MHz) δ:
0.90 (t, 3H), 1.29-1.39 (m, 22H), 1.78 (m, 2H), 3.11 (s, 9H), 3.31 (m, 2H), 3.33 (s, 3H).
Embodiment 3: the synthesis of cetyl trimethyl methyl carbonate quaternary ammonium salt
A certain amount of hexadecyldimethyl benzyl ammonium tertiary amine is added to dimethyl carbonate (DMC), being configured to mass ratio is 10%-
25% solution, is placed in reaction kettle, under nitrogen protection in 150 DEG C of reaction 3h.Cooling, suction filtration obtains white crystal, yield
85% or more.Gained cetyl trimethyl methyl carbonate quaternary ammonium salt is characterized as below:1H NMR(CD3OD, 400MHz) δ:
0.92 (t, 3H), 1.31-1.42 (m, 26H), 1.80 (m, 2H), 3.14 (s, 9H), 3.34 (m, 2H), 3.35 (s, 3H).
Embodiment 4: the synthesis of octadecyl trimethyl methyl carbonate quaternary ammonium salt
A certain amount of octadecyldimethyl tertiary amine is added to dimethyl carbonate (DMC), being configured to mass ratio is 10%-
25% solution, is placed in reaction kettle, under nitrogen protection in 150 DEG C of reaction 3h.Cooling, suction filtration obtains white crystal, yield
85% or more.Gained octadecyl trimethyl methyl carbonate quaternary ammonium salt is characterized as below:1H NMR(CDCl3, 400MHz) and δ:
0.90 (t, 3H), 1.24-1.33 (m, 30H), 1.73 (m, 2H), 3.14 (s, 9H), 3.33 (m, 2H), 3.35 (s, 3H).
The foregoing is only a preferred embodiment of the present invention, the range that the present invention that therefore, it cannot be limited according to is implemented, i.e.,
Equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be within the scope of the present invention.
Claims (6)
1. a kind of synthetic method of chain alkyl methyl carbonate quaternary ammonium salt, it is characterised in that: its reaction equation is as follows:
Wherein R is the alkyl of C12~18, and chain alkyl methyl carbonate quaternary ammonium salt is precipitated from dimethyl carbonate automatically, unreacted
Chain alkyl dimethyl tertiary amine be dissolved in dimethyl carbonate, separated with chain alkyl methyl carbonate quaternary ammonium salt, through solid-liquid point
From can be obtained chain alkyl methyl carbonate quaternary ammonium salt.
2. synthetic method as described in claim 1, characterized by the following steps:
(1) chain alkyl dimethyl tertiary amine is added in dimethyl carbonate, reacts 2.5 in 145~155 DEG C under nitrogen protection
~3.5h；
(2) by after the resulting material cooling of step (1), chain alkyl methyl carbonate quaternary ammonium salt is analysed from dimethyl carbonate automatically
Out, it is separated by solid-liquid separation to obtain the final product, unreacted chain alkyl dimethyl tertiary amine is dissolved in dimethyl carbonate.
3. synthetic method as claimed in claim 2, it is characterised in that: the step (1) are as follows: by chain alkyl dimethyl tertiary amine
It is added in dimethyl carbonate, under nitrogen protection in 150 DEG C of reaction 3h.
4. synthetic method as claimed in claim 2, it is characterised in that: described to be separated by solid-liquid separation to filter or filtering.
5. synthetic method as described in claim 1, it is characterised in that: the R is dodecyl, myristyl, cetyl
Or octadecyl.
6. the synthetic method as described in any claim in claim 1 to 5, it is characterised in that: the chain alkyl diformazan
Concentration of the base tertiary amine in the dimethyl carbonate is 10~25wt%.
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| CN201811371636.1A CN109320420A (en) | 2018-11-16 | 2018-11-16 | A kind of synthetic method of chain alkyl methyl carbonate quaternary ammonium salt |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372457A (en) * | 2008-10-29 | 2009-02-25 | 北京工商大学 | Preparation of alkyl trimethyl quaternary ammonium salt |
| JP2010095463A (en) * | 2008-10-15 | 2010-04-30 | Tosoh Corp | Method for recovering quaternary ammonium salt |
| CN102816075A (en) * | 2012-08-24 | 2012-12-12 | 四川大学 | Preparation method of long-chain quaternary ammonium surfactant |
| US20130041159A1 (en) * | 2011-08-09 | 2013-02-14 | Basf Se | Process for purifying ionic liquids |
-
2018
- 2018-11-16 CN CN201811371636.1A patent/CN109320420A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010095463A (en) * | 2008-10-15 | 2010-04-30 | Tosoh Corp | Method for recovering quaternary ammonium salt |
| CN101372457A (en) * | 2008-10-29 | 2009-02-25 | 北京工商大学 | Preparation of alkyl trimethyl quaternary ammonium salt |
| US20130041159A1 (en) * | 2011-08-09 | 2013-02-14 | Basf Se | Process for purifying ionic liquids |
| CN102816075A (en) * | 2012-08-24 | 2012-12-12 | 四川大学 | Preparation method of long-chain quaternary ammonium surfactant |
Non-Patent Citations (1)
| Title |
|---|
| 李桂芬等: "《有机化学实验》", 30 April 2010, 煤炭工业出版社 * |
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