Synthesis process of dimethyl diallyl ammonium chloride
阅读说明：本技术 一种二甲基二烯丙基氯化铵合成工艺 (Synthesis process of dimethyl diallyl ammonium chloride ) 是由 李唱 刘彭城 陈建波 汪艳 张传银 乔磊磊 张弓 于 2021-08-17 设计创作，主要内容包括：本发明公开一种二甲基二烯丙基氯化铵合成的工艺,包括以下步骤：S1：二甲胺的叔胺化：将Al(OH)-(3)溶胶与氨水组成的混合碱液加入二甲胺溶液中,搅拌均匀后,再按照0.3-0.5mL/min的速度向其中滴加与二甲胺等物质的量的烯丙基氯,控制反应温度为0℃-15℃,磁力搅拌至反应体系中烯丙基氯含量≤0.2％,得反应后溶液,分液,上层油相为粗叔胺；S2：二甲胺的季胺化：干燥粗叔胺后,与烯丙基氯加入到一定体积的有机溶剂中,充分震荡,5℃-15℃冷水浴下静置20min,结晶、活性炭脱色,即得。本发明首次采用Al(OH)-(3)溶胶与氨水配制的碱液代替NaOH中和,极大地避免了烯丙基氯的水解,无烯丙基醇和烯丙基醛等副产物产生,叔胺收率和纯度高,且季胺化产品中不含盐酸盐,合成的DMDAAC单体纯度高。(The invention discloses a process for synthesizing dimethyl diallyl ammonium chloride, which comprises the following steps: s1: tertiary amination of dimethylamine: mixing Al (OH) 3 Adding a mixed alkali solution consisting of sol and ammonia water into a dimethylamine solution, uniformly stirring, then dropwise adding allyl chloride with the amount of dimethylamine and other substances into the mixed alkali solution at the speed of 0.3-0.5mL/min, controlling the reaction temperature to be 0-15 ℃, magnetically stirring until the content of the allyl chloride in a reaction system is less than or equal to 0.2%, obtaining a reacted solution, separating the solution, and obtaining crude tertiary amine as an upper oil phase; s2: quaternization of dimethylamine: after drying the crude tertiary amine, adding to a volume with allyl chlorideFully shaking the mixture in the organic solvent, standing the mixture for 20min in a cold water bath at the temperature of between 5 and 15 ℃, crystallizing the mixture, and decoloring the crystallized mixture by using activated carbon to obtain the finished product. The invention adopts Al (OH) for the first time 3 The alkali liquor prepared by the sol and ammonia water replaces NaOH for neutralization, so that the hydrolysis of allyl chloride is greatly avoided, byproducts such as allyl alcohol and allyl aldehyde are not generated, the yield and the purity of tertiary amine are high, a quaternized product does not contain hydrochloride, and the synthesized DMDAAC monomer has high purity.)
1. A process for synthesizing dimethyldiallylammonium chloride is characterized in that: in the existing aqueous solution, dimethylamine is subjected to tertiary amination, and tertiary amine is subjected to quaternary amination after separation and purification; the method specifically comprises the following steps:
s1: tertiary amination of dimethylamine:
a. adding a certain amount of dimethylamine into deionized water, and stirring in a cold water bath at 5-15 ℃ for standby application to obtain 0.5mol/L dimethylamine solution;
b. mixing Al (OH)3Mixing the sol with ammonia water to obtain mixed alkali liquor;
c. adding the mixed alkali liquor into a dimethylamine solution, uniformly stirring, then dropwise adding allyl chloride with the amount of dimethylamine and other substances into the mixed alkali liquor at the speed of 0.3-0.5mL/min, controlling the reaction temperature to be 0-15 ℃, and magnetically stirring until the content of the allyl chloride in a reaction system is less than or equal to 0.2 percent to obtain a solution after reaction;
d. adding the reacted solution into a separating funnel, separating a water phase and an oil phase, wherein the upper oil phase is crude tertiary amine;
s2: quaternization of dimethylamine:
a. drying, dehydrating and separating the crude tertiary amine by using anhydrous magnesium sulfate, adding the obtained tertiary amine and allyl chloride with the amount of dimethylamine and the like into an organic solvent with a certain volume, fully oscillating, standing for 20min at the temperature of 5-15 ℃ in a cold water bath, and separating out colorless needle crystals, namely a dimethyl diallyl ammonium chloride product;
b. and adding water into the obtained product to prepare an aqueous solution with the mass fraction of 40%, and decoloring by using activated carbon to obtain the dimethyl diallyl ammonium chloride.
2. The process of claim 1, wherein the Al (OH) is in the form of a salt3The concentration of the sol was 78 g/L.
3. The process for synthesizing dimethyldiallylammonium chloride as claimed in claim 1 wherein the concentration of the ammonia water is 1 mol/L.
4. The process of claim 1 wherein the organic solvent comprises one or more of acetone, carbon tetrachloride and tetrahydrofuran.
5. The process of claim 1, wherein the deionized water, Al (OH)3The volume ratio of the sol to the ammonia water to the organic solvent is 100: (15-20): (5-15): 50.
6. the use of dimethyldiallylammonium chloride prepared by the process according to any of claims 1 to 5 as a polymer monomer in the paper industry.
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis process of dimethyl diallyl ammonium chloride.
Background
Dimethyldiallylammonium chloride (hereinafter referred to as DMDAAC) is a cationic monomer with high practical value, and the polymer thereof has wide application in the fields of oil exploitation, paper making, mining, textile printing and dyeing, daily chemical industry and water treatment [ Hardy L.C. treatment of clay formation with organic cationic polymers [ J ] Macromolecules,1984,17: 975-; wang L K.use of poly (DMDAAC) as coarse slope sensitivity reducer [ J ]. Ind Eng Chem product Res,1997,16(11) 317-. The synthesis and polymerization of DMDAAC was studied by doctor George b. Subsequently, Calgon and Nalco chemical company in the United states improve the synthesis method, but all have the defects of long reaction time, high cost, sodium chloride in the product and the like. In the early 90 s of the 20 th century, people in the national Ming-Yan Mei and Wang-Yaqiong province and the like adopt a one-step method, namely dimethylamine and allyl chloride are reacted in the presence of sodium hydroxide in the next step, and the final product obtained by the method is a w (DMDAAC) 50-60% aqueous solution [ Ming-Yan Mei, Chen-Luo, Huguang, and the like ] synthetic identification and measurement of dimethyl diallyl ammonium chloride and polymerization research [ J ]. Ci' an institute of Petroleum institute, 1992,7(1): 58-62; the synthesis of Wangyueqiong, Wangbaocheng, Windilong, dimethyl diallyl ammonium chloride [ J ]. proceedings of Taiyuan university of industry, 1996,27(2):86-89 ].
With the progress of the research on the polymerization of DMDAAC, researchers found that in order to prepare a polymer with stable performance, relatively high quality and easy control, in addition to the initiator and process conditions in the polymerization, the purity of DMDAAC monomer has become one of the important factors affecting the polymer performance and relative molecular quality, and thus how to prepare DMDAAC monomer with high purity and low cost has become a new issue.
At present, the DMDAAC monomer mainly takes dimethylamine and propenyl chloride as raw materials, and in the traditional process, the generated tertiary amine is directly quaternized without separation, the tertiary amination reaction is incomplete, the residual quantity of the raw materials is large, and the purity of the DMDAAC monomer is low. HCl gas generated by tertiary amination is immediately combined with dimethylamine and tertiary amine to lose nucleophilicity, and generated impurities of dimethyl hydrochloride and tertiary amine hydrochloride hinder the reaction, so that the purity and the conversion rate of the monomer are reduced. Therefore, in the prior art, HCl generated by neutralization is generally added in the reaction process, but the dosage of NaOH is not easy to control, the dosage of NaOH is too much, the NaOH is easy to hydrolyze under the action of strong alkali to generate new impurities such as allyl alcohol, allyl aldehyde and the like with strong polymerization inhibition, the dosage of NaOH is too little, the HCl cannot be completely absorbed, and the yield of tertiary amine is reduced. Therefore, how to provide a new method for synthesizing dimethyldiallylammonium chloride, which does not need NaOH to participate in the reaction and can efficiently absorb HCl generated in the tertiary amination process, is very important for preventing the generation of reaction byproducts and improving the purity of the reaction byproducts.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a synthesis process of dimethyl diallyl ammonium chloride.
The technical scheme of the invention is summarized as follows:
a process for synthesizing dimethyl diallyl ammonium chloride comprises the following steps: firstly, carrying out tertiary amination on dimethylamine in an aqueous solution, and carrying out quaternary amination reaction on the tertiary amine after separation and purification; the method specifically comprises the following steps:
s1: tertiary amination of dimethylamine:
a. adding a certain amount of dimethylamine into deionized water, and stirring in a cold water bath at 5-15 ℃ for standby application to obtain 0.5mol/L dimethylamine solution;
b. mixing Al (OH)3Mixing the sol with ammonia water to obtain mixed alkali liquor;
c. adding the mixed alkali liquor into a dimethylamine solution, uniformly stirring, then dropwise adding allyl chloride with the amount of dimethylamine and other substances into the mixed alkali liquor at the speed of 0.3-0.5mL/min, controlling the reaction temperature to be 0-15 ℃, and magnetically stirring until the content of the allyl chloride in a reaction system is less than or equal to 0.2 percent to obtain a solution after reaction;
d. adding the reacted solution into a separating funnel, separating a water phase and an oil phase, wherein the upper oil phase is crude tertiary amine;
s2: quaternization of dimethylamine:
a. drying, dehydrating and separating the crude tertiary amine by using anhydrous magnesium sulfate, adding the obtained tertiary amine and allyl chloride with the amount of dimethylamine and the like into an organic solvent with a certain volume, fully oscillating, standing for 20min in a cold water bath at the temperature of 5-15 ℃, and separating out colorless needle crystals, namely a dimethyl diallyl ammonium chloride product;
b. and adding water into the obtained product to prepare an aqueous solution with the mass fraction of 40%, and decoloring by using activated carbon to obtain the dimethyl diallyl ammonium chloride.
Preferably, the Al (OH)3The concentration of the sol was 78 g/L.
Preferably, the concentration of the ammonia water is 1 mol/L.
Preferably, the organic solvent comprises one or more of acetone, carbon tetrachloride and tetrahydrofuran.
Preferably, the deionized water, Al (OH)3The volume ratio of the sol to the ammonia water to the organic solvent is 100: (15-20): (5-15): 50.
the dimethyl diallyl ammonium chloride prepared by the preparation method is used as a polymer monomer to be applied to the paper industry.
The invention has the beneficial effects that:
1. the invention adopts Al (OH) for the first time3Alkali liquor prepared from sol and ammonia waterInstead of NaOH neutralization, hydrolysis of allyl chloride is greatly avoided, byproducts such as allyl alcohol and allyl aldehyde are not generated, the yield and purity of tertiary amine are high, and the tertiary amination reaction equation is as follows: 6CH2＝CHCH2Cl+3(CH3)2NH+Al(OH)3→3(CH2＝CHCH2)2N+(CH3)2Cl－+AlCl3+3H2O；2CH2＝CHCH2Cl+(CH3)2NH+NH3·H2O→(CH2＝CHCH2)2N+(CH3)2Cl－+NH4Cl+H2O。
2. The invention carries out tertiary amination and quaternary amination step by step through a two-step method, and respectively controls the reaction time, the reaction temperature and other process parameters of the tertiary amination and the quaternary amination, and the reaction of each step is sufficient, in addition, the tertiary amination is carried out liquid separation and purification, the generated impurities such as aluminum chloride, ammonium chloride and the like are remained in the water phase, the separated tertiary amine is carried out quaternary amination, the quaternary amination product does not contain hydrochloride, the synthesized DMDAAC monomer has high purity, purification is not needed, and the DMDAAC monomer can be directly used as a polymer monomer to be applied to the paper industry.
Drawings
FIG. 1 is a flow diagram of a new process for the synthesis of dimethyldiallylammonium chloride;
FIG. 2 is a chart of the infrared absorption spectrum of a product synthesized by the new process for synthesizing dimethyldiallylammonium chloride in example 1-3;
FIG. 3 is a NMR spectrum of a product synthesized by the new process for dimethyldiallylammonium chloride in examples 1-3;
FIG. 4 is the NMR carbon spectrum of the product synthesized by the new process for the synthesis of dimethyldiallylammonium chloride in examples 1-3.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
S1: tertiary amination of dimethylamine:
a. adding 2.254g (0.05mol) of dimethylamine into 100mL of deionized water, and stirring in a cold water bath at 5 ℃ for standby to obtain 0.5mol/L dimethylamine solution;
b. 15mL of 78g/L Al (OH)3Mixing the sol with 15mL of 1mol/L ammonia water to obtain mixed alkali liquor;
c. adding the obtained mixed alkali liquor into the obtained dimethylamine solution, and uniformly stirring to obtain a mixed solution;
then using an automatic liquid adding injector to uniformly drop 3.826g (0.05mol) of allyl chloride into the obtained mixed solution, adjusting the injection speed to be 0.3mL/min, controlling the reaction temperature to be 5 ℃, and magnetically stirring until the content of the allyl chloride in the reaction system is less than or equal to 0.2 percent to obtain the solution after the reaction;
d. adding the reacted solution into a separating funnel, separating a water phase and an oil phase, wherein the upper oil phase is crude tertiary amine;
s2: quaternization of dimethylamine:
a. drying, dehydrating and separating the crude tertiary amine by using anhydrous magnesium sulfate, adding the obtained tertiary amine and 3.826g of allyl chloride into 50mL of acetone solvent, fully oscillating, standing for 20min at 5 ℃ in a cold water bath, separating colorless needle crystals, and filtering to obtain a dimethyl diallyl ammonium chloride product;
b. adding water into the obtained product to prepare an aqueous solution with the mass fraction of 40%, decoloring by using activated carbon to obtain a dimethyl diallyl ammonium chloride product, and analyzing by using an infrared spectrum and a nuclear magnetic resonance hydrogen spectrum and a carbon spectrum.
Example 2
S1: tertiary amination of dimethylamine:
a. adding 2.254g (0.05mol) of dimethylamine into 100mL of deionized water, and stirring in a cold water bath at 10 ℃ for standby to obtain 0.5mol/L dimethylamine solution;
b. 20mL of 78g/L Al (OH)3Mixing the sol with 5mL of 1mol/L ammonia water to obtain mixed alkali liquor;
c. adding the obtained mixed alkali liquor into the obtained dimethylamine solution, and uniformly stirring to obtain a mixed solution;
then using an automatic liquid adding injector to uniformly drop 3.826g (0.05mol) of allyl chloride into the obtained mixed solution, adjusting the injection speed to be 0.5mL/min, controlling the reaction temperature to be 10 ℃, and magnetically stirring until the content of the allyl chloride in the reaction system is less than or equal to 0.2 percent to obtain the solution after the reaction;
d. adding the reacted solution into a separating funnel, separating a water phase and an oil phase, wherein the upper oil phase is crude tertiary amine;
s2: quaternization of dimethylamine:
a. drying, dehydrating and separating the crude tertiary amine by using anhydrous magnesium sulfate, adding the obtained tertiary amine and 3.826g of allyl chloride into 50mL of carbon tetrachloride solvent, fully oscillating, standing for 20min at 10 ℃ in a cold water bath, separating colorless needle crystals, and filtering to obtain a dimethyl diallyl ammonium chloride product;
b. adding water into the obtained product to prepare an aqueous solution with the mass fraction of 40%, decoloring by using activated carbon to obtain a dimethyl diallyl ammonium chloride product, and analyzing by using an infrared spectrum and a nuclear magnetic resonance hydrogen spectrum and a carbon spectrum.
Example 3
S1: tertiary amination of dimethylamine:
a. adding 2.254g (0.05mol) of dimethylamine into 100mL of deionized water, and stirring in a cold water bath at the temperature of 5-15 ℃ for standby application to obtain 0.5mol/L dimethylamine solution;
b. 15mL of 78g/L Al (OH)3Mixing the sol with 10mL of 1mol/L ammonia water to obtain mixed alkali liquor;
c. adding the obtained mixed alkali liquor into the obtained dimethylamine solution, and uniformly stirring to obtain a mixed solution;
then using an automatic liquid adding injector to uniformly drop 3.826g (0.05mol) of allyl chloride into the obtained mixed solution, adjusting the injection speed to be 0.3mL/min, controlling the reaction temperature to be 15 ℃, and magnetically stirring until the content of the allyl chloride in the reaction system is less than or equal to 0.2 percent to obtain the solution after the reaction;
d. adding the reacted solution into a separating funnel, separating a water phase and an oil phase, wherein the upper oil phase is crude tertiary amine;
s2: quaternization of dimethylamine:
a. drying, dehydrating and separating the crude tertiary amine by using anhydrous magnesium sulfate, adding the obtained tertiary amine and 3.826g of allyl chloride into 50mL of tetrahydrofuran solvent, fully oscillating, standing for 20min at 15 ℃ in a cold water bath, separating colorless needle crystals, and filtering to obtain a dimethyl diallyl ammonium chloride product;
b. adding water into the obtained product to prepare an aqueous solution with the mass fraction of 40%, decoloring by using activated carbon to obtain a dimethyl diallyl ammonium chloride product, and analyzing by using an infrared spectrum and a nuclear magnetic resonance hydrogen spectrum and a carbon spectrum.
Comparative example 50mL of a 1mol/L NaOH solution was used in place of the mixed alkali solution of example 1, and the other preparation steps were the same as in example 1.
The following table shows the yields of examples 1 to 3 and comparative examples:
example 1
Example 2
Example 3
Comparative example
Yield of tertiary amine/%
98.6
99.1
98.3
64.5
DMDAAC yield/%
94.4
95.2
94.2
57.8
As can be seen from the above table, the present invention employs Al (OH)3The compound solution of the sol and ammonia water replaces the traditional NaOH, can obviously improve the yield of tertiary amine and DMDAAC, almost has no side reaction, and realizes the maximum utilization of reaction raw materials.
Examples 1-3 initial use of Al (OH)3The alkali liquor prepared by the sol and ammonia water replaces NaOH for neutralization, so that the hydrolysis of allyl chloride is greatly avoided, byproducts such as allyl alcohol and allyl aldehyde are not generated, the yield and the purity of tertiary amine are high, and the tertiary amination reaction equation is as follows: 6CH2＝CHCH2Cl+3(CH3)2NH+Al(OH)3→3(CH2＝CHCH2)2N+(CH3)2Cl－+AlCl3+3H2O；2CH2＝CHCH2Cl+(CH3)2NH+NH3·H2O→(CH2＝CHCH2)2N+(CH3)2Cl－+NH4Cl+H2O。
In examples 1 to 3, tertiary amination and quaternary amination are performed step by a two-step process, and process parameters such as reaction time, reaction temperature and the like of the tertiary amination and the quaternary amination are respectively controlled, and the reactions of the steps are sufficient.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
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