CN111039793A - Method for continuously synthesizing dimethyl diallyl ammonium chloride - Google Patents
Method for continuously synthesizing dimethyl diallyl ammonium chloride Download PDFInfo
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- CN111039793A CN111039793A CN201811189766.3A CN201811189766A CN111039793A CN 111039793 A CN111039793 A CN 111039793A CN 201811189766 A CN201811189766 A CN 201811189766A CN 111039793 A CN111039793 A CN 111039793A
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- dimethylamine
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- ammonium 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
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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Abstract
The invention relates to a method for continuously synthesizing dimethyl diallyl ammonium chloride, which comprises the steps of adding a dimethylamine aqueous solution, a sodium hydroxide solution and chloropropene into a microreactor, and staying in the microreactor for 5-15 minutes. Controlling the temperature at 30-70 ℃, collecting reaction liquid, standing for layering, carrying out liquid separation, taking a lower-layer water phase, adjusting the pH of the water phase to 4-6 by using dilute hydrochloric acid, and filtering to remove precipitated sodium chloride to obtain clear liquid. And distilling the clear liquid under reduced pressure to remove impurities in the water phase, and filtering again to remove precipitated sodium chloride to obtain the dimethyl diallyl ammonium chloride solution. The invention solves the problems of repeated heating and cooling, alternate feeding, difficult temperature control, long reaction time and the like in the synthesis process of the dimethyl diallyl ammonium chloride.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and relates to a method for continuously producing dimethyl diallyl ammonium chloride.
Background
Dimethyl diallyl ammonium chloride is one of the most practical cationic monomers at present, the double bonds in molecules can cause the cationic monomers to generate polymerization reaction, and the homopolymer and the copolymer thereof have the advantages of high or adjustable positive charge density on a macromolecular chain, good water solubility, stable cationic structural units, easy control of relative molecular mass, high efficiency, no toxicity and the like, and are widely applied to various fields of petroleum exploitation, textile printing and dyeing, papermaking, daily chemical industry, water treatment and the like.
The synthesis process of the dimethyl diallyl ammonium chloride is various, and at present, domestic production processes are mainly alternate feeding and repeated temperature rising and falling, are difficult to control, are complex to operate, have poor field working environment and the like.
Sequentially dropwise adding allyl chloride, a sodium hydroxide aqueous solution and the rest allyl chloride into a dimethylamine aqueous solution at room temperature (20-30 ℃) under the stirring condition, adding solid sodium hydroxide, and reacting for 1 h; taking the upper oil phase, drying with sodium hydroxide solid particles, distilling, and taking 59-62 ℃ fractions as a crude tertiary amine product; drying and fractionating to obtain a fraction at 61.5-62.5 ℃ which is an intermediate product tertiary amine, wherein the yield is about 70%. Taking tertiary amine and allyl chloride refined by distillation to react in acetone subjected to distillation for 72 hours, filtering to obtain crystals, washing with cold acetone, and drying in vacuum at 60-70 ℃ to obtain a dimethyldiallylammonium chloride crystal product, wherein the yield is about 92.8%. The total yield of the two-step reaction of dimethyldiallylammonium chloride was about 64.9%.
The temperature at which the feed is added is higher (> 50 ℃) in US2923701, and more impurities are formed during the reaction. The crude product is refined by adopting a method of vacuum extraction and activated carbon filtration, and the synthesis period is as long as 42 hours.
US4151202 uses a filtered water washing process to purify chloropropene, and then reacts with dimethylamine at a higher temperature (about 47 ℃) to synthesize DMDAAC, wherein the reaction process is complex, the synthesis period is long and is about 30 hours.
In the one-step preparation process of dimethyl diallyl ammonium chloride, US3461163 adopts a method of adding chloropropene and dimethylamine according to the mass ratio of the same substances at low temperature (0-5 ℃) for reaction, and then alternately adding 50% of sodium hydroxide and chloropropene. Because the feeding temperature is low, a large amount of refrigerant needs to be added, and the energy consumption of the refrigeration equipment is high. The crude product is refined by adopting a method of vacuum extraction and activated carbon filtration, and the synthesis period is as long as 30 hours.
JP56016448 removes some unknown impurities in dimethyl diallyl ammonium chloride solution by high-temperature steam stripping, improves the polymerization reaction performance of dimethyl diallyl ammonium chloride, but new side reactions may be caused by over-alkaline medium conditions with the pH value of 10.5-11.5 and the high-temperature steam stripping at 110 DEG C
The synthesis technology adopted by the invention solves the difficult problems of repeated temperature rise, temperature reduction, alternate feeding and difficult temperature control in the prior art, and the process method is simple, simultaneously, the feeding is synthesized in one step, the conversion rate of raw materials is greatly improved, the operation is simple and convenient, and the process is safe and environment-friendly. The process has high economic and social benefits for the development of the dimethyl diallyl ammonium chloride.
Disclosure of Invention
The technical scheme of the invention is as follows: a method for continuously producing dimethyldiallylammonium chloride.
The main technical scheme of the method comprises the following contents:
a method for continuously synthesizing dimethyl diallyl ammonium chloride is characterized in that dimethylamine, sodium hydroxide and chloropropene are added into a microreactor to react, the residence time and the temperature are controlled, reaction liquid is collected and layered, a lower-layer water phase is taken out, the pH value is adjusted, precipitated sodium chloride is removed by filtration, clarified liquid is obtained and subjected to reduced pressure distillation, and the solution is filtered again to obtain the dimethyl diallyl ammonium chloride solution.
The dimethylamine is 40% aqueous solution, the sodium hydroxide is 20% aqueous solution, and the material ratio is dimethylamine: sodium hydroxide: the mol ratio of chloropropene is 1 (1-2) to (1-2.1).
And simultaneously feeding the materials of dimethylamine solution, sodium hydroxide solution and chloropropene solution.
The reaction time is 3-15 minutes.
The reaction temperature is within the range of 30-70 ℃.
And standing the reaction solution for layering, separating liquid, taking a lower-layer water phase, and adjusting the pH of the water phase to 4-6 by using dilute hydrochloric acid.
The reaction system is carried out in a micro reactor, resistance drop is generated in the micro reactor, and the resistance drop is controlled within 0.6 MPa.
The conversion rate of dimethylamine can reach more than 95 percent, and the product yield can reach more than 92 percent.
The invention solves the problems of repeated heating and cooling, alternate feeding, difficult temperature control, long reaction time and the like in the synthesis process of the dimethyl diallyl ammonium chloride.
The reaction of the invention is carried out in a microflow field, the temperature of the microflow field is controlled by water bath or heat conducting oil, the flow rate and material ratio of reactants is accurately controlled by an injection pump, and finally the effluent reaction liquid is collected. The continuous injection of reactants into the micro-flow field is realized for reaction, so that the product can be obtained by continuous operation.
Detailed Description
The process of the present invention is described in detail below with reference to examples.
Example 1
Adding 40% dimethylamine aqueous solution, 20% sodium hydroxide solution and chloropropene into a microreactor by using a pump according to a molar ratio of dimethylamine, sodium hydroxide and chloropropene of 1:1:2.1, standing for 5 minutes in the microreactor, controlling the temperature to be 30 ℃, collecting reaction liquid, standing for layering, layering the reaction liquid, separating the liquid, and recovering the upper layer; taking the lower water phase, adjusting the pH value of the water phase to 5 by using dilute hydrochloric acid, filtering to remove precipitated sodium chloride to obtain clear liquid, distilling the clear liquid under reduced pressure to remove impurities in the water phase, and filtering again to remove the precipitated sodium chloride to obtain the dimethyldiallylammonium chloride solution. The conversion rate of dimethylamine is calculated according to the content of dimethylamine in the mother liquor detected by gas chromatography. The conversion rate of dimethylamine can reach 95.3 percent, and the product yield can reach 92.2 percent.
Example 2
Adding 40% dimethylamine aqueous solution, 20% sodium hydroxide solution and chloropropene into a microreactor by using a pump according to a molar ratio of dimethylamine, sodium hydroxide and chloropropene of 1:1:2.1, standing for 5 minutes in the microreactor, controlling the temperature at 40 ℃, then collecting reaction liquid, standing, layering, separating liquid, recovering an upper layer, taking a lower-layer water phase, adjusting the pH of the water phase to 5 by using dilute hydrochloric acid, filtering to remove precipitated sodium chloride to obtain clear liquid, distilling the clear liquid under reduced pressure to remove impurities in the water phase, and filtering again to remove the precipitated sodium chloride to obtain the dimethyl diallyl ammonium chloride solution. The conversion rate of dimethylamine is calculated according to the content of dimethylamine in the mother liquor detected by gas chromatography. The conversion rate of dimethylamine can reach 95.6 percent, and the product yield can reach 92.2 percent.
Example 3
Adding 40% dimethylamine aqueous solution, 20% sodium hydroxide solution and chloropropene into a microreactor by using a pump according to a molar ratio of dimethylamine, sodium hydroxide and chloropropene of 1:1:2.1, standing for 7 minutes in the microreactor, controlling the temperature to be 50 ℃, collecting reaction liquid, standing for layering, layering the reaction liquid, separating the liquid, and recovering the upper layer; and taking the lower-layer water phase, adjusting the pH of the water phase to 4-6 by using dilute hydrochloric acid, filtering to remove precipitated sodium chloride to obtain a clear liquid, distilling the clear liquid under reduced pressure to remove impurities in the water phase, and filtering again to remove the precipitated sodium chloride to obtain the dimethyldiallylammonium chloride solution. The conversion rate of dimethylamine is calculated according to the content of dimethylamine in the mother liquor detected by gas chromatography. The conversion rate of dimethylamine can reach 96.1 percent, and the product yield can reach 92.1 percent.
Example 4
Adding 40% dimethylamine aqueous solution, 20% sodium hydroxide solution and chloropropene into a microreactor by using a pump according to a molar ratio of dimethylamine, sodium hydroxide and chloropropene of 1:1:2.1, standing for 9 minutes in the microreactor, controlling the temperature to be 60 ℃, collecting reaction liquid, standing for layering, layering the reaction liquid, separating the liquid, and recovering the upper layer; taking the lower water phase, adjusting the pH value of the water phase to 6 by using dilute hydrochloric acid, filtering to remove precipitated sodium chloride to obtain clear liquid, distilling the clear liquid under reduced pressure to remove impurities in the water phase, and filtering again to remove the precipitated sodium chloride to obtain the dimethyldiallylammonium chloride solution. The conversion rate of dimethylamine is calculated according to the content of dimethylamine in the mother liquor detected by gas chromatography. The conversion rate of dimethylamine can reach 96.7 percent, and the product yield can reach 92.3 percent.
Example 5
Adding 40% dimethylamine aqueous solution, 20% sodium hydroxide solution and chloropropene into a microreactor by using a pump according to a molar ratio of dimethylamine, sodium hydroxide and chloropropene of 1:1:2.1, standing for 5 minutes in the microreactor, controlling the temperature to be 70 ℃, collecting reaction liquid, standing for layering, layering the reaction liquid, separating the liquid, and recovering the upper layer; taking the lower water phase, adjusting the pH value of the water phase to 6 by using dilute hydrochloric acid, filtering to remove precipitated sodium chloride to obtain clear liquid, distilling the clear liquid under reduced pressure to remove impurities in the water phase, and filtering again to remove the precipitated sodium chloride to obtain the dimethyldiallylammonium chloride solution. The conversion rate of dimethylamine is calculated according to the content of dimethylamine in mother liquor detected by gas chromatography, and the concentration of product solution is titrated by sodium thiosulfate solution. The conversion rate of dimethylamine can reach 98.7 percent, and the product yield can reach 92.6 percent.
Example 6
Adding 40% dimethylamine aqueous solution, 20% sodium hydroxide solution and chloropropene into a microreactor by using a pump according to a molar ratio of dimethylamine, sodium hydroxide and chloropropene of 1:1:2.1, standing for 12 minutes in the microreactor, controlling the temperature at 45 ℃, collecting reaction liquid, standing for layering, separating liquid, and recovering the upper layer; taking the lower water phase, adjusting the pH of the water phase to 4 by using dilute hydrochloric acid, filtering to remove precipitated sodium chloride to obtain a clear liquid, distilling the clear liquid under reduced pressure to remove impurities in the water phase, and filtering again to remove the precipitated sodium chloride to obtain the dimethyldiallylammonium chloride solution. The conversion rate of dimethylamine is calculated according to the content of dimethylamine in the mother liquor detected by gas chromatography. The conversion rate of dimethylamine can reach 95.3 percent, and the product yield can reach 92.2 percent.
Example 7
Adding 40% dimethylamine aqueous solution, 20% sodium hydroxide solution and chloropropene into a microreactor by using a pump according to a molar ratio of dimethylamine, sodium hydroxide and chloropropene of 1:1:2.1, standing for 15 minutes in the microreactor, controlling the temperature to be 55 ℃, collecting reaction liquid, standing for layering, separating liquid, and recovering the upper layer; and taking the lower-layer water phase, adjusting the pH of the water phase to 4-6 by using dilute hydrochloric acid, filtering to remove precipitated sodium chloride to obtain a clear liquid, distilling the clear liquid under reduced pressure to remove impurities in the water phase, and filtering again to remove the precipitated sodium chloride to obtain the dimethyldiallylammonium chloride solution. The conversion rate of dimethylamine is calculated according to the content of dimethylamine in the mother liquor detected by gas chromatography. The conversion rate of dimethylamine can reach 96.5 percent, and the product yield can reach 92.1 percent.
Claims (8)
1. A method for continuously synthesizing dimethyl diallyl ammonium chloride is characterized in that dimethylamine, sodium hydroxide and chloropropene are added into a microreactor to react, the residence time and the temperature are controlled, reaction liquid is collected and layered, a lower-layer water phase is taken out, the pH value is adjusted, precipitated sodium chloride is removed by filtration, clarified liquid is obtained and subjected to reduced pressure distillation, and the solution is filtered again to obtain the dimethyl diallyl ammonium chloride solution.
2. The method of claim 1, wherein the dimethylamine is a 40% solution in water, the sodium hydroxide is a 20% solution in water, and the ratio of dimethylamine: sodium hydroxide: the mol ratio of chloropropene is 1 (1-2) to (1-2.1).
3. The process of claim 1, wherein the materials dimethylamine solution, sodium hydroxide solution, and chloropropene solution are fed simultaneously.
4. The method of claim 1, wherein the reaction time is 3 to 15 minutes.
5. The process according to claim 1, wherein the reaction temperature is in the range of 30 to 70 ℃.
6. The method according to claim 1, wherein the reaction solution is allowed to stand for layering, subjected to liquid separation, and the aqueous phase of the lower layer is taken out and the pH of the aqueous phase is adjusted to 4 to 6 with dilute hydrochloric acid.
7. The method of claim 1, wherein the reaction system is carried out in a microreactor and the resistance in the microreactor is controlled to fall within 0.6 MPa.
8. The process of claim 1, wherein the conversion of dimethylamine is greater than 95% and the product yield is greater than 92%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456075A (en) * | 2022-02-22 | 2022-05-10 | 山东蓝湾新材料有限公司 | Industrial synthesis method of dimethyl diallyl ammonium chloride |
| CN114539076A (en) * | 2022-03-28 | 2022-05-27 | 苏州市晶协高新电子材料有限公司 | Continuous synthesis device and process of dimethyl diallyl ammonium chloride |
| WO2023281078A1 (en) * | 2021-07-09 | 2023-01-12 | Spcm Sa | Process for obtaining bio-sourced diallyldialkylammonium halide |
Citations (3)
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| CN101648878A (en) * | 2009-06-30 | 2010-02-17 | 山东宝莫生物化工股份有限公司 | Preparation method of dimethyldiallylammonium chloride with low salt |
| CN104370754A (en) * | 2014-10-20 | 2015-02-25 | 南京工业大学 | Method for preparing dimethyl diallyl ammonium chloride |
| CN108329217A (en) * | 2018-04-10 | 2018-07-27 | 山东滨州嘉源环保有限责任公司 | A kind of method that a step produces 60% dimethyl diallyl ammonium chloride solution |
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2018
- 2018-10-12 CN CN201811189766.3A patent/CN111039793A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648878A (en) * | 2009-06-30 | 2010-02-17 | 山东宝莫生物化工股份有限公司 | Preparation method of dimethyldiallylammonium chloride with low salt |
| CN104370754A (en) * | 2014-10-20 | 2015-02-25 | 南京工业大学 | Method for preparing dimethyl diallyl ammonium chloride |
| CN108329217A (en) * | 2018-04-10 | 2018-07-27 | 山东滨州嘉源环保有限责任公司 | A kind of method that a step produces 60% dimethyl diallyl ammonium chloride solution |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023281078A1 (en) * | 2021-07-09 | 2023-01-12 | Spcm Sa | Process for obtaining bio-sourced diallyldialkylammonium halide |
| FR3125039A1 (en) * | 2021-07-09 | 2023-01-13 | Snf Sa | Process for obtaining biobased diallyldialkylammonium halide |
| CN114456075A (en) * | 2022-02-22 | 2022-05-10 | 山东蓝湾新材料有限公司 | Industrial synthesis method of dimethyl diallyl ammonium chloride |
| CN114539076A (en) * | 2022-03-28 | 2022-05-27 | 苏州市晶协高新电子材料有限公司 | Continuous synthesis device and process of dimethyl diallyl ammonium chloride |
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