阅读说明：本技术 一种双季铵盐的连续化生产方法 (Continuous production method of biquaternary ammonium salt ) 是由 程终发 周响 李响 王宁宁 齐晓婧 陈成效 于 2019-11-06 设计创作，主要内容包括：本发明专利采用先生成单季铵盐中间体,再生成目标双季铵盐产品的生产方式,整个生产过程主要通过静态混合器和连续反应器来实现连续进料、连续混料、连续反应、连续出料的连续化生产。本发明专利生产方法简单,易于操作,可合成多种双季铵盐,通过连续化生产方式极大提高设备利用率,缩短生产周期。本发明在生产过程中避免了有机溶剂的使用和回收处理,整个过程无三废产生,绿色环保。(The invention adopts a production mode of firstly generating a single-quaternary ammonium salt intermediate and then generating a target biquaternary ammonium salt product, and continuous production of continuous feeding, continuous mixing, continuous reaction and continuous discharging is realized mainly through a static mixer and a continuous reactor in the whole production process. The production method is simple and easy to operate, can synthesize various biquaternary ammonium salts, greatly improves the utilization rate of equipment by a continuous production mode, and shortens the production period. The method avoids the use and recovery treatment of the organic solvent in the production process, does not generate three wastes in the whole process, and is green and environment-friendly.)

1. A continuous production method of biquaternary ammonium salt is characterized by comprising the following steps:

(1) reacting an amine R₁Premixing the linking group C and pure water, uniformly mixing the mixture through a primary static mixer at a constant speed, reacting the mixture through a primary continuous reactor, and obtaining an intermediate mono-quaternary ammonium salt aqueous solution after reaching the reaction end point;

(2) reacting the intermediate mono-quaternary ammonium salt with an amine R₂Continuously feeding the mixture into a secondary continuous reactor for reaction, obtaining a biquaternary ammonium salt water solution at the outlet of the secondary continuous reactor, and diluting the biquaternary ammonium salt water solution by pure water or alcohol to obtain biquaternary ammonium salt products with different content specifications.

2. The continuous production method of diquaternary ammonium salt according to claim 1, wherein the method comprisesIn that the amine R₁Amine R₂Is one of the following amines: alkyl dimethyl tertiary amine containing alkyl carbon chains of 10-20, alkyl imidazoline, pyridine and alkyl derivatives thereof, and quinoline and alkyl derivatives thereof; the connecting group C is straight-chain alkane with two halogenated ends, odd-carbon straight-chain alcohol with two halogenated ends, methyl/ethyl ether with two halogenated ends, epihalohydrin and the like; the alcohol is methanol or ethanol.

3. The continuous production method of diquaternary ammonium salt according to claim 1, wherein the feeding amine R is₁Amine R₂And the amount of the substance of the linking group C_{Amine R1}：n_{Amine R2}：n_c0.8 to 1.5: 0.8-1.5: 1, the feeding amount of the pure water is 10-50% of the total mass of other feeding materials.

4. The continuous production method of diquaternary ammonium salt according to claim 1, wherein the reaction temperature of the continuous reactor is controlled to be 60-120 ℃.

5. The continuous production method of diquaternary ammonium salt according to claim 1, wherein the reaction is terminated when the raw material liquid is changed from turbid to clear when the raw material liquid passes through the continuous reactor.

6. The continuous production method of diquaternary ammonium salt according to claim 1, wherein the continuous reactor is a closed tube reactor.

7. The continuous process for producing a diquaternary ammonium salt according to claim 1 or 6, wherein the two-stage static mixer, the aqueous solution of the intermediate monoquaternary ammonium salt and the amine R are charged in a two-stage continuous reactor₂And introducing the mixture into a second-stage static mixer for mixing, and then introducing the mixture into a second-stage continuous reactor for reaction.

Technical Field

The invention relates to the technical field of fine chemicals, in particular to a continuous production method of biquaternary ammonium salt.

Background

The biquaternary ammonium salt is a product developed on the basis of a single quaternary ammonium salt, belongs to a broad-spectrum bactericide, has stronger bactericidal capacity than the single quaternary ammonium salt such as 1227, has the same action principle as the single quaternary ammonium salt, is that positive charges in molecules are selectively adsorbed by bacteria with negative charges on the surface, and penetrate through the cell surface to enter a cell membrane through the permeation and diffusion effects, so that the semi-permeation effect of the cell membrane is influenced, and further penetrate into the cell to inactivate cellular enzymes, so that the proteins are denatured, and the bacterial cells are killed. Compared with single-quaternary ammonium salt, the double-quaternary ammonium salt bactericide has the characteristics of high efficiency, low toxicity, difficult influence of pH value change and the like, and has the characteristic of difficult generation of drug resistance. The structure of the biquaternary ammonium salt generally comprises three parts, namely an end hydrophobic group consisting of an alkyl chain or a heterocycle, a hydrophilic group consisting of two quaternary ammonium positive ions and a connecting group, wherein the connecting group generally comprises polymethylene, p-xylyl, polyoxyethylene and the like, is positioned in the middle of a biquaternary ammonium salt molecule and plays a role in connecting the two hydrophilic groups. In recent years, diquaternary ammonium salts have been used as bactericides in many fields such as fresh water, seawater, wastewater, industrial water treatment and the like, and from the practical application point of view, the use performance of the diquaternary ammonium salts is not generally superior to that of symmetric diquaternary ammonium salts.

At present, certain results have been obtained by research aiming at synthesis of the biquaternary ammonium salt, particularly on the situation that the biquaternary ammonium salt is not synthesized. CN101531635B discloses an imidazoline asymmetric biquaternary ammonium salt and a preparation method thereof, the method synthesizes alkyl imidazoline with diethylenetriamine and long-chain alkyl organic acid under the condition of xylene, synthesizes an N- (3-chlorine-2-hydroxypropyl) -N, N-dimethyl long-chain alkyl quaternary ammonium salt intermediate with long-chain alkyl tertiary amine and epoxy chloropropane under the condition of ethanol, and then synthesizes the imidazoline asymmetric biquaternary ammonium salt with alkyl imidazoline under the condition of ethanol. Bin and the like synthesize an asymmetric biquaternary ammonium salt containing an imidazoline ring by taking imidazoline as a matrix and epoxy chloropropane as a linking group (fine chemical industry, 2009). Meanwhile, the diquaternary ammonium salt containing asymmetric alkyl fatty chain is also becoming a research hotspot. Lijie et al synthesized an intermediate long-chain tertiary amine from dodecylamine, formic acid and formaldehyde, and synthesized a bis-quaternary ammonium salt bactericide with 1, 3-dibromopropane under the condition of ethanol (chemical engineer, 2005). According to the royal jelly and the like, a C10-C2-C12 type asymmetric biquaternary ammonium salt surfactant (Zhengzhou university report, 2010) is synthesized by using dodecyl dimethyl tertiary amine, dodecyl dimethyl tertiary amine and 1, 2-dibromoethane under the condition of isopropanol. Xuqu et al in the synthesis of a new gemini surfactant, dodecyl dimethyl tertiary amine, hydrochloric acid, epichlorohydrin are used to synthesize a series of asymmetric biquaternary ammonium salts containing longer hydrophobic chains with different alkyl chain alkyl tertiary amines under the condition of ethanol (West Waals university report, 2004). Xuqu and the like utilize long-chain alkyl tertiary amine, hydrochloric acid and epichlorohydrin to generate intermediate long-chain alkyl single-quaternary ammonium salt, lauric acid and 2-dimethylethanol are used as solvents, dimethyl lauric acid ethyl tertiary amine is synthesized by esterification, and then the intermediate long-chain alkyl single-quaternary ammonium salt is synthesized into the ester group-containing asymmetric biquaternary ammonium salt (fine chemical industry, 2004). The synthesis process related to the biquaternary ammonium salt has made a certain progress, but is not mature enough, and the synthesis process generally has the problems of long reaction period and large use of organic solvent, so that the production cost of the existing process is high, the resource utilization rate is low, the environmental protection treatment cost is high, and the large-scale industrial production of the biquaternary ammonium salt product is limited.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides a continuous production method of the biquaternary ammonium salt, which is continuous, green and environment-friendly.

A continuous production method of biquaternary ammonium salt specifically comprises the following steps:

(1) reacting an amine R₁The linking group C and the pure water are premixed and then pass through the first stage at a constant speedUniformly mixing in a static mixer, reacting in a first-stage continuous reactor, and obtaining an intermediate mono-quaternary ammonium salt aqueous solution after reaching the reaction end point;

(2) reacting the intermediate mono-quaternary ammonium salt with an amine R₂Continuously feeding the mixture into a secondary continuous reactor for reaction, obtaining a biquaternary ammonium salt water solution at the outlet of the secondary continuous reactor, and diluting the biquaternary ammonium salt water solution by pure water or alcohol to obtain biquaternary ammonium salt products with different content specifications.

Wherein the amine R₁Amine R₂Is one of the following amines: alkyl dimethyl tertiary amine containing alkyl carbon chains of 10-20, alkyl imidazoline, pyridine and alkyl derivatives thereof, and quinoline and alkyl derivatives thereof; the connecting group C is straight-chain alkane with two halogenated ends, odd-carbon straight-chain alcohol with two halogenated ends, methyl/ethyl ether with two halogenated ends, epihalohydrin and the like; the alcohol is methanol or ethanol.

Wherein the feed amine R₁Amine R₂And the amount of the substance of the linking group C_{Amine R1}：n_{Amine R2}：n_c0.8 to 1.5: 0.8-1.5: 1, preferably n_{Amine R1}：n_{Amine R2}：n_cIs (0.9-1.2): (0.9-1.2): 1, more preferably n_{Amine R1}：n_{Amine R2}：n_cIs (0.95-1.05): (0.95-1.05): 1.

the feeding amount of the pure water is 10-50% of the total mass of other feeding materials.

Wherein the reaction temperature of the continuous reactor is controlled to be 60-120 ℃. Preferably 80-120 DEG C

Wherein, when the raw material passes through the continuous reactor, the reaction end point is that the raw material liquid is changed from turbid to clear.

Wherein, the continuous reactor is a closed tube reactor.

Wherein, a secondary static mixer, an intermediate single-quaternary ammonium salt aqueous solution and amine R are added in a secondary continuous reactor₂And introducing the mixture into a second-stage static mixer for mixing, and then introducing the mixture into a second-stage continuous reactor for reaction.

The asymmetric quaternary ammonium salt is industrially and continuously synthesized, the alcohol solvent used in the prior art is removed, water is used as one of the raw materials, the single-phase reaction in the prior art is changed into two-phase reaction, the reaction speed is increased, and the reaction balance is changed; the reaction end point is easy to be clear and convenient to master the reaction progress.

The raw materials are uniformly mixed in the first-stage static mixer, so that the phenomenon that the concentration ratio of local raw materials is too high and side reaction products are generated is prevented. And uniformly mixing the oil phase (raw material) and the water phase (quaternary ammonium salt intermediate) in a secondary static mixer, increasing the contact area of the two phases and preventing local reaction overheating and insufficient reaction.

The beneficial effects of the invention are as follows:

1. the invention realizes the industrialized flow line production of continuous feeding, continuous mixing, continuous reaction and continuous discharging through the static mixer and the continuous reactor;

2. the pure water is adopted as one of the raw materials, so that the use of an organic solvent in the prior art is avoided, the yield is improved, and the reaction end point can be determined through the turbidity degree of the raw materials, so that the reaction time in the continuous reactor is controlled.

Drawings

FIG. 1 is a reaction scheme of the present invention.

Detailed Description