阅读说明：本技术 一种活性溴季铵盐、制备方法及应用 (Active bromine quaternary ammonium salt, preparation method and application ) 是由 李涛 刘伟 王涛 吴丹 张辉 黄西平 张琦 周筝 李亚红 于 2019-02-28 设计创作，主要内容包括：本发明公开了一种活性溴季铵盐,所述活性溴季铵盐具有式(Ⅰ)所示的结构通式或式(Ⅱ)所示的结构通式：<Image he="190" wi="454" file="DDA0001981415020000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R<Sub>1</Sub>为C<Sub>12</Sub>～C<Sub>16</Sub>的烷基,R<Sub>2</Sub>和R<Sub>4</Sub>均为甲基,R<Sub>3</Sub>为甲基、苄基或对溴苯氧乙基；<Image he="175" wi="494" file="DDA0001981415020000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R<Sub>1</Sub>为C<Sub>12</Sub>～C<Sub>16</Sub>的烷基。还公开了其制备方法,包括以下步骤：步骤1制备得到有机溴化铵溶液,步骤2,向所述有机溴化铵溶液中加入NaBr,步骤3,向步骤2完成后制得的混合物中加入过硫酸氢钾复合盐水溶液,步骤4,过滤,重结晶得到所述活性溴季铵盐。本发明制备的活性溴季铵盐可作为杀菌剂,具有工艺简单,合成过程无副产物生成,产品稳定性好、活性溴含量高、杀菌能力强,是一种安全、高效的水处理药剂等特点。(The invention discloses active bromineThe quaternary ammonium salt of active bromine has a structural general formula shown in a formula (I) or a structural general formula shown in a formula (II): wherein R is 1 Is C 12 ～C 16 Alkyl of R 2 And R 4 Are each methyl, R 3 Is methyl, benzyl or p-bromophenoxyethyl; wherein R is 1 Is C 12 ～C 16 Alkyl group of (1). Also discloses a preparation method thereof, which comprises the following steps: step 1, preparing an organic ammonium bromide solution, step 2, adding NaBr into the organic ammonium bromide solution, step 3, adding a potassium hydrogen persulfate composite salt aqueous solution into the mixture prepared after the step 2 is finished, and step 4, filtering and recrystallizing to obtain the active bromine quaternary ammonium salt. The active bromine quaternary ammonium salt prepared by the invention can be used as a bactericide, and has the characteristics of simple process, no byproduct generated in the synthetic process, good product stability, high active bromine content, strong bactericidal capability, safety, high efficiency and the like.)

1. An active bromine quaternary ammonium salt, which is characterized in that the active bromine quaternary ammonium salt has a structural general formula shown in a formula (I) or a structural general formula shown in a formula (II):

wherein R is₁Is C₁₂～C₁₆Alkyl of R₂And R₄Are each methyl, R₃Is methyl, benzyl or p-bromophenoxyethyl;

2. The method for preparing the active bromine quaternary ammonium salt according to claim 1, which comprises the following steps:

step 1, dissolving organic ammonium bromide by using a solvent to prepare an organic ammonium bromide solution, wherein the mass ratio of the solvent to the organic ammonium bromide is 20-80: 1;

step 2, adding NaBr into the organic ammonium bromide solution, stirring for 0.1-0.5 hour at the stirring speed of 200-800 rpm, wherein the molar mass ratio of NaBr to organic ammonium bromide is 2-4: 1;

step 3, adding a potassium hydrogen persulfate composite salt aqueous solution into the mixture prepared after the step 2 is finished, wherein the stirring speed is 200-800 rpm, and continuing to react for 0.2-0.5 hours after the potassium hydrogen persulfate composite salt aqueous solution is added, so as to obtain a reaction product, wherein the molar mass ratio of the added potassium hydrogen persulfate composite salt to the organic ammonium bromide is 1-3: 1, and the mass content of the potassium hydrogen persulfate composite salt in the potassium hydrogen persulfate composite salt aqueous solution is 15-30%;

step 4, filtering the reaction product finally obtained in the step 3, and recrystallizing a filter cake by using an organic solvent to obtain the active bromine quaternary ammonium salt;

wherein the organic ammonium bromide has a general structural formula shown in a formula (III) or a general structural formula shown in a formula (IV):

wherein R is₁Is C₁₂～C₁₆Alkyl of R₂And R₄Are each methyl, R₃Is methyl, benzyl or p-bromophenoxyethyl;

wherein R is₁Is C₁₂～C₁₆Alkyl group of (1).

3. The method according to claim 2, wherein the solvent is water in step 1.

4. The process according to claim 2, wherein in the step 3, the aqueous solution of oxone complex salt is added dropwise to the mixture obtained after completion of the step 2.

5. The method according to claim 2, wherein in step 4, the organic solvent is methanol or acetonitrile.

6. The preparation method according to claim 2, wherein in the step 4, the recrystallization process comprises the steps of adopting methanol or acetonitrile with the mass of 1-5 times of that of the filter cake, recrystallizing for 1-3 min under the action of ultrasonic waves, and filtering to obtain the active bromine quaternary ammonium salt.

7. The method for preparing the active bromine quaternary ammonium salt according to claim 1, which comprises the following steps:

step 1, dissolving organic ammonium bromide by using water to prepare an organic ammonium bromide solution, wherein the mass ratio of the water to the organic ammonium bromide is 50: 1;

step 2, adding NaBr into the organic ammonium bromide solution, stirring for 0.1-0.3 hours at a stirring speed of 300-600 rpm, wherein the molar mass ratio of NaBr to organic ammonium bromide is 2-3: 1;

step 3, dropwise adding a potassium hydrogen persulfate composite salt aqueous solution into the mixture prepared in the step 2, wherein the stirring speed is 300-600 rpm, and continuing to react for 0.25 hour after the potassium hydrogen persulfate composite salt aqueous solution is added, so as to obtain a reaction product, wherein the mass content of the potassium hydrogen persulfate composite salt in the potassium hydrogen persulfate composite salt aqueous solution is 20%, and the molar mass ratio of the added potassium hydrogen persulfate composite salt to the organic ammonium bromide is 1-2: 1;

step 4, filtering the reaction product finally obtained in the step 3, and recrystallizing a filter cake by adopting methanol to obtain the active bromine quaternary ammonium salt;

wherein the organic ammonium bromide is represented by the general structural formula (III) or the general structural formula (IV):

wherein R is₁Is C₁₂～C₁₆Alkyl of R₂And R₄Are each methyl, R₃Is methyl, benzyl or p-bromophenoxyethyl;

8. Use of the active quaternary ammonium bromide salt according to claim 1 in seawater sterilization.

9. The use of the active quaternary ammonium bromide salt in seawater sterilization according to claim 8, wherein the active quaternary ammonium bromide salt is added into seawater by an intermittent feeding manner.

10. The application of the active bromine quaternary ammonium salt in seawater sterilization according to claim 8, wherein the adding amount of the active bromine quaternary ammonium salt is 20-30 mg/L of seawater.

Technical Field

The invention belongs to the technical field of organic chemistry, and particularly relates to an active bromine quaternary ammonium salt and application thereof.

Background

With the development of the world economic society, the problem of water resources is increasingly serious, and the problem of solving the water resource shortage becomes a common problem in the world. In the face of the shortage of fresh water resources in coastal cities in China, the development and utilization of seawater to replace fresh water as industrial water, particularly as industrial cooling water, is one of important ways for solving the crisis problem of the fresh water resources in the coastal cities and regions. The pollution of industrial circulating water systems is mainly caused by microorganisms therein. On the one hand, microorganisms cause direct pollution of the water body; on the other hand, the microorganisms in the industrial circulating water bring great harm to equipment, a large amount of slime produced by the microorganisms causes corrosion in the circulating water, the slime is accumulated to generate scale to block heat conduction, and the pipeline can be seriously blocked. Therefore, the control and treatment of the microorganisms in the industrial circulating water can not only control the deterioration of water quality, but also reduce energy consumption and prolong the service life of instruments and equipment, and is the key of the treatment of the circulating cooling water.

At present, the industries of chemical industry, petrifaction, electric power, metallurgy and the like in coastal cities and brackish water areas in China begin to utilize seawater or brackish water to replace fresh water for circulating cooling. Because the quality of seawater or brackish water is complex, the seawater or brackish water has the characteristics of high salinity, strong alkalinity and large temperature range, and the traditional chlorine bactericide cannot meet the requirement of a cooling water system on bacteria control along with the rapid development of water treatment technology and the increasing strictness of discharge standards. The sterilization mechanism of the bromine bactericide is similar to that of the chlorine bactericide, but compared with the chlorine bactericide, the bromine bactericide has incomparable advantages in the aspects of sterilization effect, application conditions, environmental protection factors and the like, so the bromine bactericide is a good substitute for the chlorine bactericide.

The active bromine bactericide is most widely applied in bromine bactericides. The active bromine is a bromine species with a valence state of +1, and the active bromine bactericide is a compound or compound capable of releasing the bromine species with the valence state of +1 in a water body. Compounds with N-Br and C-Br bonds and complexes formed by bromine and N-, O-nucleophiles can be used as sources of active bromine, but the compounds are generally poor in water solubility, have pungent odor and are unstable.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a novel active bromine quaternary ammonium salt and application of the active bromine quaternary ammonium salt in the field of seawater sterilization.

The invention is realized by the following technical scheme:

an active bromine quaternary ammonium salt has a structural general formula shown as a formula (I) or a structural general formula shown as a formula (II):

wherein R is₁Is C₁₂～C₁₆Alkyl of R₂And R₄Are each methyl, R₃Is methyl, benzyl or p-bromophenoxyethyl;

wherein R is₁Is C₁₂～C₁₆Alkyl group of (1).

A preparation method of active bromine quaternary ammonium salt comprises the following steps:

step 1, dissolving organic ammonium bromide by using a solvent to prepare an organic ammonium bromide solution, wherein the mass ratio of the solvent to the organic ammonium bromide is 20-80: 1;

step 2, adding NaBr into the organic ammonium bromide solution, stirring for 0.1-0.5 hour at the stirring speed of 200-800 rpm, wherein the molar mass ratio of NaBr to organic ammonium bromide is 2-4: 1;

step 3, adding an oxone aqueous solution into the mixture prepared after the step 2 is finished, wherein the stirring speed is 200-800 rpm, and continuing to react for 0.2-0.5 hours after the oxone aqueous solution is added, so as to obtain a reaction product, wherein the molar mass ratio of the added oxone to the organic ammonium bromide is 1-3: 1, and the mass content of the added oxone in the oxone aqueous solution is 15-30%;

step 4, filtering the reaction product finally obtained in the step 3, and recrystallizing a filter cake by using an organic solvent to obtain the active bromine quaternary ammonium salt;

wherein the organic ammonium bromide has a general structural formula shown in a formula (III) or a general structural formula shown in a formula (IV):

wherein R is₁Is C₁₂～C₁₆Alkyl of R₂And R₄Are each methyl, R₃Is methyl, benzyl or p-bromophenoxyethyl;

wherein R is₁Is C₁₂～C₁₆Alkyl group of (1).

In the above technical solution, in step 1, the solvent is water.

In the above technical scheme, in the step 3, the aqueous solution of oxone is added to the mixture obtained after the step 2, and the dropwise addition is adopted.

In the above technical scheme, in the step 4, the organic solvent is methanol or acetonitrile.

In the technical scheme, in the step 4, methanol or acetonitrile with the mass of 1-5 times of that of the filter cake is adopted in the recrystallization process, the recrystallization is carried out for 1-3 min under the action of ultrasonic waves, and the active bromine quaternary ammonium salt is obtained through filtration.

A preparation method of active bromine quaternary ammonium salt comprises the following steps:

step 1, dissolving organic ammonium bromide by using water to prepare an organic ammonium bromide solution, wherein the mass ratio of the water to the organic ammonium bromide is 50: 1;

step 2, adding NaBr into the organic ammonium bromide solution, stirring for 0.1-0.3 hours at a stirring speed of 300-600 rpm, wherein the molar mass ratio of NaBr to organic ammonium bromide is 2-3: 1;

step 3, dropwise adding an oxone aqueous solution into the mixture prepared in the step 2, wherein the stirring speed is 300-600 rpm, and continuing to react for 0.25 hour after the oxone aqueous solution is added, so as to obtain a reaction product, wherein the mass content of the oxone aqueous solution in the oxone aqueous solution is 20%, and the molar mass ratio of the added oxone aqueous solution to the organic ammonium bromide is 1-2: 1;

step 4, filtering the reaction product finally obtained in the step 3, and recrystallizing a filter cake by adopting methanol to obtain the active bromine quaternary ammonium salt;

wherein the organic ammonium bromide is represented by the general structural formula (III) or the general structural formula (IV):

wherein R is₁Is C₁₂～C₁₆Alkyl of R₂And R₄Are each methyl, R₃Is methyl, benzyl or p-bromophenoxyethyl;

wherein R is₁Is C₁₂～C₁₆Alkyl group of (1).

An application of active bromine quaternary ammonium salt in seawater sterilization.

In the technical scheme, the active bromine quaternary ammonium salt is added into seawater in an intermittent feeding mode.

In the technical scheme, the adding amount of the active bromine quaternary ammonium salt is 20-30 mg/L seawater.

The invention has the advantages and beneficial effects that:

the novel active bromine quaternary ammonium salt prepared by the invention is an ideal active bromine source, is a safe solid substance and has very low bromine vapor pressure and very high active bromine content. Studies show that tribromo negative ion (Br)₃ ^-) Is stable and Br in water₃ ^-Undergoes rapid dissociation equilibrium to produce Br^-And Br₂The latter can generate BrO according to different pH values of the environment^-HOBr or BrO^-(iii) HOBr. Because the quaternary ammonium cation is positively chargedThe negatively charged anion can be bonded by coulombic force, so that the quaternary ammonium salt can be used as Br₃ ^-A superior carrier.

The invention provides a technical scheme for controlling bacteria in industrial circulating cooling water by using the active bromine quaternary ammonium salt, which comprises the following steps: the active bromine quaternary ammonium salt is added into the water body in an impact intermittent mode, and when the content of the active bromine quaternary ammonium salt in each cubic meter of water body is 20-30 g, the removal rate of heterotrophic bacteria can reach over 90%.

The novel active bromine quaternary ammonium salt prepared by the invention can be used as a bactericide, the bactericide has the advantages of simple preparation process, no byproduct generated in the synthesis process, good product stability, high active bromine content and strong bactericidal capability, and is a safe and efficient water treatment medicament.

Drawings

FIG. 1 is a graph of the active bromine content of the compounds of examples 1-5 over time.

For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.

Detailed Description

In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.

The determination of the active bromine content in the active bromine quaternary ammonium salt provided by the invention adopts a starch-iodine titration method, and the specific operation method comprises the following steps:

0.2g of active quaternary ammonium bromide salt was weighed into an iodine measuring flask, and then 20mL of glacial acetic acid was added thereto, and after dissolution was completed, 15mL of 30% KI aqueous solution was added thereto, and the mouth of the flask was sealed with water. The solution was then stirred for 15min, the stopper and sealed area rinsed with water and washed into the bottle. The solution was titrated with 0.1N sodium thiosulfate standard solution and when a faint yellow color was observed, 1mL of 1 wt% aqueous starch solution was added to change the color of the solution from faint yellow to blue. Titration with sodium thiosulfate was continued until the blue color disappeared. The volume of sodium thiosulfate consumed was recorded, tested in triplicate, and the active bromine content of the product was calculated.

Evaluation of the Bactericidal efficacy of active Broomum Quaternary germicide the method described in ASTM E645-13 test method for efficacy of germicide for Cooling Water System was used:

the seawater for dilution is sterilized before the experiment, and then the bacterial suspension with the same amount is inoculated to ensure that the initial bacterial amount (calculated by CFU) of the experiment reaches 105-106 mL^-1Then adding bactericide for treatment. And no bactericide is added after inoculation of the blank control. After the bactericide acts for 4 hours, the bacteria in the test sample are counted by adopting a plate counting method and culturing for 72 hours at the temperature of (29 +/-1) DEG C, and the sterilization rate is calculated by controlling a blank sample.