CN111620786B - Active bromine quaternary ammonium salt, preparation method and application - Google Patents
Active bromine quaternary ammonium salt, preparation method and application Download PDFInfo
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Abstract
The invention discloses an active bromine quaternary ammonium salt, which 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.
Description
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, 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 accumulation of the slime produces scale to obstruct heat conduction, and serious pipeline blockage can be caused. 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 the bromine bactericide has incomparable advantages in the aspects of sterilization effect, application conditions, environmental protection factors and the like compared with the chlorine bactericide, so the bromine bactericide is a good substitute of 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 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;
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;
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 aqueous solution of oxone to 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 hour after the addition of the aqueous solution of oxone is finished to obtain a reaction product, wherein the molar mass ratio of the added oxone to the organic ammonium bromide is 1-3:1, wherein the mass content of the added oxone in the aqueous solution of oxone 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 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;
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 for recrystallization for 1-3 min under the action of ultrasonic waves, and the active bromine quaternary ammonium salt is obtained by filtering.
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;
step 2, adding NaBr into the organic ammonium bromide solution, stirring for 0.1-0.3 h at the 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 after the step 2 is finished, 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 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;
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 water 3 - Undergoes rapid dissociation equilibrium to produce Br - And Br 2 The latter can generate BrO according to different pH values of the environment - HOBr or BrO - (iii) HOBr. Quaternary ammonium salts can act as Br since quaternary ammonium cations are positively charged and can bind negatively charged anions by coulombic forces 3 - 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 more than 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 that those skilled in the art will better understand the technical solutions of the present invention, the technical solutions of the present invention are 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 vial, followed by addition of 20mL of glacial acetic acid thereto, addition of 15mL of 30% KI aqueous solution thereto after completion of dissolution, and sealing the mouth of the vial 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 1wt% aqueous starch solution was added to change the solution color 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 used as a sterilization place before the experimentThen, the same amount of bacterial suspension is inoculated to make the initial bacterial amount (calculated by CFU) of the experiment reach 105-106 mL -1 Then 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.
In the embodiment, the seawater used for the bactericidal performance test is taken from the sea area of Hua Ninghai power plants in Zhejiang country, and the main parameters of the water quality are as follows: pH 8.07, salinity 2.3%, total alkalinity (CaCO) 3 Meter) 159mg/L.
Example one
Preparation of lauryl trimethyl ammonium tribromide (2 a)
Step 1, dissolving 1g of lauryl trimethyl ammonium bromide by using water to prepare a lauryl trimethyl ammonium bromide solution, wherein the mass ratio of the water to the lauryl trimethyl ammonium bromide is 20;
step 2, adding NaBr into the lauryl trimethyl ammonium bromide solution, stirring for 0.1 hour at the stirring speed of 450rpm, wherein the molar mass ratio of NaBr to lauryl trimethyl ammonium bromide is 2.2;
step 3, dropwise adding an aqueous solution of oxone into the mixture prepared after the step 2 is finished, wherein the stirring speed is 450rpm, and continuing to react for 0.25 hour after the addition of the aqueous solution of oxone is finished to obtain a reaction product, wherein the molar mass ratio of the added oxone to the lauryl trimethyl ammonium bromide is 2:1, wherein the mass content of the added oxone in the aqueous solution of oxone is 30%;
and 4, filtering the reaction product finally obtained in the step 3 to obtain an orange solid filter cake, and ultrasonically recrystallizing the filter cake for 1min by adopting methanol with the mass being 2 times that of the filter cake to obtain lauryl trimethyl ammonium tribromide with the yield of 92%.
The IR and NMR data for the product are as follows:
IR(cm -1 )ν：3021，2921，2851，1484，1466，1415，1106，963，904，722，617； 1 H NMR(400MHz,CD 3 CN)δ3.31-3.18(m,2H),3.04(s,9H),1.99-1.95(m,1H),1.79-1.69(m,2H),1.35-1.31(m,17H),0.91(t,J＝6.7Hz,3H)； 13 C NMR(101MHz,CD 3 CN)δ66.72,66.69,66.67,52.99,52.95,52.91,31.68,29.37,29.25,29.11,29.06,28.75,25.80,22.55,22.43,13.46.
example two
Preparation of hexadecyltrimethylammonium tribromide (2 b)
Step 1, dissolving 1g of hexadecyl trimethyl ammonium bromide by using water to prepare a hexadecyl trimethyl ammonium bromide solution, wherein the mass ratio of the water to the hexadecyl trimethyl ammonium bromide is (80);
step 2, adding NaBr into the hexadecyl trimethyl ammonium bromide solution, stirring for 0.5 hour at the stirring speed of 600rpm, wherein the molar mass ratio of NaBr to the hexadecyl trimethyl ammonium bromide is 2.5;
step 3, dropwise adding an oxone aqueous solution into the mixture prepared after the step 2 is finished, wherein the stirring speed is 600rpm, and continuing to react for 0.5 hour 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 hexadecyl trimethyl ammonium bromide is 1.5;
and 4, filtering the reaction product finally obtained in the step 3 to obtain a filter cake, and ultrasonically recrystallizing the filter cake for 1min by adopting acetonitrile with the mass being 1 time that of the filter cake to obtain hexadecyl trimethyl ammonium tribromide, wherein the yield is 90%.
The IR and NMR data for the product are as follows:
IR(cm -1 )ν：3016，2917，2850，1484，1465，1415，962，905，725，616； 1 H NMR(400MHz,CD 3 CN)δ3.30-3.15(m,2H),3.04(s,9H),1.97(s,2H),1.74(s,2H),1.40-1.25(m,24H),0.91(s,3H)； 13 C NMR(101MHz,CD 3 CN)δ66.74,66.72,66.69,53.02,52.98,52.94,31.68,29.43,29.41,29.37,29.26,29.11,29.07,28.76,25.82,22.57,22.43,13.46.
EXAMPLE III
Preparation of dodecyl dimethyl benzyl ammonium tribromide (2 c)
Step 1, dissolving 1g of dodecyl dimethyl benzyl ammonium bromide in water to prepare a dodecyl dimethyl benzyl ammonium bromide solution, wherein the mass ratio of the water to the dodecyl dimethyl benzyl ammonium bromide is 50;
step 2, adding NaBr into the dodecyl dimethyl benzyl ammonium bromide solution, and stirring, wherein the stirring time is 0.3 hour, the stirring speed is 300rpm, and the molar mass ratio of NaBr to dodecyl dimethyl benzyl ammonium bromide is 2.2;
step 3, dropwise adding an oxone aqueous solution into the mixture prepared after the step 2 is finished, wherein the stirring speed is 300rpm, 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 15%, and the molar mass ratio of the added oxone aqueous solution to the dodecyl dimethyl benzyl ammonium bromide is 1.2;
and 4, filtering the reaction product finally obtained in the step 3 to obtain a filter cake, and ultrasonically recrystallizing the filter cake for 2min by using methanol with the mass being 3 times that of the filter cake to obtain the dodecyl dimethyl benzyl ammonium tribromide with the yield of 86%.
The IR and NMR data for the product are as follows:
IR(cm -1 )ν：3064，3031，2947，2850，1616，1583，1480，1466，1454，1429，1400，1362，1213，1156，1080，1032，1002，974，923，861，779，731，704，624； 1 H NMR(400MHz,CD 3 CN)δ7.71-7.42(m,5H),4.41(s,2H),3.37-3.07(m,2H),3.02-2.88(s,6H),2.05-1.92(m,1H),1.90-1.75(m,2H),1.40-1.26(m,17H),0.91(t,J＝6.5Hz,3H)； 13 C NMR(101MHz,CD 3 CN)δ132.98,130.75,129.23,127.39,67.70,64.58,49.75,49.71,49.67,31.68,29.37,29.24,29.11,29.06,28.77,25.90,22.43,22.32,13.45.
example four
Preparation of hexadecylpyridine tribromide (2 d)
Step 1, dissolving 1g of cetylpyridinium bromide by using water to prepare a cetylpyridinium bromide solution, wherein the mass ratio of the solvent to the cetylpyridinium bromide is 50;
step 2, adding NaBr into the cetylpyridinium bromide solution, and stirring for 0.1 hour at a stirring speed of 500rpm, wherein the molar mass ratio of NaBr to cetylpyridinium bromide is 2.2;
step 3, dropwise adding an aqueous solution of potassium hydrogen persulfate complex salt (oxone) into the mixture prepared after the step 2 is finished, wherein the stirring speed is 500rpm, and after the addition of the aqueous solution of potassium hydrogen persulfate complex salt is finished, continuing to react for 0.4 hour to obtain a reaction product, wherein the molar mass ratio of the added potassium hydrogen persulfate complex salt to the cetylpyridinium bromide is 1.2;
and 4, filtering the reaction product finally obtained in the step 3 to obtain a filter cake, and ultrasonically recrystallizing the filter cake for 2min by adopting methanol with the mass being 2 times that of the filter cake to obtain the hexadecylpyridine tribromide, wherein the yield is 88%.
The IR and NMR data for the product are as follows:
IR(cm -1 )ν：3050，2916，2849，1630，1498，1486，1464，1373，1319，1215，1176，957，866，814，776，737，721，684； 1 H NMR(400MHz,CD 3 CN)δ8.74(d,J＝5.7Hz,2H),8.53(t,J＝7.8Hz,1H),8.06(t,J＝6.9Hz,2H),4.55(t,J＝7.6Hz,2H),2.00-1.86(m,2H),1.36-1.29(m,26H),0.90(t,J＝6.7Hz,3H)； 13 C NMR(101MHz,CD 3 CN)δ145.72,144.47,128.45,61.92,31.69,31.00,29.44,29.41,29.37,29.25,29.13,29.08,28.67,25.64,22.45,13.48.
EXAMPLE five
Preparation of dodecyl-dimethyl-2- (4-bromophenoxyethyl) -ammonium tribromide (2 e)
Step 1, adding 1g of domiphen bromide into a 100mL round-bottom flask, dissolving the domiphen bromide with water to prepare a domiphen bromide solution, wherein the mass ratio of the solvent to the domiphen bromide is 60;
step 2, adding NaBr into the domiphen bromide solution, stirring for 0.3 hour at the stirring speed of 500rpm, wherein the molar mass ratio of NaBr to domiphen bromide is 4:1;
step 3, dropwise adding an oxone aqueous solution into the mixture prepared after the step 2 is finished, wherein the stirring speed is 500rpm, and continuing to react for 0.25 hour 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 domiphen bromide is 2:1, and the mass content of the added oxone in the oxone aqueous solution is 20%;
and 4, filtering the reaction product finally obtained in the step 3 to obtain an orange solid filter cake, and ultrasonically recrystallizing the filter cake for 3min by adopting methanol with the mass being 5 times that of the filter cake to obtain the dodecyl-dimethyl-2- (4-bromophenoxyethyl) -ammonium tribromide with the yield being 84%.
The IR and NMR data for the product are as follows:
IR(cm -1 )ν：2919，2851，1589，1579，1486，1468，1372，1283，1233，1174，1059，1005，967，945，931，906，880，824，804，722，647； 1 H NMR(400MHz,CD 3 CN)δ7.51(d,J＝8.9Hz,2H),6.94(d,J＝8.9Hz,2H),4.44-4.38(m,2H),3.79-3.58(m,2H),3.44-3.22(m,2H),3.11(s,6H),1.98-1.96(m,1H),1.78(s,2H),1.36-1.31(m,17H),0.91(t,J＝6.6Hz,3H)； 13 C NMR(101MHz,CD 3 CN)δ156.77,132.47,116.77,113.44,65.53,62.77,61.96,51.69,31.68,29.38,29.25,29.11,29.06,28.76,25.84,22.44,22.30,13.45.
example 6
Active bromine Quaternary ammonium salt stability test
Standing the prepared active bromine quaternary ammonium salt at 30 deg.C for 60 days, and determining its active bromine content (Br) by starch-iodine titration 2 Meter) over time. As shown in FIG. 1, the active bromine quaternary ammonium salts are stable, in which the active bromine content in 2a-2c and 2e remains substantially unchanged with time, and the active bromine content in 2d has a tendency to decrease slowly with time (the active bromine content decreases by 0.7% at 30 ℃ for 60 days).
Table 1 shows the measured and theoretical values of the active bromine contents of the compounds of examples 1 to 5.
TABLE 1
As can be seen from Table 1, the active bromine content in the product was close to the theoretical value, indicating the presence of Br in the structure 3 - . Analysis of test data combining FT-IR and NMR shows that the structure of the prepared active bromine quaternary ammonium salt is consistent with that of the target product.
Table 2 shows the results of the heterotrophic bacteria sterilization test of 2a-2e
TABLE 2
As can be seen from Table 2, when the active bromine quaternary ammonium salt provided by the invention is applied to a seawater system, an impact intermittent feeding mode is adopted, the feeding concentration is 20-30 mg/L, and the sterilization rate can reach more than 90%.
In addition, the active bromine quaternary ammonium salt in the invention can be prepared by adopting the following method:
the second preparation method comprises the following steps: the organic ammonium bromide (1 equiv) was added to the round bottom flask followed by bromine (1-3 equiv) and the flask was sealed for 24h to give an orange solid and methanol recrystallized to give the desired product.
Compared with the first preparation method, the bromine has stronger volatility and oxidizability and larger toxicity, and the preparation process has the defects of inconvenient operation, difficult metering of bromine dosage, environmental pollution and the like. Therefore, the active bromine quaternary ammonium salt is recommended to be prepared by the method in the invention.
The invention being thus described by way of example, it should be understood that any simple alterations, modifications or other equivalent alterations as would be within the skill of the art without the exercise of inventive faculty, are within the scope of the invention.
Claims (3)
1. An application of active bromine quaternary ammonium salt in seawater heterotrophic bacteria sterilization,
the active bromine quaternary ammonium salt is characterized by having a general structural formula shown in a general structural formula (I):
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.
The preparation method of the 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);
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 hour 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 formula (III):
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.
2. The use of the active quaternary ammonium bromide salt in seawater heterotrophic bacteria sterilization according to claim 1, wherein the active quaternary ammonium bromide salt is added to seawater by an intermittent feeding manner.
3. The application of the active bromine quaternary ammonium salt in seawater heterotrophic bacteria sterilization according to claim 1, wherein the adding amount of the active bromine quaternary ammonium salt is 20-30 mg/L seawater.
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| WO2004054962A1 (en) * | 2002-12-16 | 2004-07-01 | Council Of Scientific And Industrial Research | Process for preparing quaternary ammonium tribromides |
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