CN102939968A - Quaternary ammonium salt germicidal algicide and synthetic method and application thereof - Google Patents
Quaternary ammonium salt germicidal algicide and synthetic method and application thereof Download PDFInfo
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- CN102939968A CN102939968A CN2012104770618A CN201210477061A CN102939968A CN 102939968 A CN102939968 A CN 102939968A CN 2012104770618 A CN2012104770618 A CN 2012104770618A CN 201210477061 A CN201210477061 A CN 201210477061A CN 102939968 A CN102939968 A CN 102939968A
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- quaternary ammonium
- ammonium salt
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- killing agent
- biocidal algae
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Abstract
A quaternary ammonium salt germicidal algicide is represented by a chemical formula: 1-ethyl methyl ether-2-methyl-3-R based benzimidazole quaternary ammonium salt, wherein the X is -CH2OCH2CH3, and the R is selected from C3-C16 carbon alkyl. The quaternary ammonium salt germicidal algicide uses o-phenylenediamine and acetic acid as raw materials, is obtained through closed loop, substitution and quaternary ammonium salinization, is applied to industrial recycling cooling water, and is easy to degrade and environment-friendly.
Description
One, technical field
The present invention relates to a kind of water treatment agent and preparation method thereof, particularly industrial circulating cooling water inorganic agent and preparation method thereof exactly is a kind of quaternary ammonium salt Biocidal algae-killing agent and preparation method and use thereof.
Two, background technology
Jocobs synthesized quaternary ammonium salt surface active agent first in 1915, and pointed out that this compound has certain bactericidal action, but did not arouse attention.Nineteen thirty-five Domagk has further studied the relation of its bactericidal action and chemical constitution thereof, and Wetzel has progressively caused attention after having carried out the clinical disinfection test.The bactericidal action that a kind of quaternary ammonium compound-benzene is pricked bromine hinge (bromogeramine) has been studied by China in 1964, just recommendedly after 1971 use as disinfectant.
It is its important symbol that quaternary ammonium salt surface active agent all contains an Ionized nitrogen-atoms, can be divided into hydrophilic cation and hydrophobic long-chain on structure.The bactericidal mechanism of quaternary ammonium salt cationic surfactant mainly is adsorbed on the bacterium surface of negative electrical charge by cation head base, the permeability of change bacteria cell wall is finished, in addition, after quaternary ammonium salt is adsorbed onto the bacterial body surface, be conducive to lipoid layer and albumin layer that hydrophobic group and hydrophilic group go deep into respectively somatic cells, cause enzyme to lose activity and make the metabolic disorder of microorganism with protein denaturation, and can also cause aqtocytolysis and death.Because the joint effect of above-mentioned these two kinds of effects is so that quaternary ammonium salt cationic surfactant has stronger sterilizing ability.The quaternary ammonium salt bactericide is not affected by the water hardness, and low toxicity is without cumulative toxicity, and is effective especially to the bacterium algae under the meta-alkalescence condition, and has stronger foundry loam to peel off and peptizaiton.
The sorting technique of quaternary ammonium salt biocide is many, by how much dividing of long-chain in the molecule strand quaternary ammonium salt, double-chain quaternary ammonium salt two classes is arranged; Press what of azonia, can be divided into mono-quaternaries, bi-quaternary ammonium salt and three quaternary ammonium salts etc.; By the classification of its molecular structure, what hydrophobic group was entirely alkyl is called the fats quaternary ammonium salt; Contain pure ethers quaternary ammonium salt of being called of alcoholic extract hydroxyl group, what contain imidazoline structure is called the imidazolines quaternary ammonium salt, and all the other quaternary ammonium salinities are made other classes.
In recent years, the synthetic of benzimidazoles compound was a big hot topic, and how fast simple synthesizing benzimidazole and its esters are keys wherein, and method has following several:
1. synthetic take o-phenylenediamine and carboxylic acid (and derivative) as raw material;
2. synthetic take o-phenylenediamine and aldehyde as raw material;
3. synthetic take o-phenylenediamine and thiocyanic acid as raw material;
4. synthetic take adjacent halogenated nitrobenzene and aldehyde as raw material;
5. synthetic take ortho-nitraniline as raw material;
6. synthetic take amine and acyl compounds as raw material.
Wherein especially take o-phenylenediamine and carboxylic acid (and derivative) as raw material and o-phenylenediamine and aldehyde as raw material the most commonly used.And synthetic condition has heating, catalyzer usually, some special methods also occurred in recent years, such as Novel experimental methods such as photocatalysis, microwave catalysis.
Technology on circulating cooling water treatment is one of main method of Industrial Water Saving.Because industrial colling accounts for the 70-80% of industrial water consumption, thereby realize the water circuit utilization, improve concentration rate to be the key of Industrial Water Saving.If circulating cooling system is fetched water when making supplementing water from urban water supply or from well, the amount of microorganism is normally seldom in the supplementing water., unlimited recirculating cooling water system constantly has dust to enter and sends into the wind microorganism, and microbes is bred rapidly when having a certain amount of nutrients.
Adopting biocide that the microorganism in the cooling water system is controlled is a kind of generally the use at present and effective method, namely by in cooling water, adding the not biocide of same-action, thus the control microbial reproduction.
Because the oxidisability biocide has inexpensive, efficient characteristics, this high P/C is than making it still dominate so far the control of cooling water system microorganism.For large-scale cooling water system, the applicant do not see so far without the oxidisability biocide, and only uses the report of non-oxidative bactericide.Non-oxidative bactericide is another large class biocide in the cold water process, and they are organic compound basically, and with regard to some aspect, it uses more convenient and effective than oxidisability biocide.
In present employed non-oxidative bactericide, the quaternary ammonium salt biocide has the wide spectrum bactericidal performance, all effective to bacterium, algae, fungi, different from the oxidisability biocide, affected by pH little,, environmental friendliness low to the toxicity of environment, P/C is than good, and being easy to use and storing, being most widely used, is one of the main focus of research and application of killing livestock at present.
Three, summary of the invention
The present invention is directed to the deficiency of existing water quality condition and traditional non-oxidative bactericide, being intended to provides a kind of novel structure, well behaved novel non-oxidizable Biocidal algae-killing agent for recirculating cooling water system, problem to be solved is the structure of the novel quaternary ammonium salt Biocidal algae-killing agent of design and designs synthetic route and synthesize, and synthetic disinfecting algicide characterized, confirm simultaneously the activity of its sterilization algae removal.
The Biocidal algae-killing agent that the present invention is alleged belongs to quaternary ammonium salt, chemical name: 1-the first and second ethers-2-methyl-3-R base benzimidazole quaternary ammonium salt have following chemical formula:
X-the first and second ether (-CH
2OCH
2CH
3), R-alkyl (C
3-C
16); The preferred C of R
8-C
16The alkyl of carbon.
The preparation method of this compound is take o-phenylenediamine as initiation material, comprise the synthetic of the preparation of intermediate and target product and separate, washing and each unit process of purifying, to be o-phenylenediamine with acetic acid separated after 110-130 ℃ of stirring reaction 8-12 hour in mass percentage concentration 80-90% phosphoric acid and 80-90% polyphosphoric acids solvent obtains intermediate (I) 2-tolimidazole in the preparation of described intermediate, the volume ratio of phosphoric acid and polyphosphoric acids is 2:1-1:2, and reaction equation is as follows:
Intermediate (I) and chloromethyl ether obtain intermediate (II) 1-the first and second ethers-2-tolimidazole take mass percentage concentration 35-45% sodium hydroxide solution as solvent, separating under the phase transfer catalyst tetrabutyl ammonium bromide existence condition after 80-100 ℃ of stirring reaction 8-12 hour, the addition of tetrabutyl ammonium bromide is the 1-2% of intermediate (I) quality, and reaction equation is as follows:
Synthesizing of ideal product, intermediate (II) and bromoalkane (RBr, R is the alkyl of 3-16 carbon) separation obtains target product 1-the first and second ethers-2-methyl-3-R base benzimidazole quaternary ammonium salt (the lower benzimidazole quaternary ammonium salt that is called for short) after 75-85 ℃ of stirring reaction 8-12 hour in acetonitrile solvent, and reaction equation is as follows:
In the formula: the alkyl of R:3-16 carbon, X :-CH
2OC
2H
5
The introducing of aromatic ring and N atom can improve the compound bactericidal activity preferably in the benzimidazole quaternary ammonium salt of the present invention, long alkyl chain length structure is so that this bactericide can better act on microorganism, and with the structure of electron withdraw group, its bacteriostatic activity also improves a lot; In addition, it is good water-soluble that the ether that contains in the structure has it, can play better sterilization algae removal effect in water.This product is easy to degraded, environmental protection.
This benzimidazole quaternary ammonium salt and common fungicide 1227 (dodecyl benzyl dimethyl ammonium chloride) compare test to the germicidal efficiency of heterotroph, minimum using dosage is 50mg/L, the benzimidazole quaternary ammonium salt has certain germicidal efficiency to heterotroph, the length of carbochain has certain relation in the size of its germicidal efficiency and the R base, carbochain is lower than 1227 less than 7 o'clock bactericidal effects in the R base, carbon chain lengths is when 8-16 in the R base, bactericidal effect is significantly better than 1227, and carbochain is longer, bactericidal effect is relatively better, and action time is longer, still keeps 99% germicidal efficiency after 48 hours.
This benzimidazole quaternary ammonium salt and common fungicide 1227 compare test to the germicidal efficiency of sulfate reducing bacteria, when the bactericidal effect less than 7 time of carbochain in the R base was lower than that carbon chain lengths is at 8-16 in 1227, the R base, bactericidal effect was better than 1227, and carbochain is longer, and bactericidal effect is relatively better.
The purposes of this benzimidazole quaternary ammonium salt is exactly as the application of Biocidal algae-killing agent in industrial circulating cooling water system.
Four, embodiment
1, the preparation of intermediate (I) 2-tolimidazole
In the 250mL there-necked flask, add solvent quality concentration 85% phosphoric acid and mass concentration 86% polyphosphoric acids, the volume ratio 1:1 of phosphoric acid and polyphosphoric acids, with the electric jacket heating, turn on agitator adds o-phenylenediamine and acetic acid, is warming up to 120-130 ℃, reacts 10 hours.React complete, the cooling reactant liquor is poured reactant liquor in the beaker into, drips 10% sodium hydroxide solution, regulates pH to neutral, has a large amount of faint yellow flocculent deposits to occur, and continues to drop to pH to alkalescence.Treat that it is cooled to about 20～40 ℃, suction filtration gets the thick product of faint yellow mud shape.With the crude product heating and melting, add activated carbon decolorizing after the melting, cooling after the decolouring obtains intermediate (I) with the ethanol-water solution recrystallization.
The fusing point test of intermediate (I) 2-tolimidazole is 175-176 ℃.
The peak at 2920 places is CH in the infrared analysis
3The peak, stretching vibration peak, the absworption peak of the 1470th, N-C, the 1540th, the absworption peak of phenyl ring.
Tolimidazole
1The H of contraposition on the corresponding phenyl ring in δ in the HNMR spectrogram=7.2035～7.2465, the H at ortho position on the corresponding phenyl ring in δ=7.5470～7.5773, the H of 2 upper methyl on the corresponding imidazole ring in δ=2.6283～2.6944, the active H among the corresponding N-H in δ=10.6719.
2, the preparation of intermediate (II) 1-the first and second ethers-2-tolimidazole
The sodium hydroxide that in the there-necked flask of 100mL, adds mass concentration 40%, intermediate (I) 2-tolimidazole 3g, phase transfer catalyst tetrabutyl ammonium bromide 0.05g.The heating reactant liquor is treated that the 2-tolimidazole dissolves fully and is added chloromethyl ether to about 80-100 ℃, reacted 10 hours.The cooling reactant liquor, minute oil-yielding stratum, water layer are with the toluene extraction several times.The oil reservoir told is dry with anhydrous calcium chloride, and Rotary Evaporators evaporates solvent toluene and the chloromethyl ether of complete reaction not, obtains oily liquids intermediate (II).
The upward peak 2H δ of the alkyl chain of connection=5.7473～5.8165 of imidazole ring N appear in the H place on the first and second ethers, another 2H on corresponding the first and second ethers in δ=3.2865～3.3502,3H δ=0.9805～1.1235,2 upper methyl H peak 3H δ=2.5416～2.6186 of imidazole ring.
3, target product is synthetic
In the there-necked flask of 50mL, add intermediate (II) 1-the first and second ethers-2-tolimidazole, bromododecane, solvent acetonitrile is heated to 80 ℃, reacts 8-12 hour.Cool off to get white depositions, suction filtration takes out unreacted raw material and solvent, gets faint yellow head product.Obtain the crystal of white plates for three times with the acetonitrile recrystallization, suction filtration obtains product.
Benzoglioxaline salt
1In the HNMR spectrogram, the H peak 2H δ that is connected with imidazole ring N in the dodecyl=3.2654～3.5783, adjacent H peak 2H δ=1.5205～1.6015, C
3～C
11Upper H peak 2H δ=1.2014～1.3530,3H δ=0.8945～0.9566.H on the phenyl ring, 2H δ=6.4051～6.5124, H δ=6.5135～6.5895, H δ=6.5746～6.6621.
Claims (4)
1. quaternary ammonium salt Biocidal algae-killing agent is characterized in that: be 1-the first and second ethers shown in the following chemical formula-2-methyl-3-R base benzimidazole quaternary ammonium salt:
In the formula: X :-CH
2OCH
2CH
3, R is selected from C
3-C
16The alkyl of carbon.
2. Biocidal algae-killing agent according to claim 1, it is characterized in that: R is selected from C
8-C
16The alkyl of carbon.
3. the preparation method of the Biocidal algae-killing agent shown in claim 1, take o-phenylenediamine as initiation material, comprise the synthetic of the preparation of intermediate and target product and separate, washing and each unit process of purifying, it is characterized in that: to be o-phenylenediamine with acetic acid separated after 110-130 ℃ of stirring reaction 8-12 hour in mass percentage concentration 80-90% phosphoric acid and mass percentage concentration 80-90% polyphosphoric acids solvent obtains intermediate (I) 2-tolimidazole in the preparation of described intermediate; The volume ratio of phosphoric acid and polyphosphoric acids is 2:1-1:2; Intermediate (I) and chloromethyl ether obtain intermediate (II) 1-the first and second ethers-2-tolimidazole take mass percentage concentration 35-45% sodium hydroxide solution as solvent, separating under the phase transfer catalyst tetrabutyl ammonium bromide existence condition after 80-100 ℃ of stirring reaction 8-12 hour; The addition of phase transfer catalyst is the 1-2% of intermediate (I) quality; Described target product synthetic is that intermediate (II) separated after 75-85 ℃ of stirring reaction 8-12 hour in acetonitrile solvent with bromoalkane and obtains 1-the first and second ethers-2-methyl-3-R base benzimidazole quaternary ammonium salt target product.
4. the purposes of a Biocidal algae-killing agent as claimed in claim 1 is characterized in that: 1-the first and second ethers-2-methyl-3-R base benzimidazole quaternary ammonium salt in industrial circulating cooling water as the application of Biocidal algae-killing agent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107410358A (en) * | 2017-07-24 | 2017-12-01 | 江苏中浩远达环境工程有限公司 | A kind of water process non oxidizing bactericide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147484A (en) * | 2007-11-12 | 2008-03-26 | 南京工业大学 | Novel corrosion-retarding germicide and its preparation method |
| CN101391982A (en) * | 2008-11-04 | 2009-03-25 | 广东省石油化工研究院 | Alkylation reaction method of benzimidazoles compounds |
-
2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147484A (en) * | 2007-11-12 | 2008-03-26 | 南京工业大学 | Novel corrosion-retarding germicide and its preparation method |
| CN101391982A (en) * | 2008-11-04 | 2009-03-25 | 广东省石油化工研究院 | Alkylation reaction method of benzimidazoles compounds |
Non-Patent Citations (5)
| Title |
|---|
| PERNAK J, SKRZYPCZAK A, KRYSIŃSKI J, ET AL.: "Actions of new iminium compounds against bacteria and fungi，XXX：3-alkoxymethyl-1-hexyl-, 3-alkylthiomethyl-1-hexyl-, 3-alkoxymethyl-1-octyl-and 3-alkylthiomethyl-1-octylbenzimidazolium chlorides", 《ARCHIV DER PHARMAZIE》 * |
| 吴长利等: "苯并咪唑型离子液体的合成与表征", 《化学试剂》 * |
| 毛郑州等: "苯并咪唑类化合物的合成研究进展", 《有机化学》 * |
| 赵旭娜等: "季铵盐类阳离子表面活性剂的生物效应", 《中国消毒学杂志》 * |
| 郭志强: "烷基氯化铵季铵盐的抗菌性能研究", 《日用化学品科学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107410358A (en) * | 2017-07-24 | 2017-12-01 | 江苏中浩远达环境工程有限公司 | A kind of water process non oxidizing bactericide |
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Application publication date: 20130227 |