CN1057427C - Quaternary ammonium salt bactericide and preparation method - Google Patents
Quaternary ammonium salt bactericide and preparation method Download PDFInfo
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- CN1057427C CN1057427C CN95116434A CN95116434A CN1057427C CN 1057427 C CN1057427 C CN 1057427C CN 95116434 A CN95116434 A CN 95116434A CN 95116434 A CN95116434 A CN 95116434A CN 1057427 C CN1057427 C CN 1057427C
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- quaternary ammonium
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Abstract
The present invention relates to a quaternary ammonium salt bactericide containing a double-heteroatomic ring structure and a preparation method thereof. The preparation method of the bactericide has the following steps: the tertiaryamine compound containing a double-heteroatomic ring structure or the mixed trialkylamine of single and double heteroatomic ring reacts with organohalogen compound to prepare the quaternary ammonium salt product containing a double-heteroatomic ring structure; then, the quaternary ammonium salt bactericide is obtained by dissolving the reaction product in the water. The active matter of the bactericide contains quaternary ammonium salt with double heteroatomic rings. The bactericide of the present invention can be used for treating oily sewage, industrial cooling water and circulating water in the petroleum industry. Under the condition that the addition of the bactericide is not larger than 40 ppm, the bactericidal rate reaches 99%.
Description
The invention belongs to the bactericide technical field, exactly is about quaternary ammonium salt bactericide and preparation method thereof.
The existing nearly 60 years history of research antibacterial, sterilizing function that quaternary cationics has, the representative quaternary imidazoline salt (" Cosmetics and Toiletries " Vol.99,1984.6) that Mono Industries Inc. research is arranged; The alkyl pyridine cationic surfactant of Imperialchemical Industres Ltd. development (G.F.Long Man work " washing agent and detergent body analysis ", Light Industry Press); The trade mark that also has Atlas chemical IndustriesInc. development and produce is the N-cetyl N-ethylmorpholine ethyl-sulfate salt of Atlas G-263, and its chemical structural formula is
(" fine chemistry industry information ") NO.8, NO.11, nineteen ninety) and the N-dodecyl quaternary cationics (" surfactant industry " NO.4, P1,1991) of Armour Industrial Co. development.The industrial production that above-mentioned heterocycle cationic surfactant has, what have also rests on conceptual phase.In addition, according to relevant reported in literature, quaternary ammonium salt bactericide has advantages such as toxicity is low, applied range, but microorganism easily develops immunity to drugs to quaternary ammonium salt, and biocidal active is preferably only just arranged under higher concentration, is quaternary ammonium mixture as NalCO7326, JN-2 also belongs to this type of, its adding consistency need be controlled at 200～400ppm just can reach the effect of killing livestock (" petroleum refining ", 1993.12, P53～58).And for example dodecyl benzyl dimethyl ammonium chloride (1227) is a kind of quaternary ammonium salt bactericide preferably, with No. 802 oil-polluted waters of No.2 Oil Production Factory, Xinjiang Petroleum Administration Bureau is sample, it is carried out the bactericidal effect test, this bactericide quaternary ammonium salt active matter content 40%, when adding dose and be 80mg/l, can only be with the SRB bacterial number in the oil-polluted water by 10
4Individual/ml reduces to 10
3Individual/ml, and the TGB bacterial number does not change, and still is 10
3Individual/ml (" oilfield chemistry " 1994.3, P247～249).
It is raw material with N-methyl piperidine or N-methylmorpholine that the clear 53-63384 of Japan Patent discloses a kind of, make methylating reagent with chloromethanes, make thinner with water, 0～100 ℃, 1～7 the crust pressure under react, preparation N, N-dimethyl chlorination piperidines or N, the method for N-dimethyl chlorination morpholine, but can only prepare single heterocyclic quaternary ammonium product salt by this method.
The purpose of this invention is to provide a kind of preparation method who contains the quaternary ammonium salt bactericide of two heterocycle structures or single, double heterocycle structure.
Another object of the present invention provides a kind of quaternary ammonium salt bactericide product of preparation according to the method described above.
The present invention is achieved through the following technical solutions: will have the reaction of the tertiary amine compound of two heterocycle structures or single, double heterocycle mixing tertiary amine and organohalogen compound and make the quaternary ammonium salt product that contains two heterocycle structures, and then this product will be dissolved in water promptly.
The concrete preparation method of this bactericide is: will have the tertiary amine compound of two heterocycle structures
With organohalogen compound R
2X (II), R
3X (III) mixes, be warming up to 50～150 ℃, preferably 60～130 ℃ were reacted 1～3 hour, I: II: III (mol ratio)=0.8～1.0: 1.0～1.2: 1.0～1.2, also can in the presence of chloroform or other inertia halogenated hydrocarbon solvent, react, the weight ratio of I and solvent is 2～2.5: 1, reaction finishes, at first carry out air-distillation and remove solvent, decompression distillation removes unreacted organohalogen compound, make the amber dope that contains two heterocycle structure quaternary ammonium salts, yield is worked energetically 95 heavy %, then this product is dissolved in the water with any ratio, makes bactericide of the present invention.In I, II, the III formula, R
1Be selected from O-diethylidene, butylidene, one of pentylidene; R
2, R
3C for identical or different group
1～C
4Alkyl benzyl, alkyl benzyl; M=2～4; X is selected from Cl or Br.I also can be single heterocycle tertiary amine compound, or the mixture of two heterocycle tertiary amine compound and single heterocycle tertiary amine compound.
The quaternary ammonium salt bactericide of the present invention that makes according to the method described above, its active matter are the mixtures that contains one of quaternary ammonium salt with following pair of heterocycle structure or single, double heterocyclic quaternary ammonium salt:
IV, V formula are two heterocyclic quaternary ammonium salt, and the VI formula is single heterocyclic quaternary ammonium salt, and in IV, V, the VI formula, R is R
2Or R
3, n=1,2, the implication of other group is the same.
The said tertiary amine raw material with two heterocycle structures of the present invention can make with conventional method, also can be the accessory substance of producing corresponding single heterocyclic secondary or tertiary amine.
The present invention has the following advantages:
1. bactericide of the present invention is compared with conventional quaternary ammonium salt bactericide, and bactericidal effect is better.Because microorganism easily develops immunity to drugs to quaternary ammonium salt, only under higher concentration, biocidal active is preferably just arranged, 200～400ppm need be controlled at as conventional quaternary ammonium salt bactericide NalCO 7326 and JN-2 adding consistency and just the effect of killing livestock can be reached, and bactericide of the present invention adds dose≤40ppm, can the iron bacteria in the industrial sewage, sulfatereducting bacteria, heterotroph, fungi etc. be controlled within the oil-field flooding indication range, and the rate of killing livestock reaches 99%.And for example, active matter content is that 38.2% bactericide of the present invention only need add 40mg/l and just SRB, the TGB number of bacteria in No. 81 oil-polluted waters of No.2 Oil Production Factory, Xinjiang Petroleum Administration Bureau can be controlled within the injectivity index scope, brings up to 80mg/l and does not also reach above-mentioned effect and active matter content is the dose that adds of 40% dodecyl benzyl dimethyl ammonium chloride (1227) conventional sterilization agent.
2. raw material sources are easy, have the raw material that economy prepares bactericide of the present invention and can use the by product of producing corresponding single heterocyclic secondary or tertiary amine, have low price, the characteristics of economical rationality.
In a word, the quaternary ammonium salt that the present invention contains two heterocycle structures can be used as bactericide, algicide, is widely used in the processing of oil-polluted water in the petroleum industry and the processing of industrial colling and industrial circulating water.
The following examples will the invention will be further described.
Example 1
Agitator is being housed, oil water separator, in the there-necked flask of dropping funel and thermometer, add 2, two (the N-tetrahydrochysenes 1 of 2-, 4 oxazinyls) ether 122 grams are (0.5 mole, commercially available, purity 84%, single heterocycle tertiary amine 2%), be heated to 75 ± 5 ℃, begin to drip 126.5 gram (1 mole) chloro benzyl (all sharp chemical companies in Beijing, chemical pure), dropwise, reactant liquor becomes the rufous viscous fluid gradually, and reactant liquor is heated to 125 ± 5 ℃, continue reaction 2 hours, decompression distillation (100～120 ℃/8～17.3Pa), deviate from unreacted chloro benzyl, obtain 236 gram clear amber in color dopes.Dope is heated to 60 ± 5 ℃, and the water of weight such as adding dissolves it fully again, makes bactericide A of the present invention
1
According to GB 5174-85 method of testing, record A
1The quaternary ammonium salt active matter content be 38.2 heavy %.
According to the SY5329-88 method of testing, test A
1(Xinjiang Petroleum Administration recovers the oil two to No. 81 oil-polluted waters
Bactericidal effect, the results are shown in Table 1.
As can be seen from Table 1: active matter content is 382% quaternary ammonium salt bactericide A of the present invention
1No. 81 oil-polluted waters had the good sterilization effect, it adds dose only needs the 40mg/l just can be with the SRB in the oil-polluted water, the TGB number of bacteria is controlled within the injectivity index scope, and be that the dose that adds of 40% conventional sterilization agent 1227 (dodecyl benzyl dimethyl ammonium chloride) is brought up to 8mg/l with active matter content, also do not reach above-mentioned effect.
Fig. 1 is the quaternary ammonium salt bactericide A of the present invention that adopts the HP-5985BGC/MS combined instrument to record
1Mass spectrum molecule peak spectrogram.
As seen from Figure 1: 2132 for structural formula is two heterocyclic quaternary ammonium salt double-charge ions peak of (IV), its molecular weight M=213.2 * 2=426.4; 335.4 be single charge ion peak of two heterocyclic quaternary ammonium salt of (V) for structural formula, its molecular weight is exactly 335.4; 266.3 be single heterocyclic quaternary ammonium molecules of salt amount of (VI) for structural formula.
Table 1
Annotate: during (1) test, water sample is processed through Filter paper filtering, sterilization time: 4 hours.
| The sample title | Active matter content (%) | Chemical feeding quantity (mg/l) | Assay (individual/ml) | Index (individual/ml) | |||
| TGB | SRB | ||||||
| Before | After | Before | After | ||||
| A 1 | 38.2 | 40 | 1.3×10 7 | 2.5×10 2 | 6×10 3 | 0.6 | SRB＜10 2 TGB＜10 3 |
| 1227 | 40 | 80 | 10 3 | 10 3 | 10 4 | 10 3 | |
(2) 1227 is dodecyl benzyl dimethyl ammonium chloride (changzhou the 3rd chemical industry
Example 2
In the device with example 1, add 2 of 122 grams (0.5 mole), two (the N-tetrahydrochysenes-1 of 2-, the 4-oxazinyl) ether and 50 gram chloroform (Beijing chemical reagent factories, chemical pure), drip 126 gram chloro benzyls (1 mole) at 70～75 ℃, under agitation reacted 3 hours, chloroform is sloughed in air-distillation, and decompression distillation removes the chloro benzyl, obtain the amber transparent dope of 238 grams, then the water of the weight such as adding makes it to dissolve fully, makes quaternary ammonium salt bactericide A of the present invention2, its performance sees Table 2.
Table 3 has been enumerated bactericide A of the present invention1、A
2To the bactericidal effect of the iron bacteria in the sewage, sulfate reducing bacteria etc. as can be seen from Table 3: quaternary ammonium salt bactericide A of the present invention1、A
2Chemical feeding quantity≤40ppm can be to bacterial control such as the iron bacteria in the sewage, sulfate reducing bacteria, heterotroph and fungies within oilfield sewage water filling scope, the rate of killing livestock reaches 99%, reaches 200～400ppm and just can reach the effect of killing livestock and conventional quaternary ammonium salt bactericide NalCO 7326 and JN-2 add dosage.
Table 2
| Performance | Index |
| Outward appearance | Amber transparency liquid |
| Solvability in water | Can be dissolved in the water with any ratio |
| Smell | Free from extraneous odour |
| The pH value | 6～8 |
Table 3
| The medicament title | Drug concentration ppm | The rate of killing livestock (%) | |||
| Heterotroph | Fungi | Iron bacteria | Sulfate reducing | ||
| A | |||||
| 1 | 20 | 95 | 85 | 89 | 88 |
| 40 | 98 | 88 | 90 | 99 | |
| A 2 | 20 | % | 80 | 86 | 90 |
| 40 | 98 | 83 | 90 | 98 | |
| The test solution initial concentration (individual/ml) | 5.1 * 10 8 | 2 * 10 5 | 1.4 * 10 7 | 3 * 10 9 | |
| Conventional quaternary ammonium salt bactericide NalCO7326 and JN-2 add dosage and reach 200～40ppm and just can reach the effect of killing livestock. | |||||
Claims (4)
1. the preparation method of a quaternary ammonium salt bactericide is characterized in that and will have the tertiary amine compound of two heterocycle structures
(I) and organohalogen compound R
2X (II), R
3X (III) mixes, I: II: III (mol ratio)=0.8～1.0: 1.0～1.2: 1.0～1.2, be warming up to 50～150 ℃ of reactions 1～3 hour, decompression distillation then, remove unreacted organohalogen compound, make the dope that contains two heterocycle structure quaternary ammonium salts, at last this product be dissolved in the water with any ratio, make the bactericide that contains one of following pair of heterocyclic quaternary ammonium salt or single two heterocyclic quaternary ammonium salt mixtures:
Wherein, R
1Be selected from one of O-diethylidene, butylidene, pentylidene; R
2, R
3Be identical C
1～C
4Alkyl, benzyl, alkyl benzyl; M=2～4; X is selected from Cl or Br; R is R
2Or R
3, n=1 or 2.
2. according to the said preparation method of claim 1, it is characterized in that said reaction temperature is 60～130 ℃.
3. according to the said preparation method of claim 1, it is characterized in that I, II, III also can react in the presence of chloroform or other inertia halogenated hydrocarbon solvent, the weight ratio of I and solvent is 2～2.5: 1.
4. according to the said preparation method of claim 1, it is characterized in that (I) also can be the tertiary amine compound of single heterocycle structure, or the mixture of two heterocycle tertiary amine compound and single heterocycle tertiary amine compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95116434A CN1057427C (en) | 1995-09-26 | 1995-09-26 | Quaternary ammonium salt bactericide and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95116434A CN1057427C (en) | 1995-09-26 | 1995-09-26 | Quaternary ammonium salt bactericide and preparation method |
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|---|---|
| CN1146281A CN1146281A (en) | 1997-04-02 |
| CN1057427C true CN1057427C (en) | 2000-10-18 |
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| CN95116434A Expired - Fee Related CN1057427C (en) | 1995-09-26 | 1995-09-26 | Quaternary ammonium salt bactericide and preparation method |
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| CN102757558B (en) * | 2011-04-28 | 2014-07-02 | 中国石油化工股份有限公司 | A polyquaternary salt, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065861A (en) * | 1991-01-03 | 1992-11-04 | 罗姆和哈斯公司 | Antimicrobial polymeric quaternary ammonium salts |
| CN1102050A (en) * | 1993-10-30 | 1995-05-03 | 曾志雄 | Quaternary ammonium salt compound disinfectant |
-
1995
- 1995-09-26 CN CN95116434A patent/CN1057427C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065861A (en) * | 1991-01-03 | 1992-11-04 | 罗姆和哈斯公司 | Antimicrobial polymeric quaternary ammonium salts |
| CN1102050A (en) * | 1993-10-30 | 1995-05-03 | 曾志雄 | Quaternary ammonium salt compound disinfectant |
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|---|---|
| CN1146281A (en) | 1997-04-02 |
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