CN104725320A - Sulfitonetaine sterilizing agent and synthetic method thereof - Google Patents
Sulfitonetaine sterilizing agent and synthetic method thereof Download PDFInfo
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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Abstract
The invention discloses four zwitterionic sterilizing agents containing a sulfitonetaine structure and a synthetic method thereof. The synthetic method is characterized by comprising the following steps: (1) adding 1-methylimidazole (or 4-methylmorpholine, or N, N-dimethyl benzylamine, or 3-dimethylamino methylindole) in a three-necked flask and fully dissolving by 1, 4-dioxane; (2) heating till refluxing, slowly dropwise a certain amount of ethylene sulfite while stirring, and reacting for 2-5h after the dropwise adding step is finished; (3) removing the solvent, recrystallizing by using acetonitrile and performing vacuum drying to obtain the white powdered solid sterilizing agent. The sterilizing agent has the characteristics of good water solubility, good killing effect on sulfate reducting bacteria (SRB) and saprophytic bacteria (TGB) and long-lasting sterilizing effect. The oil field injected water and the oil field sewage can be well sterilized by the sterilizing agent; therefore, the sterilizing agent has a wide market application prospect.
Description
Technical field
The present invention relates to four kinds of water treatment biocides and synthetic method thereof, particularly petroleum industry oilfield injection water and oilfield sewage sterilant and synthetic method thereof.
Background technology
Along with the raising of socio-economic development and scientific and technological level, the environmental consciousness of people constantly strengthens, and has higher requirement to living environment quality.Therefore, the chemical agent with function of killing livestock is subject to people and pays close attention to, and has been widely used in the numerous areas such as energy extraction, health care and daily life.In present stage, oil is still the pillar energy promoting society's running, in oil production, improves oil recovery factor by modes such as water filling, injection of polymer solution.And in oil-field flooding, often have multiple-microorganism to grow, mainly contain sulphate reducing bacteria (SRB), saprophytic microorganism (TGB), iron bacteria (IB) etc.These bacteriums, can cause the corrosion damage of equipment, the blocking of pipeline and water injection well; Oil reservoir pore permeability is declined, reduces oil recovery factor; Weaken the end-use performance of other oil field chemical, even make chemical degrade.Meanwhile, in oil production process, oilfield sewage inevitably enters soil, has had a strong impact on environment.
Water treatment biocide refers to the class chemical reagent for controlling or kill bacterium in water.Conventional water treatment biocide kind is more, and oxidizing sterilant, as chlorine-based sterilizing agent, bromo sterilant, superoxide etc.; Non oxidizing bactericide, as quaternary ammonium salt, organosulfur compound class etc.In the sterilant of of a great variety, Various Functions, quarternary ammonium salt compound is with the bactericidal performance of its broad-spectrum high efficacy, and the advantage such as use range is wide, good water solubility, safety and low toxicity is used widely in a lot of fields.1915, Jacobs W A etc. found that quarternary ammonium salt compound has certain sterilizing ability.Nineteen thirty-five, Domagk G finds the germicidal action of alkyl dimethyl benzyl ammonium chloride, and studies the relation of its bactericidal property and structure further.In the same year, quaternary ammonium salt bactericide is used in clinical disinfection by Wetzel R.The sterilization mechanism of quaternary ammonium salt is mainly: quaternary ammonium salt is adsorbed onto phage surface, and hydrophobic group inserts class lipid layer, changes the permeability of cell walls, film, and intracellular organic matter leaks, enzyme or protein denaturation, and last thalline is dead.
At present, quaternary ammonium salt bactericide research emphasis mainly modified quaternary ammonium salt, two quaternary ammonium alkyl, polyquaternium and various quaternary ammonium salt series bactericidal agent combination.The sterilant of domestic normal use is dodecyl benzyl dimethyl ammonium chloride (geramine) and dodecyl dimethyl benzyl ammonium bromide (bromogeramine), they are wide spectrum biocides, all have to algae, fungi and heterotrophic bacterium etc. effect of killing livestock preferably, stripping effect can also be had to mud.But because it uses comparatively extensive, the time is longer, creates resistance.In recent years, the people such as Chu Bing have synthesized sulfitonetaine type sterilant ten four (six) alkyl dimethyl (2-sulfurous acid) ethyl ammonium, its sterilization effect is 2-5 times of dodecyl benzyl dimethyl ammonium chloride (1227), and sludge stripping ability is better.It is a kind of zwitter-ion, has well water-soluble, and containing organosulfur group, and then enhance the sterilization effect of quaternary ammonium salt.But less to the report of this type of sulfitonetaine sterilant, also less to the research of its bactericidal property.Based on above viewpoint, the present invention synthesizes four kinds of novel quatemay ammonium inner salt zwitterionic compound sterilant containing sulfurous acid.
Summary of the invention
The object of this invention is to provide four kinds of zwitter-ion sterilant containing sulfitonetaine structure.
Second object of the present invention is to provide four kinds of preparation methods containing the zwitter-ion sterilant of sulfitonetaine structure, and the method principle is reliable, and easy and simple to handle, productive rate is higher, and environmental protection.
For reaching above technical purpose, the invention provides following technical scheme.
The negatively charged ion of four kinds of sterilant that this patent provides is a kind of sulfite ion, and positively charged ion is four kinds of Ammonium Salt Ionic containing ring, and four kinds of sterilant contain following universal expression formula I:
Wherein the positively charged ion of four kinds of sterilant is respectively containing following structure, as expressed formula II:
Be respectively 2-(1-Methylimidazole) ethyl-sulfurous acid ester salt, 2-(4-methylmorpholine) ethyl-sulfurous acid ester salt, 2-(benzyl dimethyl is amino) ethyl-sulfurous acid ester salt and 2-((3-indyl) methyl dimethoxy base is amino) ethyl-sulfurous acid ester salt containing four kinds of sterilant of expressing (1), (2), (3) and (4) in formula II, code name is respectively IAES, MLES, BDES and IDES.
Four kinds of raw materials containing the zwitter-ion sterilant of sulfitonetaine structure provided by the present invention are 1-Methylimidazole, 4-methylmorpholine, N, N-dimethyl benzylamine, 3-dimethylamino methyl indoles and ethylene sulfite.
Four kinds of synthetic methods containing the zwitter-ion sterilant of sulfitonetaine structure provided by the present invention, comprise the following steps successively: add specified amount 1-Methylimidazole (or 4-methylmorpholine or N at there-necked flask, N-dimethyl benzylamine or 3-dimethylamino methyl indoles), a certain amount of Isosorbide-5-Nitrae-dioxane; Be heated to backflow, under constantly stirring, slowly drip a certain amount of ethylene sulfite, after dripping, reaction 2-5h; Revolve and steam except desolventizing, carry out recrystallization with acetonitrile, after vacuum-drying, namely obtain white powder sterilant.
The mol ratio of described ethylene sulfite and 1-Methylimidazole (or 4-methylmorpholine or N, N-dimethyl benzylamine or 3-dimethylamino methyl indoles) is 1 ~ 1.2:1;
Described Isosorbide-5-Nitrae-dioxane is as solvent, and wherein 1-Methylimidazole (or 4-methylmorpholine or N, N-dimethyl benzylamine or 3-dimethylamino methyl indoles) is 1:1 ~ 2 with the volume ratio of Isosorbide-5-Nitrae-dioxane.
Sterilant provided by the present invention has following beneficial effect: the introducing of (1) nitrogen-atoms improves the fungicidal activity of compound preferably; (2) sulphur atom is incorporated in compound, makes the active raising further of quaternary ammonium salt bactericide; (3) sterilant is zwitter-ion, makes it have good water-soluble, can play better sterilization effect in water; (4) sterilant carbochain is shorter, and its aqueous solution bubbles less; (5) this sterilant is easily degraded, environmental protection.
Sulfitonetaine sterilant provided by the present invention has good water-soluble, the feature such as to have good sterilizing ability, its sterilization effect time length longer to sulphate reducing bacteria (SRB), saprophytic microorganism (TGB) and iron bacteria (IB), described sterilant can carry out germicidal treatment to oilfield injection water and oilfield sewage preferably, has wide market application foreground.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of sterilant IAES of the present invention.
Fig. 2 is the infrared spectrum of sterilant MLES of the present invention.
Fig. 3 is the infrared spectrum of sterilant BDES of the present invention.
Fig. 4 is the infrared spectrum of sterilant IDES of the present invention.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with the specific embodiment of the invention and corresponding accompanying drawing, technical solution of the present invention is clearly and completely described.
The synthesis of embodiment one intermediate ethylene sulfite
The synthetic method of intermediate ethylene sulfite is specific as follows:
(1) in 250mL there-necked flask, add ethylene glycol 62.1g (1.0mol), under constantly stirring, add sulfur oxychloride 88mL (1.2mol);
(2) water bath with thermostatic control is heated to 35 ~ 40 DEG C, and irritant gas effusion, absorbs escaping gas with alkali lye;
(3) after sulfur oxychloride dropwises, temperature of reaction is raised to 70 DEG C, reaction 2h;
(4), after having reacted, underpressure distillation, collects 60-70 DEG C/3.3 × 10
3pa.
The synthesis of embodiment two sterilant
Test the synthesis of 1 sterilant 2-(1-Methylimidazole) ethyl-sulfurous acid ester salt IAES:
(1) in 250mL there-necked flask, 1-Methylimidazole 8.2g (100mmol) is added, the Isosorbide-5-Nitrae-dioxane of 20mL;
(2) be heated to reflux temperature, under constantly stirring, slowly drip 13.0g (120mmol) ethylene sulfite, after dripping, reaction 2-5h;
(3) reacted to revolve and steamed except desolventizing, carried out recrystallization 2-3 time with acetonitrile, after vacuum-drying, namely obtain faint yellow particulate solid 2-(1-Methylimidazole) ethyl-sulfurous acid ester salt.
Test the synthesis of 2 sterilant 2-(4-methylmorpholine) ethyl-sulfurous acid ester salt MLES:
(1) in 250mL there-necked flask, 4-methylmorpholine 10.1g (100mmol) is added, the Isosorbide-5-Nitrae-dioxane of 20mL;
(2) be heated to reflux temperature, under constantly stirring, slowly drip 13.0g (120mmol) ethylene sulfite, after dripping, reaction 2-5h;
(3) reacted to revolve and steamed except desolventizing, carried out recrystallization 2-3 time with acetonitrile, after vacuum-drying, namely obtain light yellow particulate solid 2-(4-methylmorpholine) ethyl-sulfurous acid ester salt.
Test the synthesis of 3 sterilant 2-(benzyl dimethyl is amino) ethyl-sulfurous acid ester salt BDES:
(1) in 250mL there-necked flask, N is added, the Isosorbide-5-Nitrae-dioxane of N-dimethyl benzylamine 13.5g (100mmol), 20mL;
(2) be heated to reflux temperature, under constantly stirring, slowly drip 13.0g (120mmol) ethylene sulfite, after dripping, reaction 2-5h;
(3) reacted to revolve and steamed except desolventizing, carried out recrystallization 2-3 time with acetonitrile, after vacuum-drying, namely obtain white powdery solids 2-(benzyl dimethyl is amino) ethyl-sulfurous acid ester salt.
Test the synthesis of 4 sterilant 2-((3-indyl) methyl dimethoxy base is amino) ethyl-sulfurous acid ester salt IDES:
(1) in 250mL there-necked flask, 3-dimethylamino methyl indoles 17.4g (100mmol) is added, the Isosorbide-5-Nitrae-dioxane of 20mL;
(2) be heated to reflux temperature, under constantly stirring, slowly drip 13.0g (120mmol) ethylene sulfite, after dripping, reaction 2-5h;
(3) reacted to revolve and steamed except desolventizing, carried out recrystallization 2-3 time with acetonitrile, after vacuum-drying, namely obtain white powdery solids 2-((3-indyl) methyl dimethoxy base is amino) ethyl-sulfurous acid ester salt.
The structural characterization of embodiment three sterilant
By infrared spectrum, structural analysis is carried out to samples prepared by test 1 in embodiment two, test 2, test 3 and test 4.Adopt KBr pressed disc method, characterized sterilant structure by WQF-520A Fourier transform infrared spectrometer, infrared spectrum as shown in Figure 1, Figure 2, Figure 3 and Figure 4.As can be seen from Figure 1, as can be seen from Figure 1,3095cm
-1for the stretching vibration of hydrogen on unsaturated carbon, 2095,2877cm
-1place is methyl stretching vibration peak, 1648cm
-1for the stretching vibration of C=C on imidazole ring, 1115cm
-1for the stretching vibration peak of S=O; As can be seen from Figure 2,2956,2881cm
-1for methyl stretching vibration peak, 1123,1031cm
-1for the vibration absorption peak of S=O, S-O; As can be seen from Figure 3,3030cm
-1for the stretching vibration of hydrogen on unsaturated carbon, 2979,2850cm
-1for methyl and methylene radical is the stretching vibration peak of C-H, 1119,1067cm
-1for the vibration absorption peak of S=O, S-O, 724,770cm
-1for the charateristic avsorption band of hydrogen on phenyl ring; As can be seen from Figure 4,3056cm
-1for the stretching vibration of hydrogen on unsaturated carbon, 2987,2937cm
-1for methyl and methylene radical is the stretching vibration peak of C-H, 1636cm
-1for the stretching vibration absorption peak of C=C, 1230,1056cm
-1for the vibration absorption peak of S=O, S-O; In Fig. 1, Fig. 2, Fig. 3 and Fig. 4,3000cm
-1below all have one to absorb very strong broad peak, this is because quaternary ammonium salt easily absorbs water, and is the stretching vibration absorption peak of O-H herein.Analyze from infrared spectrum, spectrogram all contains containing C-N, C-O, S-O, S=O ,-CH
3deng group, consistent with target product structure.
The sterilization effect of embodiment four sterilant is investigated
The present embodiment for sample, carries out effect expedition to four kinds of sterilant with Oil Field sewage.
In the present embodiment, oilfield sewage used is TulufanHami oil field temperature rice block sample, and wherein TGB content is 2.5 × 10
3individual/mL, IB content is 2.5 × 10/mL, SRB content is>=2.5 × 10
2individual/mL.
In the present embodiment, Performance Valuation of Bactericides method adopts the test bottle method of dilution-to-extinction method, with reference to SY/T 5890-1993 " bactericidal property evaluation method ", and sterilizing rate=(starter bacteria number-deposit viable count)/starter bacteria number.
Test the sterilization effect of 1 different sterilization duration
Become 50mg/L bacteria suspension to carry out the evaluation of sterilization duration with the sample preparations of test 4 preparation test 1 in embodiment two, test 2, test 3, bacteria suspension temperature 30 DEG C, pH=7, result is as table 1.
Sterilization effect under the different duration of table 1
As can be seen from Table 1: for SRB, sterilant sample all has the advantage of long timeliness, and 48h still can keep higher sterilizing rate, and IDES, BDES, IAES, MLES sterilizing rate all can be reached for 99.9%; For TGB, the sterilant sample sterilization effect time length is relatively short, and after 24h, sterilant loses germicidal action, and when 24h, IDES sterilizing rate is 97.8%, BDES sterilizing rate be 99.9%, IAES sterilizing rate be 93.4%, MLES sterilizing rate is 96.9%; For IB, the sterilant sample sterilization effect time length is the shortest, and after 4h, sterilant loses drug effect substantially to IB, and when 4h, IAES sterilizing rate is 82.5%, MLES sterilizing rate be 79.5%, BDES sterilizing rate be 91.6%, IDES sterilizing rate is 93.9%.In the present invention, sterilant IAES, MLES, BDES all have good sterilization effect, longer sterilization time length and its sterilization effect similar with IDES to sulphate reducing bacteria (SRB), saprophytic microorganism (TGB), and relatively short for action time to the sterilization effect of iron bacteria (IB), sterilizing rate is also relatively low.
Test the sterilization effect of 2 different sterilant consumptions
By in embodiment two test 1, test 2, test 3 and test 4 preparation samples be mixed with different sterilant Content inspect sterilant consumption to the impact of sterilizing rate from bacteria suspension, bacteria suspension temperature 30 DEG C, action time 1h, pH=7, result is as table 2.As can be seen from Table 2: for SRB, when sterilant IAES, MLES, BDES and IDES consumption is 50mg/L, sterilizing rate can reach about 90%, and when sterilant consumption is 100mg/L, sterilizing rate just can reach 99.9%; For TGB, when sterilant consumption is 50mg/L, sterilizing rate can reach 80%, and when sterilant consumption is 100mg/L, sterilant IAES, MLES, BDES and IDES sterilizing rate can reach more than 95% even 99.9%; For IB, sterilant sterilization effect is poor, and when sterilant consumption is 120mg/L, the sterilizing rate of IAES, MLES fails to reach 90%, MDES, the sterilizing rate of IDES also fails to reach 95%.In the present invention, sterilant sample has good sterilization effect to sulphate reducing bacteria, and sterilant consumption is less.
The sterilization effect of the different sterilant consumption of table 2
Test the sterilization effect under 3 differing tempss
Usual SRB existence is in the environment of 25 ~ 30 DEG C, but some sulphate reducing bacterias also can at 60 times, and iron bacteria survives usually under normal temperature temperature on the low side, and saprophytic microorganism survives at normal temperatures, and therefore we have carried out bactericidal assay at different temperatures to sterilant.By testing 1 in embodiment two, test 2, test 3 and test 4 preparation samples and bacteria suspension be mixed with containing 50mg/L sterilant, investigation operative temperature on the impact of sterilizing rate, action time 1h, pH=7, result is as table 3.For sulphate reducing bacteria SRB, in the scope that temperature is 20 ~ 50 DEG C, sterilant IAES, MLES, BDES and IDES all have good sterilization effect, and simultaneously at 60 DEG C, sterilant sample still has germicidal action; For saprophytic microorganism TGB, bactericidal assay is carried out in the temperature range of 20 ~ 50 DEG C, and the sterilization effect of sterilant IAES, MLES, BDES and IDES is slightly poor, is only about 80%; For iron bacteria IB, bactericidal assay is carried out in the temperature range of 20 ~ 40 DEG C, and sterilizing rate is lower.Result shows, in the present invention, sample is better to sulphate reducing bacteria sterilization effect, and stabilized at may be used for 60 DEG C.
Sterilization effect under table 3 differing temps
Test the sterilization effect under 4 different pH
Usual sulphate reducing bacteria be distributed in pH value be 6 ~ 9 soil, seawater, river, in mud river Oil/gas Well and rusty scale.And the acid environment that iron bacteria preference irony is more, take carbonate as carbon source, its optimum pH is survive in the environment of 6 ~ 8.By testing 1 in embodiment two, test 2, test 3 and test 4 preparation samples and bacteria suspension be mixed with containing 50mg/L sterilant, investigation action pH on the impact of sterilizing rate, action time 1h, temperature is 30 DEG C, and result is as table 4.For sulphate reducing bacteria SRB, in the scope that pH is 5 ~ 10, sample IAES, MLES, BDES and IDES all have certain sterilization effect, be that under the condition of 8, sterilizing rate can reach 90%, but when pH is 10, the sterilization effect of sample significantly decline at pH; For saprophytic microorganism TGB, bactericidal assay is carried out within the scope of the pH of 5 ~ 8, and the sterilization effect of sample IAES, MLES, BDES and IDES is slightly poor, and sterilizing rate is the highest in neutral conditions; For iron bacteria IB, bactericidal assay is carried out within the scope of the pH of 5 ~ 8, and sterilization effect is poor.Result shows, in the present invention, sterilant sample all has certain germicidal action to sulphate reducing bacteria, saprophytic microorganism and iron bacteria, and best to the sterilization effect of sulphate reducing bacteria.
Sterilization effect under the different pH of table 4
Although describe in detail the specific embodiment of the present invention in conjunction with specific embodiments, it is not the restriction to this patent protection domain.In claims limited range, the various amendment that those skilled in the art can make without creative work or adjustment are still by the protection of this patent.
The foregoing is only the embodiment of the application, be not limited to the application, for a person skilled in the art, the application can have various modifications and variations.Within all spirit in the application and principle, any amendment done, equivalent replacement, improvement etc., within the right that all should be included in the application.
Claims (4)
1. four kinds of zwitter-ion sterilant containing sulfitonetaine structure, its constitutional features is the negatively charged ion of sterilant is a kind of sulfite ion, and positively charged ion is four kinds of Ammonium Salt Ionic containing ring, and four kinds of sterilant contain following universal expression formula I:
2. the positively charged ion of four kinds of sterilant according to claim 1 is respectively containing following structure, as expressed formula II:
Be respectively 2-(1-Methylimidazole) ethyl-sulfurous acid ester salt, 2-(4-methylmorpholine) ethyl-sulfurous acid ester salt, 2-(benzyl dimethyl is amino) ethyl-sulfurous acid ester salt and 2-((3-indyl) methyl dimethoxy base is amino) ethyl-sulfurous acid ester salt containing four kinds of sterilant of expressing (1), (2), (3) and (4) in formula II, code name is respectively IAES, MLES, BDES and IDES.
3. four kinds of synthetic methods containing the zwitter-ion sterilant of sulfitonetaine structure according to claim 2, it is characterized in that comprising the following steps successively: (1) adds specified amount 1-Methylimidazole (or 4-methylmorpholine or N at there-necked flask, N-dimethyl benzylamine or 3-dimethylamino methyl indoles), a certain amount of Isosorbide-5-Nitrae-dioxane; (2) be heated to backflow, under constantly stirring, slowly drip a certain amount of ethylene sulfite, after dripping, reaction 2-5h; (3) except desolventizing, carry out recrystallization with acetonitrile, after vacuum-drying, namely obtain white powdery solids sterilant.
4. the mol ratio of ethylene sulfite according to claim 3 and 1-Methylimidazole (or 4-methylmorpholine or N, N-dimethyl benzylamine or 3-dimethylamino methyl indoles) is 1 ~ 1.2:1;
Described Isosorbide-5-Nitrae-dioxane is as solvent, and wherein 1-Methylimidazole (or 4-methylmorpholine or N, N-dimethyl benzylamine or 3-dimethylamino methyl indoles) is 1:1 ~ 2 with the volume ratio of Isosorbide-5-Nitrae-dioxane.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2041439A5 (en) * | 1969-04-24 | 1971-01-29 | Conservatoire Nal Arts | Aminoethane sulphonate esters taurines - and betaines |
GB1322209A (en) * | 1969-11-11 | 1973-07-04 | Basf Ag | Production of sulphitobetaines |
US4855423A (en) * | 1986-10-16 | 1989-08-08 | Basf Aktiengesellschaft | Preparation of sulfatobetaines |
CN1130176A (en) * | 1995-12-15 | 1996-09-04 | 南京化工大学 | Alkyl-dimethyl-2-(sulfurous acid) ethyl ammonium and its preparing method |
CN102696653A (en) * | 2012-05-04 | 2012-10-03 | 中国石油天然气股份有限公司 | Bactericide for oil well sulfate reducing bacteria corrosion |
-
2015
- 2015-01-05 CN CN201510002848.2A patent/CN104725320A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2041439A5 (en) * | 1969-04-24 | 1971-01-29 | Conservatoire Nal Arts | Aminoethane sulphonate esters taurines - and betaines |
GB1322209A (en) * | 1969-11-11 | 1973-07-04 | Basf Ag | Production of sulphitobetaines |
US4855423A (en) * | 1986-10-16 | 1989-08-08 | Basf Aktiengesellschaft | Preparation of sulfatobetaines |
CN1130176A (en) * | 1995-12-15 | 1996-09-04 | 南京化工大学 | Alkyl-dimethyl-2-(sulfurous acid) ethyl ammonium and its preparing method |
CN102696653A (en) * | 2012-05-04 | 2012-10-03 | 中国石油天然气股份有限公司 | Bactericide for oil well sulfate reducing bacteria corrosion |
Non-Patent Citations (3)
Title |
---|
原根明,等: "表面活性甜菜碱的合成及其应用", 《山西化工》 * |
褚兵,等: "两性表面活性剂十二烷基(2-亚硫酸)乙基二甲基铵的合成", 《精细化工》 * |
黄志宇,等: "《表面及胶体化学(第二版)》", 31 August 2012 * |
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