CN111471444B - Polyamino bactericidal surfactant and preparation method and application thereof - Google Patents
Polyamino bactericidal surfactant and preparation method and application thereof Download PDFInfo
- Publication number
- CN111471444B CN111471444B CN202010470828.9A CN202010470828A CN111471444B CN 111471444 B CN111471444 B CN 111471444B CN 202010470828 A CN202010470828 A CN 202010470828A CN 111471444 B CN111471444 B CN 111471444B
- Authority
- CN
- China
- Prior art keywords
- polyamino
- reacting
- surfactant
- stirring
- viscous liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/32—Anticorrosion additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Detergent Compositions (AREA)
Abstract
The invention relates to a polyamino bactericidal surfactant, a preparation method and application thereof, wherein the method comprises the following steps: 1) mixing dipentaerythritol and caproyl chloride, and stirring and reacting for 2-4 hours at the temperature of 30-50 ℃ to obtain a viscous liquid intermediate I; 2) adding the viscous liquid intermediate I into a first solvent, adding powdery sodium hydroxide after the viscous liquid intermediate I is completely dissolved, stirring and reacting for 0.5-1 h at the temperature of 25-35 ℃, then adding 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the solution, heating to 70-90 ℃, reacting for 5-7 h, and carrying out suction filtration on the solution to obtain a solid product intermediate II; 3) and adding the solid product intermediate II into a second solvent, adding hexamethylene diisocyanate under stirring, heating to 40-50 ℃, reacting for 3-5 hours, and performing suction filtration and drying to obtain the polyamino bactericidal surfactant. The polyamino bactericidal surfactant solves the problem that in the process of oil field exploitation, injected water is used for breeding bacteria to corrode exploitation equipment, and further the petroleum yield and the oil gas quality are reduced.
Description
Technical Field
The invention relates to an oilfield auxiliary bactericide, in particular to a polyamino bactericidal surfactant, and a preparation method and application thereof.
Background
Recovery rates have declined year by year with the continuing exploitation and utilization of oil fields, and chemical flooding is often used to increase recovery rates. However, in the process, because the injected water contains a large amount of organic compounds, a large amount of bacteria such as iron bacteria, sulfate reducing bacteria, saprophytic bacteria and the like are propagated, equipment for oil field exploitation is continuously and seriously corroded, further, pipelines are blocked, an oil layer is damaged, finally, the water injection amount, the oil yield and the oil gas quality are reduced, and serious capital loss is caused. In order to reduce the loss, the addition of a surfactant with bactericidal performance during water injection has been studied to reduce the corrosion of the pipelines of the mining equipment. At present, the research on the sterilization performance of quaternary ammonium salt surfactants has made great progress, but the development of novel efficient sterilization surfactants becomes a research hotspot of people along with the improvement of bacterial resistance, the continuous increase of dosage and the increase of input cost year by year.
Disclosure of Invention
The method aims to solve the problem that in the process of oil field exploitation, injected water is corroded by bacteria breeding to exploitation equipment, so that the petroleum yield and the oil gas quality are reduced. The invention aims to provide a polyamino bactericidal surfactant, and a preparation method and application thereof. The polyamino bactericidal surfactant is formed by N in a molecule+The cationic group is an active group, and is adsorbed and aggregated on the surface of negatively charged thallus, so that the permeability of the cell wall of the bacteria is changed, and cytoplasm flows out, and on the other hand, hydrophobic alkyl enters a lipoid layer of cells due to extremely strong hydrophobic effect, so that enzyme protein in the cells is denatured and loses activity, and the sterilization effect is achieved.
The technical scheme adopted by the invention is as follows:
the structural formula of the polyamino bactericidal surfactant is as follows:
a preparation method of a polyamino bactericidal surfactant comprises the following steps:
1) mixing dipentaerythritol and caproyl chloride, stirring and reacting for 2-4 hours at the temperature of 30-50 ℃, and cooling to room temperature; neutralizing, washing, extracting and distilling under reduced pressure to obtain a viscous liquid intermediate I;
2) adding the viscous liquid intermediate I into a first solvent, adding powdery sodium hydroxide after the viscous liquid intermediate I is completely dissolved, stirring and reacting for 0.5-1 h at the temperature of 25-35 ℃, then adding 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the solution, heating to 70-90 ℃, reacting for 5-7 h, and carrying out suction filtration on the solution to obtain a solid product intermediate II;
3) and adding the solid product intermediate II into a second solvent, adding hexamethylene diisocyanate under stirring, heating to 40-50 ℃, reacting for 3-5 hours, and performing suction filtration and drying to obtain the polyamino bactericidal surfactant.
As a further improvement of the invention, in the step 1), the molar ratio of the dipentaerythritol to the caproyl chloride is 1 (2.9-3.1).
As a further improvement of the invention, in the step 2), the adding amount molar ratio of the viscous liquid intermediate I to the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 5-1.
As a further improvement of the present invention, in step 2), the first solvent is dimethyl sulfoxide.
As a further improvement of the invention, in step 3), the solid product intermediate ii is added in an amount of 2: 1 mol.
As a further improvement of the present invention, in step 3), the second solvent is dimethylformamide.
An application of polyamino bactericidal surfactant as bactericide.
The adding mass fraction of the polyamino bactericidal surfactant is 3%, and the using temperature is 35-45%.
The adding amount of the polyamino bactericidal surfactant is 3 percent (mass fraction), and the bacterial liquid contains iron bacteria, sulfate reducing bacteria and saprophytic bacteria. The content is 50mg/L, 76mg/L and 48mg/L respectively.
Compared with the prior art, the invention has the following advantages:
the preparation reaction condition of the surfactant for multi-amino sterilization is mild, the synthetic process is simple, and the raw materials are cheap and easy to obtain. The polyamino surfactant for sterilization contains a plurality of N+On the other hand, hydrophobic alkyl enters a lipoid layer of cells due to extremely strong hydrophobic effect, so that the enzyme protein in the cells is denatured and inactivated. The polyamino surfactant for sterilization has the advantages of high efficiency, low toxicity, no accumulation, no influence of pH change and easy dispersion.
Description of the drawings:
FIG. 1 is a synthetic route of the polyamino germicidal surfactant obtained in example 4;
FIG. 2 nuclear magnetic hydrogen spectrum of a polyamino germicidal surfactant obtained in example 4;
FIG. 3 variation of the sterilization rate with contact time obtained in example 4.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a polyamino bactericidal surfactant, which has the following structural formula:
the principle is as follows: the polyamino bactericidal surfactant has excellent bactericidal performance because positively charged ionic groups in the molecular structure of the polyamino bactericidal surfactant are adsorbed on the surface of bacteria with negative charges, so that the permeability of cell walls of the bacteria is changed, cytoplasm flows out, and a bactericidal effect is achieved.
Specifically, the preparation method of the polyamino bactericidal surfactant comprises the following steps:
(1) adding dipentaerythritol and hexanoyl chloride into a three-neck flask, wherein the molar ratio of the dipentaerythritol to the hexanoyl chloride is 1 (2.9-3.1). After the addition, stirring and reacting for 2-4 h at 30-50 ℃, and cooling to room temperature. And (3) neutralizing with a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 5% (mass fraction). Washing with water, extracting with organic solvent, and distilling under reduced pressure to remove solvent to obtain viscous liquid intermediate I.
(2) Adding the viscous liquid intermediate I obtained in the step (1) into a four-neck flask, wherein the addition amount of the viscous liquid intermediate I is 0.025 mol. Then, dimethyl sulfoxide (DMSO), a first solvent, was added to the four-necked flask in an amount of 120 mL. After the sodium hydroxide is completely dissolved, adding powdery sodium hydroxide, stirring and reacting for 0.5-1 h at the temperature of 25-35 ℃, wherein the addition amount of the powdery sodium hydroxide is 4 g. Then, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is added into a solution containing a solvent such as dimethyl sulfoxide, and the addition amount of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 0.05 mol. And heating to 70-90 ℃, reacting for 5-7 h, and performing suction filtration on the solution to obtain a solid product intermediate II.
(3) And (3) adding the solid product intermediate II in the step (2) into a second solvent, wherein the addition amount of the solid product intermediate II is 0.02mol, and the second solvent is Dimethylformamide (DMF) and is 29.24 g. Hexamethylene Diisocyanate (HDI) was added with magnetic stirring in an amount of 0.01 mol. And heating to 40-50 ℃, reacting for 3-5 h, and performing suction filtration and drying to obtain the polyamino bactericidal surfactant.
4) Adding the polyamino bactericidal surfactant in the step 3) into a bacterial liquid containing iron bacteria, sulfate reducing bacteria and saprophytic bacteria, wherein the adding amount of the polyamino bactericidal surfactant is 3% (mass fraction), the bacterial content is 50mg/L, 76mg/L and 48mg/L respectively, stirring for 0-25h by using a magnetic stirrer, the stirring temperature is 40 ℃, determining the bactericidal rate, and evaluating the bactericidal effect.
The invention is further illustrated by the following specific examples and figures:
example 1
Adding dipentaerythritol and hexanoyl chloride into a three-neck flask according to the molar ratio of 1:2.9, stirring and reacting at 40 ℃ for 3 hours after the addition is finished, and cooling to room temperature. Neutralizing with 5% (mass fraction) sodium hydroxide solution, washing with water, extracting with organic solvent, and distilling under reduced pressure to remove solvent to obtain viscous liquid intermediate I. Adding 0.025mol of viscous liquid intermediate I into a four-neck flask, adding 120mL of dimethyl sulfoxide (DMSO) into the four-neck flask, adding 4g of powdered sodium hydroxide after the viscous liquid intermediate I is completely dissolved, stirring and reacting at 30 ℃ for 0.5h, then adding 0.05mol of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into a solution containing solvents such as dimethyl sulfoxide, heating to 80 ℃, reacting for 6h, and carrying out suction filtration on the solution to obtain a solid product intermediate II. Adding 0.02mol of the solid product intermediate II into 29.24g of Dimethylformamide (DMF), adding 0.01mol of Hexamethylene Diisocyanate (HDI) under magnetic stirring, heating to 45 ℃, reacting for 4h, performing suction filtration and drying to obtain the polyamino bactericidal surfactant, and obtaining 0.00831mol of solid with the calculated yield of 83.1%. Adding the obtained polyamino bactericidal surfactant into a bacterial liquid containing iron bacteria, sulfate reducing bacteria and saprophytic bacteria, wherein the addition amount is 3 percent (mass fraction), the bacterial content is 50mg/L, 76mg/L and 48mg/L respectively, stirring for 0-25h by using a magnetic stirrer, the stirring temperature is 40 ℃, measuring the bactericidal rate, and evaluating the bactericidal effect.
Example 2
Adding dipentaerythritol and hexanoyl chloride into a three-neck flask according to the molar ratio of 1:2.95, stirring and reacting at 40 ℃ for 3 hours after the addition is finished, and cooling to room temperature. Neutralizing with 5% (mass fraction) sodium hydroxide solution, washing with water, extracting with organic solvent, and distilling under reduced pressure to remove solvent to obtain viscous liquid intermediate I. Adding 0.025mol of the viscous liquid intermediate I into a four-neck flask, adding 120mL of dimethyl sulfoxide (DMSO) into the four-neck flask, adding 4g of powdered sodium hydroxide after the viscous liquid intermediate I is completely dissolved, stirring and reacting at 30 ℃ for 0.5h, then adding 0.05mol of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into a solution containing solvents such as dimethyl sulfoxide, heating to 80 ℃, reacting for 6h, and carrying out suction filtration on the solution to obtain a solid product intermediate II. Adding 0.02mol of the solid product intermediate II into 29.24g of Dimethylformamide (DMF), adding 0.01mol of Hexamethylene Diisocyanate (HDI) under magnetic stirring, heating to 45 ℃, reacting for 4h, performing suction filtration and drying to obtain the polyamino bactericidal surfactant, and obtaining 0.00834mol of solid with the calculated yield of 83.4%. Adding the obtained polyamino bactericidal surfactant into a bacterial liquid containing iron bacteria, sulfate reducing bacteria and saprophytic bacteria, wherein the addition amount is 3 percent (mass fraction), the bacterial content is 50mg/L, 76mg/L and 48mg/L respectively, stirring for 0-25h by using a magnetic stirrer, the stirring temperature is 40 ℃, measuring the bactericidal rate, and evaluating the bactericidal effect.
Example 3
Adding dipentaerythritol and hexanoyl chloride into a three-neck flask according to the molar ratio of 1:3, stirring and reacting at 40 ℃ for 3 hours after the addition is finished, and cooling to room temperature. Neutralizing with 5% (mass fraction) sodium hydroxide solution, washing with water, extracting with organic solvent, and distilling under reduced pressure to remove solvent to obtain viscous liquid intermediate I. Adding 0.025mol of viscous liquid intermediate I into a four-neck flask, adding 120mL of dimethyl sulfoxide (DMSO) into the four-neck flask, adding 4g of powdered sodium hydroxide after the viscous liquid intermediate I is completely dissolved, stirring and reacting at 30 ℃ for 0.5h, then adding 0.05mol of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into a solution containing solvents such as dimethyl sulfoxide, heating to 80 ℃, reacting for 6h, and carrying out suction filtration on the solution to obtain a solid product intermediate II. Adding 0.02mol of the solid product intermediate II into 29.24g of Dimethylformamide (DMF), adding 0.01mol of Hexamethylene Diisocyanate (HDI) under magnetic stirring, heating to 45 ℃, reacting for 4h, performing suction filtration and drying to obtain the polyamino bactericidal surfactant, and obtaining 0.00829mol of solid with the calculated yield of 82.9%. Adding the obtained polyamino bactericidal surfactant into a bacterial liquid containing iron bacteria, sulfate reducing bacteria and saprophytic bacteria, wherein the addition amount is 3 percent (mass fraction), the bacterial content is 50mg/L, 76mg/L and 48mg/L respectively, stirring for 0-25h by using a magnetic stirrer, the stirring temperature is 40 ℃, measuring the bactericidal rate, and evaluating the bactericidal effect.
Example 4
Adding dipentaerythritol and hexanoyl chloride into a three-neck flask according to the molar ratio of 1:3.05, stirring and reacting at 40 ℃ for 3 hours after the addition is finished, and cooling to room temperature. Neutralizing with 5% (mass fraction) sodium hydroxide solution, washing with water, extracting with organic solvent, and distilling under reduced pressure to remove solvent to obtain viscous liquid intermediate I. Adding 0.025mol of the viscous liquid intermediate I into a four-neck flask, adding 120mL of dimethyl sulfoxide (DMSO) into the four-neck flask, adding 4g of powdered sodium hydroxide after the viscous liquid intermediate I is completely dissolved, stirring and reacting at 30 ℃ for 0.5h, then adding 0.05mol of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into a solution containing solvents such as dimethyl sulfoxide, heating to 80 ℃, reacting for 6h, and carrying out suction filtration on the solution to obtain a solid product intermediate II. Adding 0.02mol of the solid product intermediate II into 29.24g of Dimethylformamide (DMF), adding 0.01mol of Hexamethylene Diisocyanate (HDI) under magnetic stirring, heating to 45 ℃, reacting for 4h, performing suction filtration and drying to obtain the polyamino bactericidal surfactant, and obtaining 0.00827mol of solid with the calculated yield of 82.7%. Adding the obtained polyamino bactericidal surfactant into a bacterial liquid containing iron bacteria, sulfate reducing bacteria and saprophytic bacteria, wherein the addition amount is 3 percent (mass fraction), the bacterial content is 50mg/L, 76mg/L and 48mg/L respectively, stirring for 0-25h by using a magnetic stirrer, the stirring temperature is 40 ℃, measuring the bactericidal rate, and evaluating the bactericidal effect.
Example 5
Adding dipentaerythritol and hexanoyl chloride into a three-neck flask according to the molar ratio of 1:3.1, stirring and reacting for 3 hours at 40 ℃ after the addition is finished, and cooling to room temperature. Neutralizing with 5% (mass fraction) sodium hydroxide solution, washing with water, extracting with organic solvent, and distilling under reduced pressure to remove solvent to obtain viscous liquid intermediate I. Adding 0.025mol of viscous liquid intermediate I into a four-neck flask, adding 120mL of dimethyl sulfoxide (DMSO) into the four-neck flask, adding 4g of powdered sodium hydroxide after the viscous liquid intermediate I is completely dissolved, stirring and reacting at 30 ℃ for 0.5h, then adding 0.05mol of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into a solution containing solvents such as dimethyl sulfoxide, heating to 80 ℃, reacting for 6h, and carrying out suction filtration on the solution to obtain a solid product intermediate II. Adding 0.02mol of the solid product intermediate II into 29.24g of Dimethylformamide (DMF), adding 0.01mol of Hexamethylene Diisocyanate (HDI) under magnetic stirring, heating to 45 ℃, reacting for 4h, performing suction filtration and drying to obtain the polyamino bactericidal surfactant, and obtaining 0.00821mol of solid with the calculated yield of 82.1%. Adding the obtained polyamino bactericidal surfactant into a bacterial liquid containing iron bacteria, sulfate reducing bacteria and saprophytic bacteria, wherein the addition amount is 3 percent (mass fraction), the bacterial content is 50mg/L, 76mg/L and 48mg/L respectively, stirring for 0-25h by using a magnetic stirrer, the stirring temperature is 40 ℃, measuring the bactericidal rate, and evaluating the bactericidal effect.
In order to characterize the structural characteristics of the polyamino germicidal surfactant, the polyamino germicidal surfactant synthesized in example 4 was subjected to nuclear magnetic hydrogen spectroscopy, and the results are shown in fig. 2.
FIG. 2 nuclear magnetic hydrogen spectrum of a polyamino germicidal surfactant obtained in example 4.
1H NMR(300MHz，DMSO)：δ6.76(s，2H)，5.80(s，8H)，5.37(s，4H)，4.42(m，4H)，3.94(s，16H)，3.79(s，8H)，3.63～3.25(m，56H)，2.32(t，12H)，1.66(m，12H)，1.50～1.28(m，32H)，0.88(t，18H)ppm。
FIG. 3 variation of the sterilization rate with contact time obtained in example 4. After the three bacteria are contacted with the polyamino germicidal surfactant for 15 hours, the germicidal rate is basically maintained stable, the germicidal rate is over 99 percent, and the germicidal effect is obvious.
Example 6
(1) Adding dipentaerythritol and hexanoyl chloride into a three-neck flask, wherein the molar ratio of the dipentaerythritol to the hexanoyl chloride is 1: 2.9. After the addition, the mixture was stirred at 30 ℃ for 2 hours and cooled to room temperature. And (3) neutralizing with a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 5% (mass fraction). Washing with water, extracting with organic solvent, and distilling under reduced pressure to remove solvent to obtain viscous liquid intermediate I.
(2) Adding the viscous liquid intermediate I obtained in the step (1) into a four-neck flask, wherein the addition amount of the viscous liquid intermediate I is 0.025 mol. Then, dimethyl sulfoxide (DMSO), a first solvent, was added to the four-necked flask in an amount of 120 mL. After the sodium hydroxide is completely dissolved, adding powdery sodium hydroxide, stirring and reacting for 0.5h at 25 ℃, wherein the addition amount of the powdery sodium hydroxide is 4 g. Then, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is added into a solution containing a solvent such as dimethyl sulfoxide, and the addition amount of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 0.05 mol. And (3) heating to 70 ℃, reacting for 5 hours, and then carrying out suction filtration on the solution to obtain a solid product intermediate II.
(3) And (3) adding the solid product intermediate II in the step (2) into a second solvent, wherein the addition amount of the solid product intermediate II is 0.02mol, and the second solvent is Dimethylformamide (DMF) and is 29.24 g. Hexamethylene Diisocyanate (HDI) was added with magnetic stirring in an amount of 0.01 mol. Heating to 40 ℃, reacting for 3h, filtering, and drying to obtain the polyamino bactericidal surfactant.
4) Adding the polyamino bactericidal surfactant in the step 3) into a bacterial liquid containing iron bacteria, sulfate reducing bacteria and saprophytic bacteria, wherein the adding amount of the polyamino bactericidal surfactant is 3% (mass fraction), the bacterial content is 50mg/L, 76mg/L and 48mg/L respectively, stirring for 0-25h by using a magnetic stirrer, the stirring temperature is 40 ℃, determining the bactericidal rate, and evaluating the bactericidal effect.
Example 7
(1) Adding dipentaerythritol and hexanoyl chloride into a three-neck flask, wherein the molar ratio of the dipentaerythritol to the hexanoyl chloride is 1:3. After the addition, stirring and reacting for 3 hours at the temperature of 30-50 ℃, and cooling to room temperature. And (3) neutralizing with a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 5% (mass fraction). Washing with water, extracting with organic solvent, and distilling under reduced pressure to remove solvent to obtain viscous liquid intermediate I.
(2) Adding the viscous liquid intermediate I obtained in the step (1) into a four-neck flask, wherein the addition amount of the viscous liquid intermediate I is 0.025 mol. Then, dimethyl sulfoxide (DMSO), a first solvent, was added to the four-necked flask in an amount of 120 mL. After the sodium hydroxide is completely dissolved, adding powdery sodium hydroxide, stirring and reacting for 0.7h at the temperature of 25-35 ℃, wherein the addition amount of the powdery sodium hydroxide is 4 g. Then, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is added into a solution containing a solvent such as dimethyl sulfoxide, and the addition amount of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 0.05 mol. And heating to 85 ℃, reacting for 6 hours, and performing suction filtration on the solution to obtain a solid product intermediate II.
(3) And (3) adding the solid product intermediate II in the step (2) into a second solvent, wherein the addition amount of the solid product intermediate II is 0.02mol, and the second solvent is Dimethylformamide (DMF) and is 29.24 g. Hexamethylene Diisocyanate (HDI) was added with magnetic stirring in an amount of 0.01 mol. Heating to 48 ℃, reacting for 4h, filtering, and drying to obtain the polyamino bactericidal surfactant.
4) Adding the polyamino bactericidal surfactant in the step 3) into a bacterial liquid containing iron bacteria, sulfate reducing bacteria and saprophytic bacteria, wherein the adding amount of the polyamino bactericidal surfactant is 3% (mass fraction), the bacterial content is 50mg/L, 76mg/L and 48mg/L respectively, stirring for 15 hours by using a magnetic stirrer, the stirring temperature is 40 ℃, measuring the bactericidal rate, and evaluating the bactericidal effect.
Example 8
(1) Adding dipentaerythritol and hexanoyl chloride into a three-neck flask, wherein the molar ratio of the dipentaerythritol to the hexanoyl chloride is 1: 3.1. After the addition, the reaction was stirred at 50 ℃ for 4 hours and cooled to room temperature. And (3) neutralizing with a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 5% (mass fraction). Washing with water, extracting with organic solvent, and distilling under reduced pressure to remove solvent to obtain viscous liquid intermediate I.
(2) Adding the viscous liquid intermediate I obtained in the step (1) into a four-neck flask, wherein the addition amount of the viscous liquid intermediate I is 0.025 mol. Then, dimethyl sulfoxide (DMSO), a first solvent, was added to the four-necked flask in an amount of 120 mL. After the sodium hydroxide is completely dissolved, adding powdery sodium hydroxide, stirring and reacting for 1h at the temperature of 35 ℃, wherein the addition amount of the powdery sodium hydroxide is 4 g. Then, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is added into a solution containing a solvent such as dimethyl sulfoxide, and the addition amount of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 0.05 mol. Heating to 90 ℃, reacting for 7 hours, and carrying out suction filtration on the solution to obtain a solid product intermediate II.
(3) And (3) adding the solid product intermediate II in the step (2) into a second solvent, wherein the addition amount of the solid product intermediate II is 0.02mol, and the second solvent is Dimethylformamide (DMF) and is 29.24 g. Hexamethylene Diisocyanate (HDI) was added with magnetic stirring in an amount of 0.01 mol. Heating to 50 ℃, reacting for 5h, filtering, and drying to obtain the polyamino bactericidal surfactant.
4) Adding the polyamino bactericidal surfactant in the step 3) into a bacterial liquid containing iron bacteria, sulfate reducing bacteria and saprophytic bacteria, wherein the adding amount of the polyamino bactericidal surfactant is 3% (mass fraction), the bacterial content is 50mg/L, 76mg/L and 48mg/L respectively, stirring for 25 hours by using a magnetic stirrer, the stirring temperature is 40 ℃, measuring the bactericidal rate, and evaluating the bactericidal effect.
The foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (6)
1. The polyamino germicidal surfactant is characterized in that the structural formula of the polyamino germicidal surfactant is as follows:
2. the preparation method of the polyamino germicidal surfactant as claimed in claim 1, which is characterized by comprising the following steps:
1) mixing dipentaerythritol and caproyl chloride, stirring and reacting for 2-4 hours at the temperature of 30-50 ℃, and cooling to room temperature; neutralizing, washing, extracting and distilling under reduced pressure to obtain a viscous liquid intermediate I;
2) adding the viscous liquid intermediate I into a first solvent, adding powdery sodium hydroxide after the viscous liquid intermediate I is completely dissolved, stirring and reacting for 0.5-1 h at the temperature of 25-35 ℃, then adding 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the solution, heating to 70-90 ℃, reacting for 5-7 h, and carrying out suction filtration on the solution to obtain a solid product intermediate II;
3) adding the solid product intermediate II into a second solvent, adding hexamethylene diisocyanate under stirring, heating to 40-50 ℃, reacting for 3-5 hours, and performing suction filtration and drying to obtain the polyamino bactericidal surfactant;
in the step 1), the molar ratio of dipentaerythritol to caproyl chloride is 1 (2.9-3.1);
in the step 3), the addition amount of the solid product intermediate II is 2: 1 mol;
in the step 2), the adding amount molar ratio of the viscous liquid intermediate I to the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 1:2.
3. The method according to claim 2, wherein in step 2), the first solvent is dimethyl sulfoxide.
4. The method according to claim 2, wherein the second solvent is dimethylformamide in the step 3).
5. Use of a polyamino germicidal surfactant according to claim 1 as a germicidal agent.
6. The use of claim 5, wherein the polyamino germicidal surfactant is added in an amount of 3 wt% and the use temperature is 35-45 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010470828.9A CN111471444B (en) | 2020-05-28 | 2020-05-28 | Polyamino bactericidal surfactant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010470828.9A CN111471444B (en) | 2020-05-28 | 2020-05-28 | Polyamino bactericidal surfactant and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111471444A CN111471444A (en) | 2020-07-31 |
| CN111471444B true CN111471444B (en) | 2022-03-29 |
Family
ID=71763634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010470828.9A Active CN111471444B (en) | 2020-05-28 | 2020-05-28 | Polyamino bactericidal surfactant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111471444B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019206647A (en) * | 2018-05-29 | 2019-12-05 | 東亞合成株式会社 | (meth)acrylate composition and manufacturing method therefor |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2133593C (en) * | 1994-10-04 | 1998-07-07 | Robert G. Swisher | Silylated lubricant with and without other components and on substrates and method |
| JP2005017697A (en) * | 2003-06-26 | 2005-01-20 | Konica Minolta Medical & Graphic Inc | Photosensitive lithographic printing plate and its processing method |
| CN106588723A (en) * | 2016-12-19 | 2017-04-26 | 贵州石博士科技有限公司 | Preparation method of pentaerythritol tris(3-mercaptopropionate) |
| CN107118133A (en) * | 2017-04-17 | 2017-09-01 | 中国石油大学(华东) | A kind of sulfuric ester bi-quaternary ammonium salt polymer-containing sewage in oil field efficient germicide and preparation method thereof |
| CN109021199B (en) * | 2018-07-12 | 2020-12-08 | 四川大学 | Preparation method of waterborne polyurethane leather finishing agent containing quaternary ammonium salt bactericidal group |
| CN110183678B (en) * | 2019-06-14 | 2022-01-25 | 长沙学院 | Water-based hyperbranched polyester resin and preparation method and application thereof |
-
2020
- 2020-05-28 CN CN202010470828.9A patent/CN111471444B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019206647A (en) * | 2018-05-29 | 2019-12-05 | 東亞合成株式会社 | (meth)acrylate composition and manufacturing method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111471444A (en) | 2020-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Baltazar et al. | Interfacial and micellar properties of imidazolium-based monocationic and dicationic ionic liquids | |
| CN103865511A (en) | Visco-elastic surfactant fracturing fluid, and preparation method and application thereof | |
| US5336441A (en) | Corrosion inhibition in highly acidic environments by use of pyridine salts in combination with certain cationic surfactants | |
| Song et al. | Self-aggregation and antimicrobial activity of alkylguanidium salts | |
| US4022833A (en) | N,N'-bridged-bis[2-alkyl-2-hydroxyethylamines] | |
| US20190256458A1 (en) | Synthesis and evaluation of novel amido-amine cationic gemini surfactants containing flexible and rigid spacers | |
| CN108840803B (en) | Method for synthesizing asymmetric biquaternary ammonium salt bactericide | |
| Hussain et al. | Synthesis and evaluation of novel Amido-amine cationic Gemini surfactants containing flexible and rigid spacers | |
| CN111518130B (en) | Symmetrical long-chain siloxane sulfonic surfactant and preparation method and application thereof | |
| CN111321412B (en) | High-salt-content weak-acid oil field water quality corrosion inhibitor with chloride ion content of more than 5 ten thousand ppm | |
| CN111471444B (en) | Polyamino bactericidal surfactant and preparation method and application thereof | |
| CN111559970B (en) | Surface wetting agent with polysulfonic acid structure and preparation method thereof | |
| CN102531928B (en) | Asymmetric bis-quaternary ammonium salt as well as preparation method and application thereof | |
| CN103570561A (en) | Synthesis of tetrameric quaternary ammonium salt | |
| US5000873A (en) | N-(hydrophobe aromatic)pyridinium compounds | |
| CN103288659A (en) | Chloro-dialkyl/aryl dimethyldimethylhydroxypropyldiamine and preparation method thereof | |
| CN102351755B (en) | Fluorine-containing imine cationic surfactant preparation method and application thereof | |
| CN106268495B (en) | A kind of N, N, N- cocoyl-ethoxy-methyl-N ', N ', N ' the double chlorination ammonium surfactants of-dihydroxy ethyl-methyl trimethylene and preparation method | |
| CN111468033B (en) | Silicon-containing surfactant and preparation method and application thereof | |
| CN101648118A (en) | Cation Gemini surfactant containing ethylenic bond spacer group and preparation method thereof | |
| Gab-Allah et al. | Three novel gemini amide amphiphilics synthesis, characterization, thermodynamics, surface properties and biological activity | |
| CN117143332B (en) | Preparation method of corrosion inhibitor for oilfield sewage containing sulfate reducing bacteria | |
| US2310789A (en) | Linear polymeric amidine salts | |
| CN109987723A (en) | A kind of non-phosphorus scale and corrosion inhibitor and its preparation method and application | |
| US4312831A (en) | Quaternaries of tertiary amino-substituted thiazines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220610 Address after: Room 1301, block F, Changhe international, No. 180, Fengcheng 8th Road, Xi'an Economic and Technological Development Zone, Shaanxi 710000 Patentee after: XI'AN AODE PETROLEUM ENGINEERING TECHNOLOGY CO.,LTD. Address before: 710021 Shaanxi province Xi'an Weiyang University Park Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
|
| TR01 | Transfer of patent right |