Slow-release sterilization type foam drainage agent and preparation method thereof

Abstract

The application discloses a slow-release bactericidal foam drainage agent and a preparation method thereof, and belongs to the technical field of foam drainage agent preparation. The slow-release bactericidal foam drainage agent is composed of the following components in parts by weight: 30-50 parts of distilled water, 6-12 parts of a surfactant, 4-10 parts of a slow-release bactericide, 3-11 parts of a protective agent, 1-4 parts of a stabilizer and 0.4-2 parts of a pH regulator. The slow-release bactericide is prepared from 3-chloropropionic acid, dipentaerythritol, triallylamine, cetyltrimethylammonium bromide, tetraethyl orthosilicate and gamma-aminoethylaminopropyltrimethoxysilane; and the protective agent is prepared from p-cycloaromatic hydrocarbon, 1,1-dichlorodimethyl ether, p-toluenesulfonamide, diethylamine and p-toluenesulfisothiocyanate. The foam drainage agent prepared by the method has excellent bactericidal effect and can well protect the pipeline from corrosion.

Description

Technical Field

[0001] This invention belongs to the field of foam drainage agent preparation technology, specifically relating to a slow-release bactericidal foam drainage agent and its preparation method. Background Technology

[0002] With the rapid development of industrial production, especially in fields such as oil extraction, chemical production, food processing, and water treatment, the performance requirements for drainage agents are increasingly stringent. Traditional foam drainage agents mainly focus on drainage, but in practical applications, they often face problems such as microbial contamination, equipment corrosion, and high costs due to large dosages. Therefore, developing a slow-release bactericidal foam drainage agent that can effectively drain water while also possessing bactericidal and slow-release functions has become crucial for solving these problems.

[0003] In the field of water treatment, especially in the treatment of urban sewage and industrial wastewater, the application of foam drainage agents is becoming increasingly widespread. However, traditional foam drainage agents often generate a large amount of foam during the treatment process, which not only affects treatment efficiency but may also cause secondary pollution to the environment. At the same time, these foam drainage agents often lack bactericidal functions and cannot effectively inhibit the growth of microorganisms in the water, increasing the difficulty and cost of subsequent treatment. Therefore, there is an urgent need to develop a slow-release bactericidal foam drainage agent that can both efficiently drain water and kill microorganisms while being environmentally friendly.

[0004] Patent CN114736663B discloses a bactericidal foam drainage agent with corrosion-inhibiting function and its preparation method, comprising the following raw materials in parts by weight: 15-30 parts of cocamidopropyl dimethyl tertiary amine, 10-25 parts of lauramide propyl dimethyl tertiary amine, 10-20 parts of hydrogen peroxide, 10-15 parts of benzalkonium bromide, 5-15 parts of glutaraldehyde, 5-15 parts of pyridine quaternary ammonium salt, and 10-37 parts of water. This drainage agent effectively solves the problems of incompatibility between the foaming agent and the bactericide in the prior art, which affect the foaming and bactericidal effects, as well as the large dosage and high cost. However, there is still room for improvement in the bactericidal effect and the protection effect on the pipeline of the drainage agent prepared by this method. Summary of the Invention

[0005] The purpose of this invention is to provide a slow-release bactericidal foam drainage agent and its preparation method, in order to solve the technical problems of poor bactericidal effect and poor protection effect on pipelines in the prior art.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a slow-release bactericidal foam drainage agent, composed of the following components in parts by weight: 30-50 parts distilled water, 6-12 parts surfactant, 4-10 parts slow-release bactericide, 3-11 parts protectant, 1-4 parts stabilizer, and 0.4-2 parts pH adjuster. The slow-release bactericide is prepared from 3-chloropropionic acid, dipentaerythritol, triallylamine, hexadecyltrimethylammonium bromide, tetraethyl orthosilicate, and γ-aminoethylaminopropyltrimethoxysilane. The protectant is prepared from p-cycloaramine, 1,1-dichlorodimethyl ether, p-toluenesulfonamide, diethylamine, and p-toluene isothiocyanate.

[0007] Preferably, the method for preparing the slow-release bactericide includes the following steps: Q1: Add 3-chloropropionic acid to a container equipped with a stirring reflux device, heat and add dipentaerythritol, heat to react, wash, dissolve, dry, filter, and reduce pressure to obtain intermediate 1; add intermediate 1 to chloroform, stir to dissolve, and slowly add triallylamine dropwise using a constant pressure dropping funnel. After the addition is complete, reflux to react, reduce pressure, recrystallize, and dry under vacuum to obtain intermediate 2; Q2: Hexadecyltrimethylammonium bromide was added to a round-bottom flask containing ultrapure water and ultrasonically dispersed. Then, it was placed in an oil bath and magnetically stirred. Sodium hydroxide solution was then added and heated. Tetraethyl orthosilicate, ethyl acetate, and γ-aminoethylaminopropyltrimethoxysilane were added in sequence. After stirring, the mixture was centrifuged, washed, and the precipitate was added to anhydrous ethanol. Hydrochloric acid was added, and the mixture was heated, stirred, and refluxed. After centrifugation, the precipitate was collected, washed, dried, and calcined to obtain intermediate 3. Q3: Add intermediate 2 to ultrapure water, stir to obtain a mixed solution, add intermediate 3 to the mixed solution, continue stirring, centrifuge, and dry to obtain a slow-release bactericide.

[0008] In the above process, firstly, using pentaerythritol as the core, intermediate 2 is obtained through esterification with 3-chloropropionic acid, followed by quaternization with triallylamine. Then, intermediate 3 is prepared by hydrolyzing tetraethyl orthosilicate using the Stober method. Intermediate 2 is then loaded onto intermediate 3 by stirring to obtain a slow-release bactericide. The synthesis reaction formula of intermediate 2 is as follows:

[0009] The mass spectrometry analysis results of intermediate 1 were as follows: m / z: 796.06 (100.0%), 798.05 (78.8%), 794.06 (51.4%), 800.05 (33.6%), 797.06 (30.8%), 799.06 (25.4%), 795.06 (15.8%), 801.05 (10.2%), 802.05 (8.0%), 798.06 (7.1%), 800.06 (5.8%), 803.05 (2.5%), 802.06 (2.5%), 796.07 (2.4%), 804.05 (1.6%), 801.06 (1.3%); the mass spectrometry analysis results of intermediate 1 were as follows: m / z: 234.49 (100.0%), 234.66 (91.4%), 234.83 (40.6%), 235.00 (14.4%), 234.83 (4.7%), 235.16 (3.8%), 234.66 (1.5%).

[0010] Preferably, in Q1, the molar ratio of 3-chloropropionic acid to dipentaerythritol is (6-8.5):(1-1.5), the reaction temperature is 120-140℃, the reaction time is 8-10h, the product is washed with a 1:1 mixture of methanol and distilled water, dissolved in chloroform, and dried with anhydrous sodium sulfate; the molar ratio of intermediate 1 to triallylamine is (1-1.2):(6-7.5), the reaction time is refluxed for 8-10h, and acetone is added for recrystallization.

[0011] Preferably, in Q2, the ratio of hexadecyltrimethylammonium bromide, ultrapure water, sodium hydroxide solution, tetraethyl orthosilicate, ethyl acetate, γ-aminoethylaminopropyltrimethoxysilane, anhydrous ethanol, and hydrochloric acid is (1-2) g : (380-750) mL : (2.5-5) mL : (5-9) mL : (10-22) mL : (0.5-0.9) mL : (300-550) mL : (0.32-0.63) mL, the ultrasonic dispersion time is 20-30 min, the magnetic stirring speed is 600-800 rpm, and the hydrogen-oxygen... The sodium chloride solution concentration is 2 mol / L, the heating temperature is 80-90℃, the stirring time is 2-4 h, the centrifugation speed is 10000-12000 rpm, the centrifugation time is 5-8 min, and the solution is washed 3-5 times alternately with ultrapure water and anhydrous ethanol. The hydrochloric acid concentration is 5 mol / L, the heating and stirring reflux temperature is 60-65℃, the time is 10-12 h, the centrifugation speed is 8000-12000 rpm, the time is 8-12 min, the drying temperature is 80-90℃, the time is 12-15 h, and the calcination temperature is 400-500℃.

[0012] Preferably, in Q3, the ratio of intermediate 2, ultrapure water and intermediate 3 is (20-40) mg: (100-150) mL: (40-55) mg, the stirring time is 10-12 h, the stirring time is continued for 20-24 h, the centrifugation speed is 8000-10000 rpm, the time is 5-7 min, the drying temperature is 50-60℃, and the time is 10-12 h.

[0013] Preferably, the method for preparing the protective agent includes the following steps: S1: Add p-cycloarane and dichloromethane to a round-bottom flask and stir at low temperature. Then add titanium tetrachloride and 1,1-dichlorodimethyl ether. After the addition is complete, stir to react. After the reaction is complete, add distilled water, extract, collect the organic phase by separation, wash, dry, filter, concentrate under reduced pressure to obtain product A. Then add product A and p-toluenesulfonamide to a container, add tetraethyl silicate, heat and stir in an oil bath, cool, add petroleum ether, filter, recrystallize to obtain product B. S2: Add product B, diazabicyclohexane, and 4A molecular sieve to a container, then add a mixed solution of toluene and diethylamine, seal the container, and place it in a low-temperature stirrer. Stir the reaction until the reaction is complete, and then perform chromatography to obtain product C. Add product C to tetrahydrofuran, then add lithium aluminum hydride, heat and stir to quench the reaction, extract, wash, dry, filter, rotary evaporate, and perform chromatography to obtain product D. S3: Add product D to dichloromethane, then add p-toluene isothiocyanate, stir at room temperature, concentrate under vacuum, and chromatographically to obtain the protective agent.

[0014] The synthesis reaction formula for the protective agent in the above process is as follows:

[0015] The mass spectrometry analysis results for product A were: m / z: 236.12 (100.0%), 237.12 (18.4%), 238.13 (1.6%); for product B: m / z: 389.14 (100.0%), 390.15 (26.3%), 391.14 (4.5%), 391.15 (4.0%), 392.14 (1.2%), 390.14 (1.2%); for product C: m / z: 233.12 (100.0%), 234.12 (18.8%), 235.13 (1.6%); and for product D: m / z: 247.14 (100.0%), 248.14 (19.7%). 249.14 (1.9%); The mass spectrometry analysis results of the protective agent were: m / z: 386.18 (100.0%), 387.19 (27.3%), 388.18 (4.9%), 388.19 (3.6%), 387.18 (1.5%), 389.18 (1.2%).

[0016] Preferably, in S1, the molar ratio of p-cycloarane, titanium tetrachloride, and 1,1-dichlorodimethyl ether is (1-1.4):(2-2.5):(1-1.3), the reaction time is 6-8 h, extraction is performed with dichloromethane, washing is performed with saturated sodium chloride, and drying is performed with anhydrous sodium sulfate; the molar ratio of product A and p-toluenesulfonamide is (1-1.5):(1-1.6), the oil bath heating and stirring temperature is 150-170℃, the time is 4-6 h, and recrystallization is performed with ethyl acetate.

[0017] Preferably, in S2, the molar ratio of product B, diazabicyclohexane, and diethylamine is (1-1.3):(0.2-0.23):(0.5-0.75), the stirring temperature is -10~-13℃, and the time is 10-12h; the molar ratio of product C and lithium aluminum hydride is (0.4-0.6):(0.17-0.22), the heating and stirring temperature is 28-32℃, and the time is 5-7h. The reaction is quenched with distilled water, extracted with ethyl acetate, washed with saturated sodium chloride, and dried with anhydrous sodium sulfate.

[0018] Preferably, in step S3, the molar ratio of product D to p-toluene isothiocyanate is (1-1.4):(0.9-1.3), and the stirring time is 1-2 h.

[0019] Preferably, the preparation method of the slow-release bactericidal foam drainage agent includes the following steps: Step 1: Add distilled water to the reaction vessel, heat to 50-60℃, then add surfactant, slow-release bactericide, protectant and stabilizer in sequence, stir to obtain a mixture; Step 2: Add pH adjuster to the mixture to adjust the pH to 6.8-7.5, stir completely, homogenize, filter, and fill to obtain slow-release bactericidal foam drainage agent.

[0020] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: 1. This invention first prepares a slow-release bactericide using 3-chloropropionic acid, dipentaerythritol, triallylamine, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate as raw materials. Subsequently, a protective agent is prepared using p-cycloaramine, 1,10-dioxane, p-toluenesulfonamide, diethylamine, and p-toluene isothiocyanate as raw materials. Adding the slow-release bactericide and the protective agent to the foam drainage agent can effectively improve its slow-release bactericidal ability and protect metal pipes from corrosion.

[0021] 2. This invention uses pentaerythritol as its core component. Through esterification with 3-chloropropionic acid and the introduction of a quaternary ammonium salt structure, the resulting intermediate 2 not only exhibits increased molecular complexity and steric hindrance due to the introduction of the ester bond and quaternary ammonium salt structure, thus slowing the release rate of the bactericidal component and achieving a sustained-release effect, but also combines the bactericidal activity of 3-chloropropionic acid with the spectral bactericidal effect of the quaternary ammonium salt, producing a synergistic bactericidal effect and significantly improving bactericidal performance. Furthermore, intermediate 3, prepared via the Stobol method, serves as a carrier, utilizing its porosity and large specific surface area to adsorb and immobilize intermediate 2, further enhancing the sustained-release effect.

[0022] 3. This invention adds the prepared protective agent to the foam drainage agent, which can effectively improve its protective effect on metal pipes. The thiourea group contained in the protective agent has strong coordination and hydrogen bonding capabilities, which can firmly adsorb onto the surface of the metal pipe to form a dense protective film, effectively blocking corrosive media. It can also reduce the corrosion tendency by changing the metal electrode potential. At the same time, its active sites interact with vacancies and defects on the metal surface, changing the chemical properties of the metal and further enhancing the protective effect. Moreover, the protective agent has a simple molecular structure and contains easily degradable functional groups (thiourea group, amino group), which can be efficiently and environmentally degraded by microorganisms in the natural environment into small molecule compounds without causing secondary pollution. Detailed Implementation

[0023] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] Example 1: This example discloses a method for preparing a slow-release bactericide, including the following steps: Q1: 1.573 g of 3-chloropropionic acid was added to a container equipped with a stirring reflux device. After heating, 0.635 g of dipentaerythritol was added, and the mixture was heated at 130 °C for 10 h. The mixture was washed with a 1:1 mixture of methanol and distilled water, dissolved in chloroform, dried with anhydrous sodium sulfate, filtered, and subjected to reduced pressure to obtain intermediate 1. 1.094 g of intermediate 1 was added to 5 mL of chloroform and stirred to dissolve. 1.154 g of triallylamine was slowly added dropwise using a constant pressure dropping funnel. After the addition was complete, the mixture was refluxed for 10 h, subjected to reduced pressure, recrystallized with acetone, and dried under vacuum to obtain intermediate 2. Q2: 1.5 g of hexadecyltrimethylammonium bromide was added to a round-bottom flask containing 560 mL of ultrapure water and ultrasonically dispersed for 30 min. Then, it was placed in an oil bath and magnetically stirred at 800 rpm. Subsequently, 3.75 mL of 2 mol / L sodium hydroxide solution was added, and the mixture was heated to 80 °C. Then, 7 mL of tetraethyl orthosilicate, 16 mL of ethyl acetate, and 0.7 mL of γ-aminoethylaminopropyltrimethoxysilane were added sequentially. After stirring for 4 h, the mixture was centrifuged at 12000 rpm for 8 min and washed 5 times alternately with ultrapure water and anhydrous ethanol. The precipitate was added to 475 mL of anhydrous ethanol and 0.48 mL of 5 mol / L hydrochloric acid was added. The mixture was heated and refluxed at 65 °C for 12 h, centrifuged at 8000 rpm for 12 min, the precipitate was collected, washed, dried at 90 °C for 12 h, and calcined at 450 °C to obtain intermediate 3. Q3: Add 30 mg of intermediate 2 to 125 mL of ultrapure water and stir for 12 h to obtain a mixed solution. Add 45 mg of intermediate 3 to the mixed solution and continue stirring for 24 h. Centrifuge at 10000 rpm for 7 min and dry at 60 °C for 12 h to obtain a slow-release bactericide.

[0025] This embodiment discloses a method for preparing a protective agent, including the following steps: S1: 1.253 g of p-cycloarane and 300 mL of dichloromethane were added to a round-bottom flask and stirred at low temperature. Then, 2.13 g of titanium tetrachloride and 0.663 g of 1,1-dichlorodimethyl ether were added. After the addition was complete, the mixture was stirred for 8 h. After the reaction was completed, the mixture was added to distilled water and extracted with dichloromethane. The organic phase was collected by separation, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain product A. Then, 1.475 g of product A and 1.11 g of p-toluenesulfonamide were added to a container, followed by 0.85 g of tetraethyl silicate. The mixture was heated and stirred in an oil bath at 170 °C for 6 h. After cooling, petroleum ether was added, the mixture was filtered, and recrystallized with ethyl acetate to obtain product B. S2: 14.91g of product B, 1.1g of diazabicyclohexane, and 0.15g of 4A molecular sieve were added to a container, followed by the addition of a mixed solution of 0.15mL toluene and 1.53g of diethylamine. The container was sealed and placed in a low-temperature stirrer at -10℃ for 12h. After the reaction was completed, the mixture was subjected to chromatography to obtain product C. 0.953g of product C was added to 10mL of tetrahydrofuran, followed by the addition of 0.06g of lithium aluminum hydride. The mixture was heated and stirred at 32℃ for 7h. The reaction was quenched with distilled water, extracted with ethyl acetate, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, filtered, evaporated by rotary evaporation, and subjected to chromatography to obtain product D. S3: Add 1.453 g of product D to 5 mL of dichloromethane, then add 0.77 g of p-toluene isothiocyanate, stir at room temperature for 2 h, concentrate under vacuum, and chromatographically to obtain the protective agent.

[0026] This embodiment discloses a slow-release bactericidal foam drainage agent, which is composed of the following components in parts by weight: 40 parts distilled water, 9 parts sodium dodecyl sulfate, 7 parts slow-release bactericide, 7 parts protectant, 2.5 parts calcium stearate, and 1.2 parts sodium bicarbonate.

[0027] This embodiment discloses a method for preparing a slow-release bactericidal foam drainage agent, including the following steps: Step 1: Add distilled water to the reaction vessel, heat to 55°C, then add sodium dodecyl sulfate, slow-release bactericide, preservative and calcium stearate in sequence, stir to obtain a mixture; Step 2: Add sodium bicarbonate to the mixture, adjust the pH to 7.2, stir thoroughly, homogenize, filter, and fill to obtain a slow-release bactericidal foam drainage agent.

[0028] Example 2: This example discloses a method for preparing a slow-release bactericide, including the following steps: Q1: 1.302 g of 3-chloropropionic acid was added to a container equipped with a stirring reflux device. After heating, 0.508 g of dipentaerythritol was added. The mixture was heated at 130 °C for 10 h. The product was washed with a 1:1 mixture of methanol and distilled water, dissolved in chloroform, dried with anhydrous sodium sulfate, filtered, and subjected to reduced pressure to obtain intermediate 1. 0.995 g of intermediate 1 was added to 5 mL of chloroform and stirred to dissolve. 1.028 g of triallylamine was slowly added dropwise using a constant pressure dropping funnel. After the addition was complete, the mixture was refluxed for 10 h, subjected to reduced pressure, recrystallized with acetone, and dried under vacuum to obtain intermediate 2. Q2: 1 g of hexadecyltrimethylammonium bromide was added to a round-bottom flask containing 380 mL of ultrapure water and ultrasonically dispersed for 30 min. Then, it was placed in an oil bath and magnetically stirred at 800 rpm. Subsequently, 5 mL of 2 mol / L sodium hydroxide solution was added, and the mixture was heated to 80 °C. Then, 9 mL of tetraethyl orthosilicate, 22 mL of ethyl acetate, and 0.9 mL of γ-aminoethylaminopropyltrimethoxysilane were added sequentially. After stirring for 4 h, the mixture was centrifuged at 12000 rpm for 8 min and washed 5 times alternately with ultrapure water and anhydrous ethanol. The precipitate was added to 300 mL of anhydrous ethanol and 0.32 mL of 5 mol / L hydrochloric acid was added. The mixture was heated and refluxed at 65 °C for 12 h and centrifuged at 8000 rpm for 12 min. The precipitate was collected, washed, dried at 90 °C for 12 h, and calcined at 450 °C to obtain intermediate 3. Q3: Add 20 mg of intermediate 2 to 150 mL of ultrapure water and stir for 12 h to obtain a mixed solution. Add 55 mg of intermediate 3 to the mixed solution and continue stirring for 24 h. Centrifuge at 10000 rpm for 7 min and dry at 60 °C for 12 h to obtain a slow-release bactericide.

[0029] This embodiment discloses a method for preparing a protective agent, including the following steps: S1: 1.04 g of p-cycloarane and 300 mL of dichloromethane were added to a round-bottom flask and stirred at low temperature. Then, 1.897 g of titanium tetrachloride and 0.575 g of 1,1-dichlorodimethyl ether were added. After the addition was complete, the mixture was stirred for 8 h. After the reaction was completed, the mixture was added to distilled water and extracted with dichloromethane. The organic phase was collected by separation, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain product A. Then, 1.18 g of product A and 0.855 g of p-toluenesulfonamide were added to a container, followed by 0.85 g of tetraethyl silicate. The mixture was heated and stirred in an oil bath at 170 °C for 6 h. After cooling, petroleum ether was added, the mixture was filtered, and recrystallized with ethyl acetate to obtain product B. S2: 12.97g of product B, 1.02g of diazabicyclohexane, and 0.15g of 4A molecular sieve were added to a container, followed by the addition of a mixed solution of 0.15mL toluene and 1.22g of diethylamine. The container was sealed and placed in a low-temperature stirrer at -10℃ for 12h. After the reaction was completed, the mixture was subjected to chromatography to obtain product C. 0.777g of product C was added to 10mL of tetrahydrofuran, followed by the addition of 0.05g of lithium aluminum hydride. The mixture was heated and stirred at 32℃ for 7h. The reaction was quenched with distilled water, extracted with ethyl acetate, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, filtered, evaporated by rotary evaporation, and subjected to chromatography to obtain product D. S3: Add 1.235g of product D to 5mL of dichloromethane, then add 0.67g of p-toluene isothiocyanate, stir at room temperature for 2h, concentrate under vacuum, and chromatographically to obtain the protective agent.

[0030] This embodiment discloses a slow-release bactericidal foam drainage agent, which is composed of the following components in parts by weight: 30 parts distilled water, 12 parts sodium dodecyl sulfate, 10 parts slow-release bactericide, 11 parts protectant, 1 part calcium stearate, and 2 parts sodium bicarbonate.

[0031] This embodiment discloses a method for preparing a slow-release bactericidal foam drainage agent, including the following steps: Step 1: Add distilled water to the reaction vessel, heat to 55°C, then add sodium dodecyl sulfate, slow-release bactericide, preservative and calcium stearate in sequence, stir to obtain a mixture; Step 2: Add sodium bicarbonate to the mixture, adjust the pH to 7.2, stir thoroughly, homogenize, filter, and fill to obtain a slow-release bactericidal foam drainage agent.

[0032] Example 3: This example discloses a method for preparing a slow-release bactericide, including the following steps: Q1: 1.844 g of 3-chloropropionic acid was added to a container equipped with a stirring reflux device. After heating, 0.762 g of dipentaerythritol was added, and the mixture was heated at 130 °C for 10 h. The mixture was washed with a 1:1 mixture of methanol and distilled water, dissolved in chloroform, dried with anhydrous sodium sulfate, filtered, and subjected to reduced pressure to obtain intermediate 1. 1.194 g of intermediate 1 was added to 5 mL of chloroform and stirred to dissolve. 1.28 g of triallylamine was slowly added dropwise using a constant pressure dropping funnel. After the addition was complete, the mixture was refluxed for 10 h, subjected to reduced pressure, recrystallized with acetone, and dried under vacuum to obtain intermediate 2. Q2: Add 2g of hexadecyltrimethylammonium bromide to a round-bottom flask containing 750mL of ultrapure water, sonicate for 30min, then place in an oil bath and stir magnetically at 800rpm. Then add 2.5mL of 2mol / L sodium hydroxide solution, heat at 80℃, and add 5mL of tetraethyl orthosilicate, 10mL of ethyl acetate and 0.5mL of γ-aminoethylaminopropyltrimethoxysilane in sequence. After stirring for 4h, centrifuge at 12000rpm for 8min, wash 5 times alternately with ultrapure water and anhydrous ethanol, add the precipitate to 550mL of anhydrous ethanol, add 0.63mL of 5mol / L hydrochloric acid, heat and stir under reflux at 65℃ for 12h, centrifuge at 8000rpm for 12min, collect the precipitate, wash, dry at 90℃ for 12h, and calcine at 450℃ to obtain intermediate 3; Q3: Add 40 mg of intermediate 2 to 100 mL of ultrapure water and stir for 12 h to obtain a mixed solution. Add 40 mg of intermediate 3 to the mixed solution and continue stirring for 24 h. Centrifuge at 10000 rpm for 7 min and dry at 60 °C for 12 h to obtain a slow-release bactericide.

[0033] This embodiment discloses a method for preparing a protective agent, including the following steps: S1: 1.456 g of p-cycloarane and 300 mL of dichloromethane were added to a round-bottom flask and stirred at low temperature. Then, 2.37 g of titanium tetrachloride and 0.75 g of 1,1-dichlorodimethyl ether were added. After the addition was complete, the mixture was stirred for 8 h. After the reaction was completed, the mixture was added to distilled water and extracted with dichloromethane. The organic phase was collected by separation, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain product A. Then, 1.77 g of product A and 1.37 g of p-toluenesulfonamide were added to a container, and 0.85 g of tetraethyl silicate was added. The mixture was heated and stirred in an oil bath at 170 °C for 6 h. After cooling, petroleum ether was added, the mixture was filtered, and recrystallized with ethyl acetate to obtain product B. S2: 16.86g of product B, 1.17g of diazabicyclohexane, and 0.15g of 4A molecular sieve were added to a container, followed by the addition of a mixed solution of 0.15mL toluene and 1.83g of diethylamine. The container was sealed and placed in a low-temperature stirrer at -10℃ for 12h. After the reaction was completed, the mixture was subjected to chromatography to obtain product C. 1.165g of product C was added to 10mL of tetrahydrofuran, followed by the addition of 0.07g of lithium aluminum hydride. The mixture was heated and stirred at 32℃ for 7h. The reaction was quenched with distilled water, extracted with ethyl acetate, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, filtered, evaporated by rotary evaporation, and subjected to chromatography to obtain product D. S3: Add 1.729 g of product D to 5 mL of dichloromethane, then add 0.97 g of p-toluene isothiocyanate, stir at room temperature for 2 h, concentrate under vacuum, and chromatographically to obtain the protective agent.

[0034] This embodiment discloses a slow-release bactericidal foam drainage agent, which is composed of the following components in parts by weight: 50 parts distilled water, 6 parts sodium dodecyl sulfate, 4 parts slow-release bactericide, 3 parts protectant, 4 parts calcium stearate, and 0.4 parts sodium bicarbonate.

[0035] This embodiment discloses a method for preparing a slow-release bactericidal foam drainage agent, including the following steps: Step 1: Add distilled water to the reaction vessel, heat to 55°C, then add sodium dodecyl sulfate, slow-release bactericide, preservative and calcium stearate in sequence, stir to obtain a mixture; Step 2: Add sodium bicarbonate to the mixture, adjust the pH to 7.2, stir thoroughly, homogenize, filter, and fill to obtain a slow-release bactericidal foam drainage agent.

[0036] Example 4: This example discloses a method for preparing a slow-release bactericide, including the following steps: Q1: 1.433 g of 3-chloropropionic acid was added to a container equipped with a stirring reflux device. After heating, 0.567 g of dipentaerythritol was added, and the mixture was heated at 130 °C for 10 h. The mixture was washed with a 1:1 mixture of methanol and distilled water, dissolved in chloroform, dried with anhydrous sodium sulfate, filtered, and subjected to reduced pressure to obtain intermediate 1. 1.045 g of intermediate 1 was added to 5 mL of chloroform and stirred to dissolve. 1.217 g of triallylamine was slowly added dropwise using a constant pressure dropping funnel. After the addition was complete, the mixture was refluxed for 10 h, subjected to reduced pressure, recrystallized with acetone, and dried under vacuum to obtain intermediate 2. Q2: 1.2 g of hexadecyltrimethylammonium bromide was added to a round-bottom flask containing 420 mL of ultrapure water and ultrasonically dispersed for 30 min. Then, it was placed in an oil bath and magnetically stirred at 800 rpm. Subsequently, 2.8 mL of 2 mol / L sodium hydroxide solution was added, and the mixture was heated to 80 °C. Then, 6 mL of tetraethyl orthosilicate, 14 mL of ethyl acetate, and 0.6 mL of γ-aminoethylaminopropyltrimethoxysilane were added sequentially. After stirring for 4 h, the mixture was centrifuged at 12000 rpm for 8 min and washed 5 times alternately with ultrapure water and anhydrous ethanol. The precipitate was added to 350 mL of anhydrous ethanol and 0.38 mL of 5 mol / L hydrochloric acid was added. The mixture was heated and refluxed at 65 °C for 12 h, centrifuged at 8000 rpm for 12 min, the precipitate was collected, washed, dried at 90 °C for 12 h, and calcined at 450 °C to obtain intermediate 3. Q3: Add 25 mg of intermediate 2 to 110 mL of ultrapure water and stir for 12 h to obtain a mixed solution. Add 42 mg of intermediate 3 to the mixed solution and continue stirring for 24 h. Centrifuge at 10000 rpm for 7 min and dry at 60 °C for 12 h to obtain a slow-release bactericide.

[0037] This embodiment discloses a method for preparing a protective agent, including the following steps: S1: 1.14 g of p-cycloarane and 300 mL of dichloromethane were added to a round-bottom flask and stirred at low temperature. Then, 2.05 g of titanium tetrachloride and 0.621 g of 1,1-dichlorodimethyl ether were added. After the addition was complete, the mixture was stirred for 8 h. After the reaction was completed, the mixture was added to distilled water and extracted with dichloromethane. The organic phase was collected by separation, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain product A. Then, 1.252 g of product A and 1.24 g of p-toluenesulfonamide were added to a container, followed by 0.85 g of tetraethyl silicate. The mixture was heated and stirred in an oil bath at 170 °C for 6 h. After cooling, petroleum ether was added, the mixture was filtered, and recrystallized with ethyl acetate to obtain product B. S2: 13.94 g of product B, 1.08 g of diazabicyclohexane, and 0.15 g of 4A molecular sieve were added to a container, followed by the addition of a mixed solution of 0.15 mL of toluene and 1.37 g of diethylamine. The container was sealed and placed in a low-temperature stirrer at -10 °C for 12 h. After the reaction was completed, the mixture was subjected to chromatography to obtain product C. 0.882 g of product C was added to 10 mL of tetrahydrofuran, followed by the addition of 0.05 g of lithium aluminum hydride. The mixture was heated and stirred at 32 °C for 7 h. The reaction was quenched with distilled water, extracted with ethyl acetate, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, filtered, rotary evaporated, and subjected to chromatography to obtain product D. S3: Add 1.315g of product D to 5mL of dichloromethane, then add 0.83g of p-toluene isothiocyanate, stir at room temperature for 2h, concentrate under vacuum, and chromatographically to obtain the protective agent.

[0038] This embodiment discloses a slow-release bactericidal foam drainage agent, which is composed of the following components in parts by weight: 35 parts distilled water, 7 parts sodium dodecyl sulfate, 6 parts slow-release bactericide, 5 parts protectant, 1.5 parts calcium stearate, and 0.8 parts sodium bicarbonate.

[0039] This embodiment discloses a method for preparing a slow-release bactericidal foam drainage agent, including the following steps: Step 1: Add distilled water to the reaction vessel, heat to 55°C, then add sodium dodecyl sulfate, slow-release bactericide, preservative and calcium stearate in sequence, stir to obtain a mixture; Step 2: Add sodium bicarbonate to the mixture, adjust the pH to 7.2, stir thoroughly, homogenize, filter, and fill to obtain a slow-release bactericidal foam drainage agent.

[0040] Comparative Example 1: Compared with Example 1, Comparative Example 1 did not add dipentaerythritol during the preparation of the slow-release bactericide, and all other conditions remained unchanged.

[0041] Comparative Example 2: Compared with Example 1, Comparative Example 2 did not add p-cycloarane during the preparation of the modified thickener, and all other conditions remained unchanged.

[0042] Comparative Example 3: Compared with Example 1, Comparative Example 3 did not add a slow-release bactericide during the preparation of the foam drainage agent, and all other conditions remained unchanged.

[0043] Comparative Example 4: Compared with Example 1, Comparative Example 4 did not add a protective agent during the preparation of the foam drainage agent, and all other conditions remained unchanged.

[0044] project Sterilization rate / % Corrosion rate (mm / year) Example 1 98.86 0.034 Example 2 98.42 0.036 Example 3 98.34 0.035 Example 4 98.73 0.036 Comparative Example 1 84.74 0.037 Comparative Example 2 98.42 0.045 Comparative Example 3 80.12 0.036 Comparative Example 4 98.33 0.047 As shown in Table 1, the foam drainage agents prepared in Examples 1-4 of this invention exhibit excellent bactericidal properties and superior protection for pipelines. A comparison between Comparative Example 1 and Examples 1-4 shows that adding pentaerythritol effectively improves the bactericidal properties of the foam drainage agent; a comparison between Comparative Example 2 and Examples 1-4 shows that adding p-cycloarane effectively improves the protective effect of the foam drainage agent on pipelines; a comparison between Comparative Example 3 and Examples 1-4 shows that adding a slow-release bactericide effectively improves the bactericidal properties of the foam drainage agent; and a comparison between Comparative Example 4 and Examples 1-4 shows that adding a protective agent effectively improves the protective effect of the foam drainage agent on pipelines.

[0045] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

[0046] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A slow-release bactericidal foam drainage agent, characterized in that, It is composed of the following components by weight: 30-50 parts distilled water, 6-12 parts surfactant, 4-10 parts slow-release bactericide, 3-11 parts protectant, 1-4 parts stabilizer, and 0.4-2 parts pH adjuster. The slow-release bactericide is prepared from 3-chloropropionic acid, dipentaerythritol, triallylamine, hexadecyltrimethylammonium bromide, tetraethyl orthosilicate, and γ-aminoethylaminopropyltrimethoxysilane. The protectant is prepared from p-cycloarane, 1,1-dichlorodimethyl ether, p-toluenesulfonamide, diethylamine, and p-toluene isothiocyanate.

2. The slow-release bactericidal foam drainage agent according to claim 1, characterized in that, The method for preparing the sustained-release bactericide includes the following steps: Q1: Add 3-chloropropionic acid to a container equipped with a stirring reflux device, heat and add dipentaerythritol, heat to react, wash, dissolve, dry, filter, and reduce pressure to obtain intermediate 1; add intermediate 1 to chloroform, stir to dissolve, and slowly add triallylamine dropwise using a constant pressure dropping funnel. After the addition is complete, reflux to react, reduce pressure, recrystallize, and dry under vacuum to obtain intermediate 2; Q2: Hexadecyltrimethylammonium bromide was added to a round-bottom flask containing ultrapure water and ultrasonically dispersed. Then, it was placed in an oil bath and magnetically stirred. Sodium hydroxide solution was then added and heated. Tetraethyl orthosilicate, ethyl acetate, and γ-aminoethylaminopropyltrimethoxysilane were added in sequence. After stirring, the mixture was centrifuged, washed, and the precipitate was added to anhydrous ethanol. Hydrochloric acid was added, and the mixture was heated, stirred, and refluxed. After centrifugation, the precipitate was collected, washed, dried, and calcined to obtain intermediate 3. Q3: Add intermediate 2 to ultrapure water, stir to obtain a mixed solution, add intermediate 3 to the mixed solution, continue stirring, centrifuge, and dry to obtain a slow-release bactericide.

3. The slow-release bactericidal foam drainage agent according to claim 2, characterized in that, In Q1, the molar ratio of 3-chloropropionic acid to dipentaerythritol is (6-8.5):(1-1.5), the reaction temperature is 120-140℃, the reaction time is 8-10h, the product is washed with a 1:1 mixture of methanol and distilled water, dissolved in chloroform, and dried with anhydrous sodium sulfate; the molar ratio of intermediate 1 to triallylamine is (1-1.2):(6-7.5), the reaction time is refluxed for 8-10h, and acetone is added for recrystallization.

4. The slow-release bactericidal foam drainage agent according to claim 2, characterized in that, In Q2, the ratio of hexadecyltrimethylammonium bromide, ultrapure water, sodium hydroxide solution, tetraethyl orthosilicate, ethyl acetate, γ-aminoethylaminopropyltrimethoxysilane, anhydrous ethanol, and hydrochloric acid is (1-2) g : (380-750) mL : (2.5-5) mL : (5-9) mL : (10-22) mL : (0.5-0.9) mL : (300-550) mL : (0.32-0.63) mL. The ultrasonic dispersion time is 20-30 min, the magnetic stirring speed is 600-800 rpm, and the sodium hydroxide... The solution concentration is 2 mol / L, the heating temperature is 80-90℃, the stirring time is 2-4 h, the centrifugation speed is 10000-12000 rpm, the centrifugation time is 5-8 min, and the solution is washed 3-5 times alternately with ultrapure water and anhydrous ethanol. The hydrochloric acid concentration is 5 mol / L, the heating and stirring reflux temperature is 60-65℃, the time is 10-12 h, the centrifugation speed is 8000-12000 rpm, the time is 8-12 min, the drying temperature is 80-90℃, the time is 12-15 h, and the calcination temperature is 400-500℃.

5. The slow-release bactericidal foam drainage agent according to claim 2, characterized in that, In Q3, the ratio of intermediate 2, ultrapure water and intermediate 3 is (20-40) mg: (100-150) mL: (40-55) mg, the stirring time is 10-12 h, the stirring time is continued for 20-24 h, the centrifugation speed is 8000-10000 rpm, the time is 5-7 min, the drying temperature is 50-60℃, and the time is 10-12 h.

6. The slow-release bactericidal foam drainage agent according to claim 1, characterized in that, The method for preparing the protective agent includes the following steps: S1: Add p-cycloarane and dichloromethane to a round-bottom flask and stir at low temperature. Then add titanium tetrachloride and 1,1-dichlorodimethyl ether. After the addition is complete, stir to react. After the reaction is complete, add distilled water, extract, collect the organic phase by separation, wash, dry, filter, concentrate under reduced pressure to obtain product A. Then add product A and p-toluenesulfonamide to a container, add tetraethyl silicate, heat and stir in an oil bath, cool, add petroleum ether, filter, recrystallize to obtain product B. S2: Add product B, diazabicyclohexane, and 4A molecular sieve to a container, then add a mixed solution of toluene and diethylamine, seal the container, and place it in a low-temperature stirrer. Stir the reaction until the reaction is complete, and then perform chromatography to obtain product C. Add product C to tetrahydrofuran, then add lithium aluminum hydride, heat and stir to quench the reaction, extract, wash, dry, filter, rotary evaporate, and perform chromatography to obtain product D. S3: Add product D to dichloromethane, then add p-toluene isothiocyanate, stir at room temperature, concentrate under vacuum, and chromatographically to obtain the protective agent.

7. The slow-release bactericidal foam drainage agent according to claim 6, characterized in that, In S1, the molar ratio of p-cycloarane, titanium tetrachloride, and 1,1-dichlorodimethyl ether is (1-1.4):(2-2.5):(1-1.3), the reaction time is 6-8 h, extraction is performed with dichloromethane, washing is performed with saturated sodium chloride, and drying is performed with anhydrous sodium sulfate; the molar ratio of product A and p-toluenesulfonamide is (1-1.5):(1-1.6), the oil bath heating and stirring temperature is 150-170℃, the time is 4-6 h, and recrystallization is performed with ethyl acetate.

8. The slow-release bactericidal foam drainage agent according to claim 6, characterized in that, In S2, the molar ratio of product B, diazabicyclohexane, and diethylamine is (1-1.3):(0.2-0.23):(0.5-0.75), the stirring temperature is -10~-13℃, and the time is 10-12h; the molar ratio of product C and lithium aluminum hydride is (0.4-0.6):(0.17-0.22), the heating and stirring temperature is 28-32℃, and the time is 5-7h. The reaction is quenched with distilled water, extracted with ethyl acetate, washed with saturated sodium chloride, and dried with anhydrous sodium sulfate.

9. The slow-release bactericidal foam drainage agent according to claim 6, characterized in that, In step S3, the molar ratio of product D to p-toluene isothiocyanate is (1-1.4):(0.9-1.3), and the stirring time is 1-2 h.

10. The method for preparing the slow-release bactericidal foam drainage agent according to any one of claims 1-9, characterized in that, Includes the following steps: Step 1: Add distilled water to the reaction vessel, heat to 50-60℃, then add surfactant, slow-release bactericide, protectant and stabilizer in sequence, stir to obtain a mixture; Step 2: Add pH adjuster to the mixture to adjust the pH to 6.8-7.5, stir completely, homogenize, filter, and fill to obtain slow-release bactericidal foam drainage agent.

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