Bactericide for water injection treatment and preparation method thereof

Abstract

The invention relates to the technical field of industrial bactericides, in particular to a bactericide for water injection treatment and a preparation method thereof. The preparation method comprises the following steps: carrying out a reaction on 2, 4-imidazoline diketone and 3-chloropropionaldehyde, so as to prepare 5-chloropropenyl-2, 4-imidazoline diketone; the preparation method comprises the following steps: reacting 5-chloropropenyl-2, 4-imidazoline diketone with 1, 4-dibromobutane, so as to obtain 3-bromobutyl-5-chloropropenyl-2, 4-imidazoline diketone; the preparation method comprises the following steps: reacting 2-(4-aminophenyl)-5-aminobenzimidazole with hydrochloric acid and cyanamide to prepare imidazole guanidine salt, and reacting 3-bromobutyl-5-chloropropenyl-2, 4-imidazolinedione with the imidazole guanidine salt, a cortex phellodendri extracting solution and a radix sophorae flavescentis extracting solution to obtain the bactericide for water injection treatment. The prepared bactericide for water injection treatment not only has excellent bactericidal performance, can effectively inhibit and kill sulfate reducing bacteria, saprophytic bacteria and iron bacteria, but also has good corrosion inhibition performance.

Description

Technical Field

[0001] The invention relates to the technical field of industrial fungicides, and in particular to a fungicide for water injection treatment and a preparation method thereof. Background Art

[0002] In the process of oil extraction, in order to ensure a high oil recovery rate, it is necessary to inject water into the oil layer to replenish and maintain the oil layer pressure. However, in the oil field reinjection water system, the oil field wastewater contains a large number of microorganisms, among which the large-scale growth and reproduction of sulfate-reducing bacteria (SRB), saprophytic bacteria (TGB) and iron bacteria (IB) in the water injection system will cause corrosion of metal equipment. Adding fungicides can effectively inhibit the growth and reproduction of microorganisms and achieve the protection of equipment.

[0003] Chinese patent CN115568480B discloses a plant-based composite antibacterial agent for oil fields. The composite antibacterial agent includes bimetallic nanoparticles and plant extracts. The metal ions in the metal salt solution are reduced by the active substances with reducing power contained in the plant extracts, so that the metal ions become zero-valent elemental metals. The plant-based composite antibacterial agent is obtained by reducing the metal silver ion and metal copper ion solutions. The antibacterial effect only depends on the bimetallic nanoparticles, the antibacterial components are single, and the antibacterial performance is insufficient. In addition, the corrosion inhibition performance of the antibacterial agent also needs to be improved. Summary of the invention

[0004] The present invention aims at the deficiencies of the prior art and provides a bactericide for water injection treatment to solve the problem that the antibacterial performance and corrosion inhibition performance of the bactericide for water injection treatment in the prior art need to be improved.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows: A method for preparing a fungicide for water injection treatment comprises the following steps: Step (1), adding 2,4-imidazolidinedione (hydantoin) into deionized water, heating and stirring until dissolved, adjusting the pH value to 6.5-7.5, adding ethanolamine, heating to a first set temperature, adding dropwise 3-chloropropanal solution, and after the dropwise addition is completed, heating to a second set temperature, reacting, cooling, filtering, washing, and drying to obtain 5-chloropropenyl-2,4-imidazolidinedione; Step (2), adding potassium carbonate to acetone, ultrasonically dispersing, adding 5-chloropropenyl-2,4-imidazolidinedione, reacting, and after the reaction is completed, adding 1,4-dibromobutane dropwise, and continuing the reaction after the addition is complete. After the reaction is completed, filtering, rotary evaporation, and purification to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione; Step (3), dissolving cyanamide in ethanol to obtain a cyanamide solution; 2-(4-aminophenyl)-5-aminobenzimidazole is added to ethanol, stirred, and then a hydrochloric acid solution is added dropwise. After the addition is complete, the temperature is raised to a set temperature, and an aminocyanide solution is added dropwise. After the addition is complete, the reaction is carried out, and after the reaction is completed, the reaction is cooled, precipitated, and purified to obtain an imidazole guanidine salt; The imidazole guanidine salt, the Phellodendron amurense extract, the Sophora flavescens extract and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione are mixed and reacted, and after the reaction is completed, rotary evaporation is performed to obtain a fungicide for water injection treatment.

[0006] Preferably, in step (1), the mass ratio of 2,4-imidazolidinedione, deionized water, ethanolamine and 3-chloropropanal solution is 10:(400-600):(10-12):(65-67.5), the heating and stirring conditions are heating and stirring at a temperature of 65-75°C and a speed of 150-250 r / min, the first set temperature is 80-100°C, the dripping time of 3-chloropropanal solution is 30-60 min, the reaction conditions are reflux reaction at the second set temperature for 10-15 h, and the second set temperature is 110-130°C; The 3-chloropropanal solution is prepared from 3-chloropropanal and ethanol, and the mass percentage of 3-chloropropanal in the 3-chloropropanal solution is 15%.

[0007] Preferably, in step (2), the mass ratio of 5-chloropropenyl-2,4-imidazolidinedione, 1,4-dibromobutane, potassium carbonate and acetone is 18:(39-47):(45-55):(900-1100), the ultrasonic dispersion is performed at a frequency of 50 kHz for 30 min, the reaction is performed under reflux at 60-80° C. for 40-80 min, the addition time of 1,4-dibromobutane is 20-40 min, and the reaction is continued under reflux at 60-80° C. for 3-5 h.

[0008] Preferably, in step (3), the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide is 1:1:(1.1-1.2), the mass of ethanol is 50-60 times the mass of 2-(4-aminophenyl)-5-aminobenzimidazole, the mass percentage of cyanamide in the cyanamide solution is 30%-50%, the dripping time of the cyanamide solution is 40-60 min, the reaction conditions are to control the pH value of the reaction system between 2-3, react at a set temperature for 4-6 h, the set temperature is 80-90° C., and the hydrochloric acid solution comprises a 30wt% hydrochloric acid solution.

[0009] Preferably, in step (3), the mass ratio of imidazole guanidine salt, Phellodendron chinense extract, Sophora flavescens extract and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione is (10-20):(300-500):(250-350):(50-70), and the reaction is carried out at a temperature of 55-65°C for 2-4 hours.

[0010] Preferably, the Phellodendron chinense extract in step (3) is prepared by the following steps: The Chinese medicinal material Phellodendron chinense was crushed, added into an ethanol aqueous solution, heated under reflux for extraction, and after the extraction was completed, the filtrate was filtered to obtain a Phellodendron chinense extract; The mass ratio of Phellodendron chinense to ethanol aqueous solution is 1:(8-12), and the heating reflux extraction condition is reflux extraction at 60-80°C for 6-10h; The ethanol aqueous solution includes 75wt% ethanol aqueous solution.

[0011] Preferably, the Sophora flavescens extract in step (3) is prepared by the following steps: The Chinese medicinal material Sophora flavescens was crushed, added into an ethanol aqueous solution, heated under reflux for extraction, and after the extraction was completed, the filtrate was filtered to obtain a Sophora flavescens extract; The mass ratio of bitter ginseng to ethanol aqueous solution is 1:(8-12), and the heating reflux extraction condition is reflux extraction at 60-70°C for 3-5h; The mass percentage of ethanol in the ethanol aqueous solution is 50%-70%.

[0012] The invention also discloses a fungicide for water injection treatment prepared by adopting the preparation method of the fungicide for water injection treatment as mentioned above.

[0013] Compared with the prior art, the present invention has the following beneficial effects: The bactericidal components in the present invention include plant-derived bactericidal components and imidazole compounds, which have an effective inhibitory effect on microorganisms; wherein the plant-derived bactericidal components include phellodendron extract and sophora flavescens extract, the phellodendron extract contains a variety of alkaloids such as phellodendronine and magnolamine, and has excellent bactericidal effect, and the sophora flavescens extract contains matrine, which also has excellent bactericidal effect; hydantoin, as a kind of imidazole compound, has good bactericidal performance; in addition, the heteroatoms in the hydantoin ring contain multiple lone pairs of electrons, which can be combined with the empty d orbitals of the metal to form coordination bonds, and can be adsorbed on the metal surface to form a dense adsorption film, thereby increasing the activation energy of the corrosion reaction, reducing the corrosion rate, and having a corrosion inhibition effect; 2-(4-aminophenyl)-5-aminobenzimidazole, as a kind of imidazole compound, also has good bactericidal performance; 2-(4-aminophenyl)-5-aminobenzimidazole reacts with hydrochloric acid and aminocyanide through the amino groups on both sides to generate imidazole guanidine salt, which can effectively improve the bactericidal performance; The molecular structure of hydantoin has the characteristics of keto-enol tautomerism. In an alkaline environment, it undergoes an aldol condensation reaction with the aldehyde group on the 3-chloropropanal molecule to generate an unsaturated substitution product 5-chloropropenyl-2,4-imidazolidinedione, introducing a chlorine element into the hydantoin molecule. Furthermore, through the active NH bond at the 3-position on the 5-chloropropenyl-2,4-imidazolidinedione molecule, it undergoes a substitution reaction with 1,4-dibromobutane to generate 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione, introducing a bromine element into the hydantoin molecule. The chlorine and bromine elements on the 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione molecule can form quaternary ammonium salts with the tertiary amine groups on the phellodendrine, matrine and imidazole guanidine molecules, further improving the bactericidal performance; at the same time, since the generated quaternary ammonium salt is cationic, and the solid surface in the water medium is generally negatively charged, the positively charged quaternary ammonium salt can adsorb on the surface of solid equipment to enhance the corrosion inhibition performance, and the introduction of alkyl chains on the hydantoin molecule can form a hydrophobic film on the metal surface, further improving the corrosion inhibition performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 The present invention is a flow chart of the preparation process of the fungicide for water injection treatment; Figure 2 It is a bar chart showing the test results of the bactericidal performance of the bactericides for water injection treatment prepared in Examples 1-5 of the present invention and Comparative Examples 1-2; Figure 3 It is a bar chart showing the corrosion inhibition performance test results of the fungicide for water injection treatment prepared in Examples 1-5 of the present invention and Comparative Examples 1-2. DETAILED DESCRIPTION Example 1

[0015] This embodiment discloses a method for preparing a fungicide for water injection treatment, comprising the following steps: Step (1), adding 2,4-imidazolidinedione to deionized water, heating and stirring at 65°C and 250r / min until dissolved, adding saturated NaHCO3 aqueous solution to adjust the pH value to 6.5, adding ethanolamine, heating to 80°C, and dripping 3-chloropropanal solution, the mass ratio of 2,4-imidazolidinedione, deionized water, ethanolamine, and 3-chloropropanal solution is 10:400:10:65, and the dripping time of 3-chloropropanal solution is 30min. After the dripping is completed, heating to 110°C, reflux reaction at 110°C for 15h, after the reaction is completed, cooling to 0°C, filtering and collecting the cooling precipitate, washing the cooling precipitate with 20wt% ethanol aqueous solution, and drying at 50°C and -0.09MPa for 12h to obtain 5-chloropropenyl-2,4-imidazolidinedione; The 3-chloropropanal solution is prepared from 3-chloropropanal and ethanol, and the mass percentage of 3-chloropropanal in the 3-chloropropanal solution is 15%; Step (2), adding potassium carbonate to acetone, ultrasonically dispersing at a frequency of 50kHz for 30min, then adding 5-chloropropenyl-2,4-imidazolidinedione, reflux reaction at 60°C for 80min, after the reaction is completed, adding 1,4-dibromobutane dropwise, the mass ratio of 5-chloropropenyl-2,4-imidazolidinedione, 1,4-dibromobutane, potassium carbonate and acetone is 18:39:45:900, the dropping time of 1,4-dibromobutane is 20min, after the dropwise addition is completed, reflux reaction is carried out at 60°C for 5h, after the reaction is completed, filtering, and the filtrate is rotary evaporated at 40°C to remove the solvent acetone, and the residual part is separated by column chromatography, the eluent is prepared by petroleum ether and ethyl acetate in a volume ratio of 2:1, and rotary evaporated at 50°C to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione; Step (3), dissolving cyanamide in ethanol to obtain a cyanamide solution, wherein the mass percentage of cyanamide in the cyanamide solution is 30%; 2-(4-aminophenyl)-5-aminobenzimidazole is added to ethanol, the mass of ethanol is 50 times the mass of 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and 300r / min for 30min, 30wt% hydrochloric acid solution is added dropwise to precipitate white insoluble matter, after the addition is completed, the temperature is raised to 80°C, and cyanamide solution is added dropwise, the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide is 1:1:1.1, and the addition time of the cyanamide solution is 40min. After the addition is completed, the pH value of the reaction system is controlled to be between 2-3, and the reaction is refluxed at 80°C for 6h. After the reaction is completed, it is cooled to room temperature, ether is added for precipitation until the precipitate no longer increases, filtered, the precipitate is dissolved with methanol, and reprecipitated, and the dissolution-precipitation process is repeated 3 times, and the purified precipitate is placed in a 50°C vacuum drying oven and dried for 12h to obtain imidazole guanidine salt; Mix imidazole guanidine salt, Phellodendron amurense extract, Sophora flavescens extract, and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione in a mass ratio of 10:300:250:50, react at 55° C. for 4 hours, and after the reaction, remove ethanol by rotary evaporation at 50° C. to obtain a fungicide for water injection treatment; The cortex phellodendri extract is prepared by the following steps: The Chinese medicinal material Phellodendron chinense was crushed, and then added to a 75wt% ethanol aqueous solution, the mass ratio of Phellodendron chinense to the 75wt% ethanol aqueous solution was 1:10, and refluxed for extraction at 70°C for 8h. After the extraction was completed, the filtrate was filtered to obtain a Phellodendron chinense extract; The sophora flavescens extract is prepared by the following steps: The Chinese medicinal material Sophora flavescens was crushed, and then added to an ethanol aqueous solution, the mass ratio of Sophora flavescens to the ethanol aqueous solution was 1:10, and refluxed for 4 hours at 65°C. After the extraction was completed, the filtrate was filtered to obtain a Sophora flavescens extract; Wherein, the mass percentage of ethanol in the ethanol aqueous solution is 60%. Example 2

[0016] This embodiment discloses a method for preparing a fungicide for water injection treatment, comprising the following steps: Step (1), adding 2,4-imidazolidinedione to deionized water, heating and stirring at 75°C and 150r / min until dissolved, adding saturated NaHCO3 aqueous solution to adjust the pH value to 7.5, adding ethanolamine, heating to 100°C, and dripping 3-chloropropanal solution, the mass ratio of 2,4-imidazolidinedione, deionized water, ethanolamine, and 3-chloropropanal solution is 10:600:12:67.5, and the dripping time of 3-chloropropanal solution is 60min. After the dripping is completed, the temperature is raised to 130°C, and refluxed at 130°C for 10h. After the reaction is completed, the mixture is cooled to 0°C, and the cooled precipitate is filtered out, and the cooled precipitate is washed with 20wt% ethanol aqueous solution, and dried at 50°C and -0.09MPa for 12h to obtain 5-chloropropenyl-2,4-imidazolidinedione; The 3-chloropropanal solution is prepared from 3-chloropropanal and ethanol, and the mass percentage of 3-chloropropanal in the 3-chloropropanal solution is 15%; Step (2), adding potassium carbonate to acetone, ultrasonically dispersing at a frequency of 50kHz for 30min, then adding 5-chloropropenyl-2,4-imidazolidinedione, reflux reaction at 80°C for 40min, after the reaction is completed, adding 1,4-dibromobutane dropwise, the mass ratio of 5-chloropropenyl-2,4-imidazolidinedione, 1,4-dibromobutane, potassium carbonate and acetone is 18:47:55:1100, the dropping time of 1,4-dibromobutane is 40min, after the dropwise addition is completed, reflux reaction is carried out at 80°C for 3h, after the reaction is completed, filtering, and the filtrate is rotary evaporated at 40°C to remove the solvent acetone, and the residual part is separated by column chromatography, the eluent is prepared by petroleum ether and ethyl acetate in a volume ratio of 2:1, and rotary evaporated at 50°C to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione; Step (3), dissolving cyanamide in ethanol to obtain a cyanamide solution, wherein the mass percentage of cyanamide in the cyanamide solution is 50%; 2-(4-aminophenyl)-5-aminobenzimidazole is added to ethanol, the mass of ethanol is 60 times the mass of 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and 300r / min for 30min, 30wt% hydrochloric acid solution is added dropwise to precipitate white insoluble matter, after the addition is completed, the temperature is raised to 90°C, and cyanamide solution is added dropwise, the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide is 1:1:1.2, and the addition time of the cyanamide solution is 60min. After the addition is completed, the pH value of the reaction system is controlled to be between 2-3, and the reaction is refluxed at 90°C for 4h. After the reaction is completed, it is cooled to room temperature, ether is added for precipitation until the precipitate no longer increases, filtered, the precipitate is dissolved with methanol, and reprecipitated, and the dissolution-precipitation process is repeated 3 times, and the purified precipitate is placed in a 50°C vacuum drying oven and dried for 12h to obtain imidazole guanidine salt; Mix imidazole guanidine salt, Phellodendron amurense extract, Sophora flavescens extract, and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione in a mass ratio of 20:500:350:70, react at 65°C for 2h, and after the reaction, remove ethanol by rotary evaporation at 50°C to obtain a fungicide for water injection treatment; The preparation methods of the Phellodendron amurense extract and Sophora flavescens extract are the same as those in Example 1. Example 3

[0017] This embodiment discloses a method for preparing a fungicide for water injection treatment, comprising the following steps: Step (1), adding 2,4-imidazolidinedione to deionized water, heating and stirring at 70°C and 200r / min until dissolved, adding saturated NaHCO3 aqueous solution to adjust the pH value to 7, adding ethanolamine, heating to 90°C, and dripping 3-chloropropanal solution, the mass ratio of 2,4-imidazolidinedione, deionized water, ethanolamine, and 3-chloropropanal solution is 10:450:10.5:65.5, and the dripping time of 3-chloropropanal solution is 45min. After the dripping is completed, the temperature is raised to 120°C, and refluxed at 120°C for 12h. After the reaction is completed, the temperature is cooled to 0°C, and the cooled precipitate is filtered out, and the cooled precipitate is washed with 20wt% ethanol aqueous solution, and dried at 50°C and -0.09MPa for 12h to obtain 5-chloropropenyl-2,4-imidazolidinedione; The 3-chloropropanal solution is prepared from 3-chloropropanal and ethanol, and the mass percentage of 3-chloropropanal in the 3-chloropropanal solution is 15%; Step (2), adding potassium carbonate to acetone, ultrasonically dispersing at a frequency of 50 kHz for 30 minutes, then adding 5-chloropropenyl-2,4-imidazolidinedione, reflux reaction at 70°C for 60 minutes, after the reaction is completed, adding 1,4-dibromobutane dropwise, the mass ratio of 5-chloropropenyl-2,4-imidazolidinedione, 1,4-dibromobutane, potassium carbonate and acetone is 18:41:48:950, and the dropping time of 1,4-dibromobutane is 30 minutes. After the dropwise addition is completed, reflux reaction is carried out at 70°C for 4 hours. After the reaction is completed, filtering, the filtrate is rotary evaporated at 40°C to remove the solvent acetone, and the residual part is separated by column chromatography, the eluent is prepared by petroleum ether and ethyl acetate in a volume ratio of 2:1, and rotary evaporated at 50°C to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione; Step (3), dissolving cyanamide in ethanol to obtain a cyanamide solution, wherein the mass percentage of cyanamide in the cyanamide solution is 40%; 2-(4-aminophenyl)-5-aminobenzimidazole is added to ethanol, the mass of ethanol is 55 times the mass of 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and 300r / min for 30min, 30wt% hydrochloric acid solution is added dropwise to precipitate white insoluble matter, after the addition is completed, the temperature is raised to 85°C, and cyanamide solution is added dropwise, the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide is 1:1:1.12, and the addition time of the cyanamide solution is 50min. After the addition is completed, the pH value of the reaction system is controlled to be between 2-3, and the reaction is refluxed at 85°C for 5h. After the reaction is completed, it is cooled to room temperature, ether is added for precipitation until the precipitate no longer increases, filtered, the precipitate is dissolved with methanol, and reprecipitated, and the dissolution-precipitation process is repeated 3 times, and the purified precipitate is placed in a 50°C vacuum drying oven and dried for 12h to obtain imidazole guanidine salt; Mix imidazole guanidine salt, Phellodendron amurense extract, Sophora flavescens extract, and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione in a mass ratio of 12:350:275:55, react at 60°C for 3h, and after the reaction, remove ethanol by rotary evaporation at 50°C to obtain a fungicide for water injection treatment; The preparation methods of the Phellodendron amurense extract and Sophora flavescens extract are the same as those in Example 1. Example 4

[0018] This embodiment discloses a method for preparing a fungicide for water injection treatment, comprising the following steps: Step (1), adding 2,4-imidazoline dione to deionized water, heating and stirring at 70°C and 200r / min until dissolved, adding saturated NaHCO3 aqueous solution to adjust the pH value to 7, adding ethanolamine, heating to 90°C, and dripping 3-chloropropanal solution, the mass ratio of 2,4-imidazoline dione, deionized water, ethanolamine, and 3-chloropropanal solution is 10:500:11:66, and the dripping time of 3-chloropropanal solution is 45min. After the dripping is completed, the temperature is raised to 120°C, and refluxed at 120°C for 12h. After the reaction is completed, the temperature is cooled to 0°C, and the cooled precipitate is filtered out, and the cooled precipitate is washed with 20wt% ethanol aqueous solution, and dried at 50°C and -0.09MPa for 12h to obtain 5-chloropropenyl-2,4-imidazoline dione; The 3-chloropropanal solution is prepared from 3-chloropropanal and ethanol, and the mass percentage of 3-chloropropanal in the 3-chloropropanal solution is 15%; Step (2), adding potassium carbonate to acetone, ultrasonically dispersing at a frequency of 50kHz for 30min, then adding 5-chloropropenyl-2,4-imidazolidinedione, reflux reaction at 70°C for 60min, after the reaction is completed, adding 1,4-dibromobutane dropwise, the mass ratio of 5-chloropropenyl-2,4-imidazolidinedione, 1,4-dibromobutane, potassium carbonate and acetone is 18:43:50:1000, the dropping time of 1,4-dibromobutane is 30min, after the dropwise addition is completed, reflux reaction is carried out at 70°C for 4h, after the reaction is completed, filtering, and the filtrate is rotary evaporated at 40°C to remove the solvent acetone, and the residual part is separated by column chromatography, the eluent is prepared by petroleum ether and ethyl acetate in a volume ratio of 2:1, and rotary evaporated at 50°C to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione; Step (3), dissolving cyanamide in ethanol to obtain a cyanamide solution, wherein the mass percentage of cyanamide in the cyanamide solution is 40%; 2-(4-aminophenyl)-5-aminobenzimidazole is added to ethanol, the mass of ethanol is 55 times the mass of 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and 300r / min for 30min, 30wt% hydrochloric acid solution is added dropwise to precipitate white insoluble matter, after the addition is completed, the temperature is raised to 85°C, and cyanamide solution is added dropwise, the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide is 1:1:1.15, and the addition time of the cyanamide solution is 50min. After the addition is completed, the pH value of the reaction system is controlled to be between 2-3, and the reaction is refluxed at 85°C for 5h. After the reaction is completed, it is cooled to room temperature, ether is added for precipitation until the precipitate no longer increases, filtered, the precipitate is dissolved with methanol, and reprecipitated, and the dissolution-precipitation process is repeated 3 times, and the purified precipitate is placed in a 50°C vacuum drying oven and dried for 12h to obtain imidazole guanidine salt; Mix imidazole guanidine salt, Phellodendron amurense extract, Sophora flavescens extract, and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione in a mass ratio of 15:400:300:60, react at 60°C for 3h, and after the reaction, remove ethanol by rotary evaporation at 50°C to obtain a fungicide for water injection treatment; The preparation methods of the Phellodendron amurense extract and Sophora flavescens extract are the same as those in Example 1. Example 5

[0019] This embodiment discloses a method for preparing a fungicide for water injection treatment, comprising the following steps: Step (1), adding 2,4-imidazoline dione to deionized water, heating and stirring at 70°C and 200r / min until dissolved, adding saturated NaHCO3 aqueous solution to adjust the pH value to 7, adding ethanolamine, heating to 90°C, and dripping 3-chloropropanal solution, the mass ratio of 2,4-imidazoline dione, deionized water, ethanolamine, and 3-chloropropanal solution is 10:550:11.5:67, and the dripping time of 3-chloropropanal solution is 45min. After the dripping is completed, the temperature is raised to 120°C, and refluxed at 120°C for 12h. After the reaction is completed, the temperature is cooled to 0°C, and the cooled precipitate is filtered out, and the cooled precipitate is washed with 20wt% ethanol aqueous solution, and dried at 50°C and -0.09MPa for 12h to obtain 5-chloropropenyl-2,4-imidazoline dione; The 3-chloropropanal solution is prepared from 3-chloropropanal and ethanol, and the mass percentage of 3-chloropropanal in the 3-chloropropanal solution is 15%; Step (2), adding potassium carbonate to acetone, ultrasonically dispersing at a frequency of 50kHz for 30min, then adding 5-chloropropenyl-2,4-imidazolidinedione, reflux reaction at 70°C for 60min, after the reaction, adding 1,4-dibromobutane dropwise, the mass ratio of 5-chloropropenyl-2,4-imidazolidinedione, 1,4-dibromobutane, potassium carbonate and acetone is 18:45:52:1050, the dropping time of 1,4-dibromobutane is 30min, after the dropwise addition is completed, reflux reaction is carried out at 70°C for 4h, after the reaction is completed, filtering, and the filtrate is rotary evaporated at 40°C to remove the solvent acetone, and the residual part is separated by column chromatography, the eluent is prepared by petroleum ether and ethyl acetate in a volume ratio of 2:1, and rotary evaporated at 50°C to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione; Step (3), dissolving cyanamide in ethanol to obtain a cyanamide solution, wherein the mass percentage of cyanamide in the cyanamide solution is 40%; 2-(4-aminophenyl)-5-aminobenzimidazole is added to ethanol, the mass of ethanol is 55 times the mass of 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and 300r / min for 30min, 30wt% hydrochloric acid solution is added dropwise to precipitate white insoluble matter, after the addition is completed, the temperature is raised to 85°C, and cyanamide solution is added dropwise, the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide is 1:1:1.18, and the addition time of the cyanamide solution is 50min. After the addition is completed, the pH value of the reaction system is controlled to be between 2-3, and the reaction is refluxed at 85°C for 5h. After the reaction is completed, it is cooled to room temperature, ether is added for precipitation until the precipitate no longer increases, filtered, the precipitate is dissolved with methanol, and reprecipitated, and the dissolution-precipitation process is repeated 3 times, and the purified precipitate is placed in a 50°C vacuum drying oven and dried for 12h to obtain imidazole guanidine salt; Mix imidazole guanidine salt, Phellodendron amurense extract, Sophora flavescens extract, and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione in a mass ratio of 18:450:330:65, react at 60°C for 3h, and after the reaction, remove ethanol by rotary evaporation at 50°C to obtain a fungicide for water injection treatment; The preparation methods of the Phellodendron amurense extract and Sophora flavescens extract are the same as those in Example 1.

[0020] Comparative Example 1 This comparative example discloses a method for preparing a fungicide for water injection treatment, comprising the following steps: Step (1), adding 2,4-imidazolidinedione to deionized water, heating and stirring at 65°C and 250r / min until dissolved, adding saturated NaHCO3 aqueous solution to adjust the pH value to 6.5, adding ethanolamine, heating to 80°C, and dripping 3-chloropropanal solution, the mass ratio of 2,4-imidazolidinedione, deionized water, ethanolamine, and 3-chloropropanal solution is 10:400:10:65, and the dripping time of 3-chloropropanal solution is 30min. After the dripping is completed, heating to 110°C, reflux reaction at 110°C for 15h, after the reaction is completed, cooling to 0°C, filtering and collecting the cooling precipitate, washing the cooling precipitate with 20wt% ethanol aqueous solution, and drying at 50°C and -0.09MPa for 12h to obtain 5-chloropropenyl-2,4-imidazolidinedione; The 3-chloropropanal solution is prepared from 3-chloropropanal and ethanol, and the mass percentage of 3-chloropropanal in the 3-chloropropanal solution is 15%; Step (2), dissolving cyanamide in ethanol to obtain a cyanamide solution, wherein the mass percentage of cyanamide in the cyanamide solution is 30%; 2-(4-aminophenyl)-5-aminobenzimidazole is added to ethanol, the mass of ethanol is 50 times the mass of 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and 300r / min for 30min, 30wt% hydrochloric acid solution is added dropwise to precipitate white insoluble matter, after the addition is completed, the temperature is raised to 80°C, and cyanamide solution is added dropwise, the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide is 1:1:1.1, and the addition time of the cyanamide solution is 40min. After the addition is completed, the pH value of the reaction system is controlled to be between 2-3, and the reaction is refluxed at 80°C for 6h. After the reaction is completed, it is cooled to room temperature, ether is added for precipitation until the precipitate no longer increases, filtered, the precipitate is dissolved with methanol, and reprecipitated, and the dissolution-precipitation process is repeated 3 times, and the purified precipitate is placed in a 50°C vacuum drying oven and dried for 12h to obtain imidazole guanidine salt; Mix imidazole guanidine salt, Phellodendron amurense extract, Sophora flavescens extract, and 5-chloropropenyl-2,4-imidazolidinedione in a mass ratio of 10:300:250:28.3, react at 55° C. for 4 hours, and after the reaction, remove ethanol by rotary evaporation at 50° C. to obtain a fungicide for water injection treatment; The preparation methods of the Phellodendron amurense extract and Sophora flavescens extract are the same as those in Example 1.

[0021] Comparative Example 2 This comparative example discloses a method for preparing a fungicide for water injection treatment, comprising the following steps: Step (1), dissolving cyanamide in ethanol to obtain a cyanamide solution, wherein the mass percentage of cyanamide in the cyanamide solution is 30%; 2-(4-aminophenyl)-5-aminobenzimidazole is added to ethanol, the mass of ethanol is 50 times the mass of 2-(4-aminophenyl)-5-aminobenzimidazole, after stirring at room temperature and 300r / min for 30min, 30wt% hydrochloric acid solution is added dropwise to precipitate white insoluble matter, after the addition is completed, the temperature is raised to 80°C, and cyanamide solution is added dropwise, the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide is 1:1:1.1, and the addition time of the cyanamide solution is 40min. After the addition is completed, the pH value of the reaction system is controlled to be between 2-3, and the reaction is refluxed at 80°C for 6h. After the reaction is completed, it is cooled to room temperature, ether is added for precipitation until the precipitate no longer increases, filtered, the precipitate is dissolved with methanol, and reprecipitated, and the dissolution-precipitation process is repeated 3 times, and the purified precipitate is placed in a 50°C vacuum drying oven and dried for 12h to obtain imidazole guanidine salt; Step (2), mixing imidazole guanidine salt, Phellodendron amurense extract, Sophora flavescens extract, and 2,4-imidazolidinedione, wherein the mass ratio of imidazole guanidine salt, Phellodendron amurense extract, Sophora flavescens extract, and 2,4-imidazolidinedione is 10:300:250:16.4, and keeping the mixture at 55° C. for 4 hours. After the reaction is completed, removing ethanol by rotary evaporation at 50° C. to obtain a fungicide for water injection treatment; The preparation methods of the Phellodendron amurense extract and Sophora flavescens extract are the same as those in Example 1.

[0022] In the above embodiments and comparative examples: 2,4-imidazolidinedione was purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd., CAS No.: 61-72-3; 3-chloropropanal was purchased from Hubei Qifei Pharmaceutical Chemical Co., Ltd., CAS No.: 19434-65-2; 1,4-dibromobutane was purchased from Shanghai Yihe Biotechnology Co., Ltd., CAS No.: 110-52-1; 2-(4-aminophenyl)-5-aminobenzimidazole was purchased from Hubei Xinyuhong Biopharmaceutical Technology Co., Ltd., item number: xyh001, CAS No.: 7621-86-5; cyanamide was purchased from Shanghai Ciyu Chemical Technology Co., Ltd., CAS No.: 420-04-2; Phellodendron chinense and Sophora flavescens were both purchased from Anhui Kangweifu Pharmaceutical Co., Ltd.

[0023] Test Case The performance tests were performed on the fungicides for water injection treatment prepared in Examples 1-5 and Comparative Examples 1-2: (1) Bactericidal performance: The bactericidal performance of the bactericides for water injection treatment prepared in Examples 1-5 and Comparative Examples 1-2 was determined with reference to the standard SY / T5757-2010 "General Technical Requirements for Bactericides for Oilfield Injection Water". The initial bacterial count of sulfate-reducing bacteria in the water sample was 8.1×10 6 / mL, the initial number of saprophytic bacteria was 9.2×10 6 / mL, the initial number of iron bacteria was 5.1×10 7 / mL, add fungicide at an effective dosage concentration of 20mg / L, culture at a constant temperature of 65±5℃, culture sulfate-reducing bacteria for 14 days, saprophytic bacteria and iron bacteria for 7 days, measure and record the total number of bacteria and calculate the bactericidal rate. The results of bactericidal rate determination are shown in Table 1: Table 1

[0024] As shown in Table 1, the bactericide prepared by the present invention has a good bactericidal effect, and can effectively inhibit and kill sulfate-reducing bacteria, saprophytes and iron bacteria. Compared with Example 1, in Comparative Example 1, 5-chloropropenyl-2,4-imidazolidinedione does not further react with 1,4-dibromobutane to introduce bromine, and the quaternary ammonium salt formed by reacting with the tertiary amine groups contained in other bactericidal components is reduced, and the bactericidal performance is reduced; compared with Comparative Example 1, in Comparative Example 2, 2,4-imidazolidinedione does not react with 3-chloropropanal to introduce chlorine, and cannot react with the tertiary amine groups contained in other bactericidal components to form quaternary ammonium salts, and the bactericidal performance is further reduced.

[0025] (2) Corrosion inhibition performance: The static uniform corrosion inhibition rate of the bactericide for water injection treatment prepared in Examples 1-5 and Comparative Examples 1-2 on Q235 steel was measured with reference to SY / T5273-2014 "Performance Indicators and Evaluation Methods for Corrosion Inhibitors for Oilfield Produced Water Treatment". The corrosion inhibition rate was measured after standing for 10 days. The results are shown in Table 2: Table 2

[0026] As shown in Table 2, the bactericide prepared by the present invention has good corrosion inhibition performance. Compared with Example 1, in Comparative Example 1, 5-chloropropenyl-2,4-imidazolidinedione does not further react with 1,4-dibromobutane to introduce bromine element, and the quaternary ammonium salt formed by reacting with the tertiary amine groups contained in other bactericidal components is reduced, the adsorption capacity of metal equipment is weakened, and the introduced alkyl chains are reduced, the hydrophobicity of the metal surface is reduced, and the corrosion inhibition performance is reduced; Compared with Comparative Example 1, in Comparative Example 2, 2,4-imidazolidinedione does not react with 3-chloropropanal to introduce chlorine element, and cannot react with the tertiary amine groups contained in other bactericidal components to form quaternary ammonium salt, the adsorption capacity of metal equipment is further weakened, and no alkyl chain is introduced, and a hydrophobic film cannot be formed on the metal surface, and the corrosion inhibition performance is further reduced.

[0027] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a fungicide for water injection treatment, characterized in that: The following steps are involved: Step (1), adding 2,4-imidazolidinedione to deionized water, heating and stirring until dissolved, adjusting the pH value to 6.5-7.5, adding ethanolamine, heating to a first set temperature, dropping 3-chloropropanal solution, after the dropwise addition is complete, heating to a second set temperature, reacting, cooling, filtering, washing, and drying to obtain 5-chloropropenyl-2,4-imidazolidinedione; Step (2), adding potassium carbonate to acetone, ultrasonically dispersing, adding 5-chloropropenyl-2,4-imidazolidinedione, reacting, and after the reaction is completed, adding 1,4-dibromobutane dropwise, and continuing the reaction after the addition is complete. After the reaction is completed, filtering, rotary evaporation, and purification to obtain 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione; Step (3), dissolving cyanamide in ethanol to obtain a cyanamide solution; 2-(4-aminophenyl)-5-aminobenzimidazole is added to ethanol, stirred, and then a hydrochloric acid solution is added dropwise. After the addition is complete, the temperature is raised to a set temperature, and an aminocyanide solution is added dropwise. After the addition is complete, the reaction is carried out, and after the reaction is completed, the reaction is cooled, precipitated, and purified to obtain an imidazole guanidine salt; The imidazole guanidine salt, the Phellodendron amurense extract, the Sophora flavescens extract and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione are mixed and reacted, and after the reaction is completed, rotary evaporation is performed to obtain a fungicide for water injection treatment.

2. The method for preparing a fungicide for water injection treatment according to claim 1, characterized in that: In the step (1), the mass ratio of 2,4-imidazolidinedione, deionized water, ethanolamine, and 3-chloropropanal solution is 10:(400-600):(10-12):(65-67.5); The 3-chloropropanal solution is prepared from 3-chloropropanal and ethanol, and the mass percentage of 3-chloropropanal in the 3-chloropropanal solution is 15%.

3. The method for preparing a fungicide for water injection treatment according to claim 1, characterized in that: In the step (1), the heating and stirring conditions are: heating and stirring at a temperature of 65-75°C and a speed of 150-250 r / min, the first set temperature is 80-100°C, the dripping time of the 3-chloropropanal solution is 30-60 min, the reaction conditions are reflux reaction at the second set temperature for 10-15 h, and the second set temperature is 110-130°C.

4. The method for preparing a fungicide for water injection treatment according to claim 1, characterized in that: In the step (2), the mass ratio of 5-chloropropenyl-2,4-imidazolidinedione, 1,4-dibromobutane, potassium carbonate and acetone is 18:(39-47):(45-55):(900-1100), the ultrasonic dispersion is performed at a frequency of 50 kHz for 30 min, the reaction is performed at a temperature of 60-80° C. for reflux reaction for 40-80 min, the dripping time of 1,4-dibromobutane is 20-40 min, and the reaction is continued at a temperature of 60-80° C. for reflux reaction for 3-5 h.

5. The method for preparing a fungicide for water injection treatment according to claim 1, characterized in that: In the step (3), the molar ratio of 2-(4-aminophenyl)-5-aminobenzimidazole, hydrogen chloride in the hydrochloric acid solution, and cyanamide is 1:1:(1.1-1.2); The mass of ethanol is 50-60 times that of 2-(4-aminophenyl)-5-aminobenzimidazole; The mass percentage of cyanamide in the cyanamide solution is 30%-50%; The hydrochloric acid solution includes a 30wt% hydrochloric acid solution.

6. The method for preparing a fungicide for water injection treatment according to claim 1, characterized in that: In the step (3), the duration of dripping the cyanamide solution is 40-60 minutes, and the reaction conditions are to control the pH value of the reaction system between 2-3 and react at a set temperature for 4-6 hours, wherein the set temperature is 80-90°C.

7. The method for preparing a fungicide for water injection treatment according to claim 1, characterized in that: In the step (3), the mass ratio of imidazole guanidine salt, Phellodendron chinense extract, Sophora flavescens extract, and 3-bromobutyl-5-chloropropenyl-2,4-imidazolidinedione is (10-20):(300-500):(250-350):(50-70), and the reaction is carried out at a temperature of 55-65° C. for 2-4 hours.

8. The method for preparing a fungicide for water injection treatment according to claim 1, characterized in that: The cortex phellodendri extract in step (3) is prepared by the following steps: The Chinese medicinal material Phellodendron amurense was crushed, added into an ethanol aqueous solution, heated under reflux for extraction, and after the extraction was completed, the filtrate was filtered to obtain a Phellodendron amurense extract; The mass ratio of Phellodendron chinense to ethanol aqueous solution is 1:(8-12), and the heating reflux extraction condition is reflux extraction at 60-80°C for 6-10h; The ethanol aqueous solution includes 75wt% ethanol aqueous solution.

9. The method for preparing a fungicide for water injection treatment according to claim 1, characterized in that: The Sophora flavescens extract in step (3) is prepared by the following steps: The Chinese medicinal material Sophora flavescens was crushed, added into an ethanol aqueous solution, heated under reflux for extraction, and after the extraction was completed, the filtrate was filtered to obtain a Sophora flavescens extract; The mass ratio of bitter ginseng to ethanol aqueous solution is 1:(8-12), and the heating reflux extraction condition is reflux extraction at 60-70°C for 3-5h; The mass percentage of ethanol in the ethanol aqueous solution is 50%-70%.

10. A fungicide for water injection treatment prepared by the method for preparing a fungicide for water injection treatment according to any one of claims 1 to 9.

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