Oilfield water injection bactericide containing plant sterilization components and preparation method of oilfield water injection bactericide

Abstract

The invention relates to the technical field of bactericides, and discloses an oilfield flooding bactericide containing plant bactericidal components and a preparation method thereof. The preparation method comprises the following steps: loading the plant-based traditional Chinese medicine extract and the isothiazolinone-based corrosion inhibitor on the silver-loaded cyclodextrin metal organic framework to prepare an antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material, and mixing the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material with methyl methacrylate to prepare the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material. The bactericide obtained by carrying out copolymerization reaction on modified hydroxyquinoline, vinyl quaternary phosphonium salt and methacrylic acid through an in-situ polymerization method can effectively kill and inhibit the breeding of sulfate reducing bacteria and other bacteria in oilfield reinjection water, and has a certain corrosion inhibition effect.

Description

Technical Field

[0001] The invention relates to the technical field of fungicides, and in particular to an oilfield water injection fungicide containing plant fungicidal components and a preparation method thereof. Background Art

[0002] Oilfield water injection bactericide refers to a chemical agent that can effectively kill sulfate-reducing bacteria (SRB), iron bacteria (TGB), saprophytic bacteria (FB) and other bacteria in oilfield wastewater by adding a small amount. At present, there are two types of bactericides used in oilfields, one is oxidizing bactericides and the other is non-oxidizing bactericides. Among them, non-oxidizing bactericides are further divided into adsorption bactericides and penetrating bactericides. Oxidizing bactericides have the characteristics of strong action, low cost, simple configuration process and easy operation, but they have the disadvantages of short efficacy time and severe corrosion; most of the adsorption bactericides are ionic bactericides, and the penetrating bactericides are mainly organic aldehyde compounds, heterocyclic compounds and cyanide compounds.

[0003] In order to reduce the losses caused by corrosion of the water injection system and reduce the harm caused by microorganisms to the oilfield water system, it is necessary to develop a bactericide with a certain corrosion inhibition effect to effectively control chemical corrosion and achieve the purpose of sterilization. Prior art such as Chinese patent CN104106602A discloses a high-efficiency oilfield reinjection water bactericide and its preparation method. By adding bactericidal components such as plant-based antibacterial extracts to the bactericide, the prepared bactericide can effectively kill and inhibit sulfate-reducing bacteria in the oilfield, and has a significant inhibitory effect on the growth of other bacteria, and has stable chemical properties, long-term sterilization time, safety and environmental protection, and has a certain anti-scaling and anti-scaling effect. However, although the bactericide prepared by this method has a certain corrosion inhibition and anti-scaling effect, it still needs to be compounded with a corrosion inhibitor to achieve an efficient corrosion inhibition effect, which limits the application of the material. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide an oilfield water injection fungicide containing plant fungicide components and a preparation method thereof, which can effectively kill and inhibit the growth of sulfate-reducing bacteria and other bacteria in oilfield reinjection water and has a certain corrosion inhibition effect.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows: A method for preparing an oilfield water injection fungicide containing a plant fungicide component comprises the following steps: Step (1), mixing cyclodextrin metal organic framework, silver nitrate and ethanol, reacting, centrifuging, filtering and drying after the reaction is completed to obtain a silver-loaded cyclodextrin metal organic framework; The silver-loaded cyclodextrin metal organic framework, the plant-based Chinese medicine extract, and the isothiazolinone-based corrosion inhibitor are mixed and loaded, and after the loading is completed, centrifuged, filtered, and dried to obtain an antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material; Step (2), mixing the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material with methyl methacrylate, and ultrasonically dispersing the mixture to obtain modified methyl methacrylate; The modified hydroxyquinoline, tetrahydrofuran, vinyl quaternary phosphonium salt, modified methyl methacrylate, methacrylic acid and an initiator are mixed and reacted, and after the reaction is completed, rotary evaporation is performed to obtain an oilfield water injection fungicide containing plant fungicide components.

[0006] Preferably, in step (1), the mass ratio of cyclodextrin metal organic framework, silver nitrate and ethanol is 10:0.8-1:400-500; and the reaction conditions are: in a light-proof environment, at a rotation speed of 180-220 r / min and a temperature of 35-37° C., for 12-16 hours.

[0007] Preferably, in the step (1), the mass ratio of the silver-loaded cyclodextrin metal organic framework, the plant-based Chinese medicine extract, and the isothiazolinone-based corrosion inhibitor is 1:180-200:10-15, and the plant-based Chinese medicine extract is prepared by mixing a polygonum cuspidatum extract, a pomegranate peel extract, a terminalia chebula extract, and ethanol in a mass ratio of 8-10:1:1:200-220; and the loading conditions are: in a light-proof environment, at a rotation speed of 180-220 r / min, and at room temperature for 12-16 h.

[0008] Preferably, the isothiazolinone-based corrosion inhibitor in step (1) is prepared by the following steps: S11, mixing 12-bromodeoxyuric acid methyl ester, acetonitrile and 2-methyl-4-isothiazoline-3-one, stirring and reacting, and after the reaction is completed, rotary evaporation, washing and drying are performed to obtain an intermediate product; S12, mixing the intermediate product, ethylenediamine and methanol, reacting, and after the reaction, rotary evaporating, extracting and drying to obtain an isothiazolinone-based corrosion inhibitor.

[0009] Preferably, when preparing the isothiazolinone-based corrosion inhibitor in step (1), in S11: the mass ratio of 12-bromodeoxyuric acid methyl ester, acetonitrile, and 2-methyl-4-isothiazoline-3-one is 29.3-30:65-75:18-20; and the reaction conditions are: reacting at a temperature of 80-90° C. for 8-10 hours.

[0010] Preferably, when preparing the isothiazolinone-based corrosion inhibitor in step (1), in S12: the mass ratio of the intermediate product, ethylenediamine, and methanol is 20-21:7-8:180-220; and the reaction conditions are: reacting at a temperature of 70-80°C for 10-12h.

[0011] Preferably, the extractant used in the extraction operation comprises diethyl ether.

[0012] Preferably, in step (2), the mass ratio of the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material to methyl methacrylate is 1:8-10; the mass ratio of modified hydroxyquinoline, tetrahydrofuran, vinyl quaternary phosphonium salt, modified methyl methacrylate, methacrylic acid, and initiator is 0.8-1:60-70:0.8-1:2.2-2.5:1-1.2:0.05-0.06; and the reaction conditions are: reacting in a nitrogen atmosphere at a temperature of 70-80°C for 6-8h.

[0013] Preferably, the initiator comprises azobisisobutyronitrile.

[0014] Preferably, the vinyl quaternary phosphonium salt in step (2) is prepared by the following steps: Vinylbenzyl chloride and N,N-dimethylformamide are mixed, and a triphenylphosphine / N,N-dimethylformamide mixed solution is added dropwise. After the addition is complete, the mixture is reacted. After the reaction is completed, the mixture is rotary evaporated to obtain a vinyl quaternary phosphonium salt.

[0015] Preferably, when preparing the vinyl quaternary phosphonium salt in step (2): the molar ratio of vinyl benzyl chloride to triphenylphosphine is 1-1.01:1; the mass ratio of vinyl benzyl chloride to N,N-dimethylformamide is 1:8-10; the mass ratio of triphenylphosphine to N,N-dimethylformamide in the triphenylphosphine / N,N-dimethylformamide mixed solution is 1:2.8-3, and the dripping conditions are: dripping at a temperature of 100-120°C for 10-20min; and the reaction conditions are: reacting at a temperature of 100-120°C for 12-14h.

[0016] Preferably, the modified hydroxyquinoline in step (2) is prepared by the following steps: Hydroxyethyl methacrylate, sodium acetate and p-hydroxyanisole are mixed and stirred, and 5-chloromethyl-8-hydroxyquinoline hydrochloride is added to react. After the reaction is completed, the mixture is purified to obtain modified hydroxyquinoline.

[0017] Preferably, in the step (2) of preparing modified hydroxyquinoline, the mass ratio of hydroxyethyl methacrylate, sodium acetate, p-hydroxyanisole and 5-chloromethyl-8-hydroxyquinoline hydrochloride is 22-25:1.7-1.8:0.1-0.12:5; the stirring and mixing conditions are: mixing for 1-1.5 hours at a temperature of 50-60° C. in a nitrogen atmosphere; and the reaction conditions are: reacting at a temperature of 50-60° C. for 6-8 hours.

[0018] Preferably, the purification operation comprises: adding 0.1 mol / L ammonia water to the reaction product obtained after the reaction is completed to neutralize it to neutrality, adding 0°C water 8-10 times the mass of the reaction product to precipitate, filtering, taking the filter cake, and adding petroleum ether 5-6 times the mass of the filter cake to recrystallize.

[0019] Preferably, an oilfield water injection fungicide containing plant fungicide components is prepared by the method for preparing an oilfield water injection fungicide containing plant fungicide components as described above.

[0020] Compared with the prior art, the present invention has the following beneficial effects: A metal organic framework is a porous crystalline material, which is formed by self-assembly of an inorganic metal center and a bridging organic ligand to form a periodic three-dimensional network structure, has a large surface area ratio and a cavity structure, and can form a stable inclusion complex with a guest molecule; the cyclodextrin metal organic framework used in the present invention is a repeating unit structure formed by connecting cyclodextrin molecules and potassium ions through a bridging action. The present invention first loads silver particles on the cyclodextrin metal organic framework to obtain a silver-loaded cyclodextrin metal organic framework, and then uses the cyclodextrin metal organic framework as a carrier to form an antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material through the formation of hydrogen bonds between the hydroxyl groups on the carrier molecules and the active groups of the plant-based traditional Chinese medicine extract and the isothiazolinone-based corrosion inhibitor.

[0021] Among them, the plant-based Chinese medicine extract is prepared by mixing Polygonum cuspidatum extract, Pomegranate peel extract, Terminalia chebula extract and solvent. Polygonum cuspidatum extract is rich in resveratrol, which not only has excellent antibacterial properties, but can also effectively kill sulfate-reducing bacteria and other bacteria in oilfield reinjection water, and also has a corrosion-inhibiting effect on the water injection system; Pomegranate peel extract is rich in polyphenols, and Terminalia chebula extract is rich in terminalia chebula tannic acid. The combination of the two has a synergistic antibacterial effect, which further improves the bactericidal performance of the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material.

[0022] The isothiazolinone-based corrosion inhibitor is prepared by a quaternization reaction of 12-bromodeoxyuric acid methyl ester and 2-methyl-4-isothiazoline-3-one, followed by an amidation reaction of the ester group with ethylenediamine. As a heterocyclic quaternary ammonium salt, the isothiazolinone-based corrosion inhibitor can form hydrogen bonds with the bases in sulfate-reducing bacteria through the active part on the heterocycle, adsorb on the bacterial cells and destroy the structure of the bacteria, and has strong bactericidal properties; O and N in its molecules both have lone pairs of electrons, which are easy to form coordination bonds with the metal surface and form an adsorption film, thereby reducing the metal surface energy and inhibiting metal corrosion; and the quaternary ammonium salt structure in the isothiazolinone-based corrosion inhibitor improves its solubility, thereby enhancing the corrosion inhibition and bactericidal effect in oilfield reinjection water.

[0023] The invention mixes an antibacterial agent / silver-carrying cyclodextrin metal organic framework composite material with methyl methacrylate, and then copolymerizes the composite material with modified hydroxyquinoline containing carbon-carbon double bonds, vinyl quaternary phosphonium salt and methacrylic acid through an in-situ polymerization method, thereby effectively improving the structural stability of the antibacterial agent / silver-carrying cyclodextrin metal organic framework composite material, making it difficult to disintegrate in water, avoiding the sudden release of bactericidal effective components in water, and improving the sustained release performance of the composite material; and because the modified hydroxyquinoline contains an 8-hydroxyquinoline structure with antibacterial and corrosion inhibition functions, it has synergistic antibacterial performance with the vinyl quaternary phosphonium salt and the antibacterial agent / silver-carrying cyclodextrin metal organic framework composite material, and further improves the corrosion inhibition effect of the bactericide; the oilfield water injection bactericide containing plant bactericidal components prepared by the invention has excellent bactericidal performance, can effectively kill and inhibit the growth of sulfate-reducing bacteria and other bacteria in oilfield reinjection water, and has a certain corrosion inhibition effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a process flow chart for preparing an oilfield water injection fungicide containing a plant fungicide component in the present invention; Figure 2 It is a histogram of the sterilization rates of the embodiments and comparative examples in the performance test of the present invention; Figure 3 It is a bar graph of the corrosion inhibition rates of the embodiments and comparative examples in the performance test of the present invention. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Example 1

[0026] This embodiment discloses a method for preparing an oilfield water injection fungicide containing a plant fungicide component, comprising the following steps: Step (1), mixing cyclodextrin metal organic framework, silver nitrate and ethanol in a mass ratio of 10:0.8:400, reacting for 16 hours in a light-proof environment at a speed of 180 r / min and a temperature of 35° C., centrifuging after the reaction, filtering, taking the filter cake, and drying at a temperature of 50° C. for 8 hours to obtain a silver-loaded cyclodextrin metal organic framework; The silver-loaded cyclodextrin metal organic framework, the plant-based traditional Chinese medicine extract, and the isothiazolinone-based corrosion inhibitor were mixed in a mass ratio of 1:180:10, and loaded for 16 hours at a speed of 180 r / min and room temperature in a light-proof environment. After the loading was completed, the mixture was centrifuged, filtered, and the filter cake was taken and dried at 50° C. for 3 hours to obtain an antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material; Among them, the plant-based Chinese medicine extract is prepared by mixing Polygonum cuspidatum extract, Pomegranate peel extract, Terminalia chebula extract, and ethanol in a mass ratio of 8:1:1:220; The isothiazolinone-based corrosion inhibitor is prepared by the following steps: S11, 12-bromodedecanoic acid methyl ester, acetonitrile, and 2-methyl-4-isothiazoline-3-one were mixed and stirred in a mass ratio of 29.3:65:18, and reacted at 80° C. for 10 h. After the reaction was completed, the solvent acetonitrile was removed by rotary evaporation at 60° C. to obtain an intermediate crude product, and acetone of 5 times the mass of the reaction crude product was added for washing, and dried at 50° C. for 8 h to obtain an intermediate product; S12, the intermediate product, ethylenediamine, and methanol are mixed in a mass ratio of 20:7:180, and reacted at 70°C for 12 hours. After the reaction is completed, the solvent methanol is removed by rotary evaporation at 30°C to obtain a reaction product, and ether with a mass of 5 times that of the reaction product is added for extraction, and the organic phase is taken and dried at 50°C for 8 hours to obtain an isothiazolinone-based corrosion inhibitor; Step (2), mixing the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material with methyl methacrylate at a mass ratio of 1:10, and ultrasonically dispersing for 1.5 hours to obtain modified methyl methacrylate; Modified hydroxyquinoline, tetrahydrofuran, vinyl quaternary phosphonium salt, modified methyl methacrylate, methacrylic acid, and initiator azobisisobutyronitrile are mixed in a mass ratio of 0.8:60:0.8:2.2:1.2:0.05, reacted at 70°C for 8 hours in a nitrogen atmosphere, and after the reaction, the solvent tetrahydrofuran is removed by rotary evaporation at 30°C to obtain an oilfield water injection fungicide containing a plant fungicide component; Wherein, the vinyl quaternary phosphonium salt comprises the following steps to prepare: Vinylbenzyl chloride and N,N-dimethylformamide are mixed in a mass ratio of 1:8, and a triphenylphosphine / N,N-dimethylformamide mixed solution prepared by mixing triphenylphosphine and N,N-dimethylformamide in a mass ratio of 1:2.8 is added dropwise at 100°C, the molar ratio of vinylbenzyl chloride to triphenylphosphine is 1:1, and the dropping time is 10 minutes. After the dropping is completed, the mixture is reacted at 100°C for 14 hours. After the reaction is completed, the solvent N,N-dimethylformamide is removed by rotary evaporation at 120°C to obtain a vinyl quaternary phosphonium salt; The modified hydroxyquinoline is prepared by the following steps: Mix hydroxyethyl methacrylate, sodium acetate and p-hydroxyanisole, stir and mix for 1.5 h in a nitrogen atmosphere at 50°C, add 5-chloromethyl-8-hydroxyquinoline hydrochloride, the mass ratio of hydroxyethyl methacrylate, sodium acetate, p-hydroxyanisole and 5-chloromethyl-8-hydroxyquinoline hydrochloride is 22:1.7:0.1:5, react at 50°C for 8 h, and after the reaction is completed, obtain a reaction product, add 0.1 mol / L ammonia water to neutralize to neutrality, and add 0°C water precipitate 8 times the mass of the reaction product, filter, take the filter cake, add petroleum ether 5 times the mass of the filter cake for recrystallization, and obtain modified hydroxyquinoline. Example 2

[0027] This embodiment discloses a method for preparing an oilfield water injection fungicide containing a plant fungicide component, comprising the following steps: Step (1), mixing cyclodextrin metal organic framework, silver nitrate and ethanol in a mass ratio of 10:0.85:450, reacting for 14 hours in a light-proof environment at a speed of 200 r / min and a temperature of 36° C., centrifuging after the reaction, filtering, taking the filter cake, and drying at a temperature of 55° C. for 6 hours to obtain a silver-loaded cyclodextrin metal organic framework; The silver-loaded cyclodextrin metal organic framework, the plant-based traditional Chinese medicine extract, and the isothiazolinone-based corrosion inhibitor were mixed in a mass ratio of 1:185:11, and loaded for 14 hours at a speed of 200 r / min and room temperature in a light-proof environment. After the loading was completed, the mixture was centrifuged, filtered, and the filter cake was taken and dried at 55° C. for 2 hours to obtain an antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material; Among them, the plant-based Chinese medicine extract is prepared by mixing Polygonum cuspidatum extract, Pomegranate peel extract, Terminalia chebula extract, and ethanol in a mass ratio of 8.5:1:1:210; The isothiazolinone-based corrosion inhibitor is prepared by the following steps: S11, 12-bromodedecanoic acid methyl ester, acetonitrile, and 2-methyl-4-isothiazoline-3-one were mixed and stirred in a mass ratio of 29.4:68:18.5, and reacted at 85° C. for 9 h. After the reaction was completed, the solvent acetonitrile was removed by rotary evaporation at 65° C. to obtain an intermediate crude product, and acetone of 6 times the mass of the reaction crude product was added for washing, and dried at 55° C. for 7 h to obtain an intermediate product; S12, the intermediate product, ethylenediamine, and methanol were mixed in a mass ratio of 20.3:7.3:200, and the mixture was reacted at 75°C for 11 hours. After the reaction was completed, the solvent methanol was removed by rotary evaporation at 35°C to obtain a reaction product, and ether was added in an amount 5 times the mass of the reaction product for extraction, and the organic phase was taken and dried at 55°C for 7 hours to obtain an isothiazolinone-based corrosion inhibitor; Step (2), mixing the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material with methyl methacrylate at a mass ratio of 1:9.5, and ultrasonically dispersing for 1.5 hours to obtain modified methyl methacrylate; Modified hydroxyquinoline, tetrahydrofuran, vinyl quaternary phosphonium salt, modified methyl methacrylate, methacrylic acid, and initiator azobisisobutyronitrile are mixed in a mass ratio of 0.85:65:0.85:2.3:1.05:0.05, reacted at 75°C for 7 hours in a nitrogen atmosphere, and after the reaction, the solvent tetrahydrofuran is removed by rotary evaporation at 35°C to obtain an oilfield water injection fungicide containing a plant fungicide component; Wherein, the vinyl quaternary phosphonium salt comprises the following steps to prepare: Vinylbenzyl chloride and N,N-dimethylformamide are mixed in a mass ratio of 1:8, and a triphenylphosphine / N,N-dimethylformamide mixed solution prepared by mixing triphenylphosphine and N,N-dimethylformamide in a mass ratio of 1:2.9 is added dropwise at 110°C, the molar ratio of vinylbenzyl chloride to triphenylphosphine is 1:1, and the dropping time is 15min. After the dropping is completed, the mixture is reacted at 110°C for 13h. After the reaction is completed, the solvent N,N-dimethylformamide is removed by rotary evaporation at 125°C to obtain a vinyl quaternary phosphonium salt; The modified hydroxyquinoline is prepared by the following steps: Mix hydroxyethyl methacrylate, sodium acetate and p-hydroxyanisole, stir and mix for 1 h in a nitrogen atmosphere at 55°C, add 5-chloromethyl-8-hydroxyquinoline hydrochloride, the mass ratio of hydroxyethyl methacrylate, sodium acetate, p-hydroxyanisole and 5-chloromethyl-8-hydroxyquinoline hydrochloride is 23:1.73:0.11:5, react at 55°C for 7 h, and after the reaction is completed, obtain a reaction product, add 0.1 mol / L ammonia water to neutralize to neutrality, and add 0°C water precipitate 8 times the mass of the reaction product, filter, take the filter cake, add petroleum ether 5 times the mass of the filter cake for recrystallization, and obtain modified hydroxyquinoline. Example 3

[0028] This embodiment discloses a method for preparing an oilfield water injection fungicide containing a plant fungicide component, comprising the following steps: Step (1), mixing cyclodextrin metal organic framework, silver nitrate and ethanol in a mass ratio of 10:0.9:450, reacting for 14 hours in a light-proof environment at a speed of 200 r / min and a temperature of 36° C., centrifuging after the reaction, filtering, taking the filter cake, and drying at a temperature of 55° C. for 6 hours to obtain a silver-loaded cyclodextrin metal organic framework; The silver-loaded cyclodextrin metal organic framework, the plant-based traditional Chinese medicine extract, and the isothiazolinone-based corrosion inhibitor were mixed in a mass ratio of 1:190:13, and loaded for 14 hours at a speed of 200 r / min and room temperature in a light-proof environment. After the loading was completed, the mixture was centrifuged, filtered, and the filter cake was taken and dried at 55° C. for 2.5 hours to obtain an antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material; Among them, the plant-based Chinese medicine extract is prepared by mixing Polygonum cuspidatum extract, Pomegranate peel extract, Terminalia chebula extract, and ethanol in a mass ratio of 9:1:1:210; The isothiazolinone-based corrosion inhibitor is prepared by the following steps: S11, 12-bromodedecanoic acid methyl ester, acetonitrile, and 2-methyl-4-isothiazoline-3-one were mixed and stirred in a mass ratio of 29.6:70:19, and reacted at 85° C. for 9 h. After the reaction was completed, the solvent acetonitrile was removed by rotary evaporation at 65° C. to obtain an intermediate crude product, and acetone of 6 times the mass of the reaction crude product was added for washing, and dried at 55° C. for 7 h to obtain an intermediate product; S12, the intermediate product, ethylenediamine, and methanol were mixed in a mass ratio of 20.5:7.5:200, and the mixture was reacted at 75°C for 11 hours. After the reaction was completed, the solvent methanol was removed by rotary evaporation at 35°C to obtain a reaction product, and ether was added with a mass of 5 times that of the reaction product for extraction, and the organic phase was taken and dried at 55°C for 7 hours to obtain an isothiazolinone-based corrosion inhibitor; Step (2), mixing the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material with methyl methacrylate in a mass ratio of 1:9, and ultrasonically dispersing for 1.5 hours to obtain modified methyl methacrylate; Modified hydroxyquinoline, tetrahydrofuran, vinyl quaternary phosphonium salt, modified methyl methacrylate, methacrylic acid, and initiator azobisisobutyronitrile are mixed in a mass ratio of 0.9:65:0.9:2.35:1.1:0.05, reacted at 75°C for 7 hours in a nitrogen atmosphere, and after the reaction, the solvent tetrahydrofuran is removed by rotary evaporation at 35°C to obtain an oilfield water injection fungicide containing a plant fungicide component; Wherein, the vinyl quaternary phosphonium salt comprises the following steps to prepare: Vinylbenzyl chloride and N,N-dimethylformamide are mixed in a mass ratio of 1:9, and a triphenylphosphine / N,N-dimethylformamide mixed solution prepared by mixing triphenylphosphine and N,N-dimethylformamide in a mass ratio of 1:2.9 is added dropwise at 110°C, the molar ratio of vinylbenzyl chloride to triphenylphosphine is 1:1, and the dropping time is 15min. After the dropping is completed, the mixture is reacted at 110°C for 13h. After the reaction is completed, the solvent N,N-dimethylformamide is removed by rotary evaporation at 125°C to obtain a vinyl quaternary phosphonium salt; The modified hydroxyquinoline is prepared by the following steps: Mix hydroxyethyl methacrylate, sodium acetate and p-hydroxyanisole, stir and mix for 1 h in a nitrogen atmosphere at 55°C, add 5-chloromethyl-8-hydroxyquinoline hydrochloride, the mass ratio of hydroxyethyl methacrylate, sodium acetate, p-hydroxyanisole and 5-chloromethyl-8-hydroxyquinoline hydrochloride is 23.5:1.75:0.11:5, react at 55°C for 7 h, and after the reaction is completed, obtain a reaction product, add 0.1 mol / L ammonia water to neutralize to neutrality, and add 0°C water precipitate of 9 times the mass of the reaction product, filter, take the filter cake, add petroleum ether of 5 times the mass of the filter cake for recrystallization, and obtain modified hydroxyquinoline. Example 4

[0029] This embodiment discloses a method for preparing an oilfield water injection fungicide containing a plant fungicide component, comprising the following steps: Step (1), mixing cyclodextrin metal organic framework, silver nitrate and ethanol in a mass ratio of 10:0.95:450, reacting for 14 hours in a light-proof environment at a speed of 200 r / min and a temperature of 36° C., centrifuging after the reaction, filtering, taking the filter cake, and drying at a temperature of 55° C. for 6 hours to obtain a silver-loaded cyclodextrin metal organic framework; The silver-loaded cyclodextrin metal organic framework, the plant-based traditional Chinese medicine extract, and the isothiazolinone-based corrosion inhibitor were mixed in a mass ratio of 1:195:14, and loaded for 14 hours at a speed of 200 r / min and room temperature in a light-proof environment. After the loading was completed, the mixture was centrifuged, filtered, and the filter cake was taken and dried at 55° C. for 3 hours to obtain an antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material; Among them, the plant-based Chinese medicine extract is prepared by mixing Polygonum cuspidatum extract, Pomegranate peel extract, Terminalia chebula extract, and ethanol in a mass ratio of 9.5:1:1:210; The isothiazolinone-based corrosion inhibitor is prepared by the following steps: S11, 12-bromodedecanoic acid methyl ester, acetonitrile, and 2-methyl-4-isothiazoline-3-one were mixed and stirred in a mass ratio of 29.8:73:19.5, and reacted at 85° C. for 9 h. After the reaction was completed, the solvent acetonitrile was removed by rotary evaporation at 65° C. to obtain an intermediate crude product, and acetone in an amount of 8 times the mass of the crude product was added for washing, and dried at 55° C. for 7 h to obtain an intermediate product; S12, the intermediate product, ethylenediamine, and methanol were mixed in a mass ratio of 20.8:7.8:200, and the mixture was reacted at 75°C for 11 hours. After the reaction was completed, the solvent methanol was removed by rotary evaporation at 35°C to obtain a reaction product, and ether was added in an amount 5 times the mass of the reaction product for extraction, and the organic phase was taken and dried at 55°C for 7 hours to obtain an isothiazolinone-based corrosion inhibitor; Step (2), mixing the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material with methyl methacrylate at a mass ratio of 1:9.5, and ultrasonically dispersing for 2 hours to obtain modified methyl methacrylate; Modified hydroxyquinoline, tetrahydrofuran, vinyl quaternary phosphonium salt, modified methyl methacrylate, methacrylic acid, and initiator azobisisobutyronitrile are mixed in a mass ratio of 0.95:65:0.95:2.4:1.15:0.06, reacted at 75°C for 7 hours in a nitrogen atmosphere, and after the reaction, the solvent tetrahydrofuran is removed by rotary evaporation at 35°C to obtain an oilfield water injection fungicide containing a plant fungicide component; Wherein, the vinyl quaternary phosphonium salt comprises the following steps to prepare: Vinylbenzyl chloride and N,N-dimethylformamide are mixed in a mass ratio of 1:10, and a triphenylphosphine / N,N-dimethylformamide mixed solution prepared by mixing triphenylphosphine and N,N-dimethylformamide in a mass ratio of 1:3 is added dropwise at 110°C, the molar ratio of vinylbenzyl chloride to triphenylphosphine is 1.01:1, and the dropping time is 15min. After the dropping is completed, the mixture is reacted at 110°C for 13h. After the reaction is completed, the solvent N,N-dimethylformamide is removed by rotary evaporation at 125°C to obtain a vinyl quaternary phosphonium salt; The modified hydroxyquinoline is prepared by the following steps: Mix hydroxyethyl methacrylate, sodium acetate and p-hydroxyanisole, stir and mix for 1 h in a nitrogen atmosphere at 55°C, add 5-chloromethyl-8-hydroxyquinoline hydrochloride, the mass ratio of hydroxyethyl methacrylate, sodium acetate, p-hydroxyanisole and 5-chloromethyl-8-hydroxyquinoline hydrochloride is 24:1.78:0.12:5, react at 55°C for 7 h, and after the reaction is completed, obtain a reaction product, add 0.1 mol / L ammonia water to neutralize to neutrality, and add 0°C water precipitate with 10 times the mass of the reaction product, filter, take the filter cake, add petroleum ether with 5 times the mass of the filter cake for recrystallization, and obtain modified hydroxyquinoline. Example 5

[0030] This embodiment discloses a method for preparing an oilfield water injection fungicide containing a plant fungicide component, comprising the following steps: Step (1), mixing cyclodextrin metal organic framework, silver nitrate and ethanol in a mass ratio of 10:1:500, reacting for 12 hours in a light-proof environment at a speed of 220 r / min and a temperature of 37° C., centrifuging after the reaction, filtering, taking the filter cake, and drying at a temperature of 60° C. for 5 hours to obtain a silver-loaded cyclodextrin metal organic framework; The silver-loaded cyclodextrin metal organic framework, the plant-based traditional Chinese medicine extract, and the isothiazolinone-based corrosion inhibitor were mixed at a mass ratio of 1:200:15, and loaded for 12 hours at a speed of 220 r / min and room temperature in a light-proof environment. After the loading was completed, the mixture was centrifuged, filtered, and the filter cake was taken and dried at 60° C. for 2 hours to obtain an antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material; Among them, the plant-based Chinese medicine extract is prepared by mixing Polygonum cuspidatum extract, Pomegranate peel extract, Terminalia chebula extract, and ethanol in a mass ratio of 10:1:1:200; The isothiazolinone-based corrosion inhibitor is prepared by the following steps: S11, 12-bromodedecanoic acid methyl ester, acetonitrile, and 2-methyl-4-isothiazoline-3-one were mixed and stirred in a mass ratio of 30:75:20, and reacted at 90° C. for 8 h. After the reaction was completed, the solvent acetonitrile was removed by rotary evaporation at 70° C. to obtain an intermediate crude product, and acetone in an amount of 8 times the mass of the crude product was added for washing, and dried at 60° C. for 6 h to obtain an intermediate product; S12, the intermediate product, ethylenediamine, and methanol are mixed in a mass ratio of 21:8:220, and reacted at 80°C for 10 hours. After the reaction is completed, the solvent methanol is removed by rotary evaporation at 40°C to obtain a reaction product, and ether of 6 times the mass of the reaction product is added for extraction, and the organic phase is taken and dried at 60°C for 6 hours to obtain an isothiazolinone-based corrosion inhibitor; Step (2), mixing the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material with methyl methacrylate in a mass ratio of 1:8, and ultrasonically dispersing for 2 hours to obtain modified methyl methacrylate; Modified hydroxyquinoline, tetrahydrofuran, vinyl quaternary phosphonium salt, modified methyl methacrylate, methacrylic acid, and initiator azobisisobutyronitrile are mixed in a mass ratio of 1:70:1:2.5:1:0.06, reacted at 80°C for 6 hours in a nitrogen atmosphere, and after the reaction, the solvent tetrahydrofuran is removed by rotary evaporation at 40°C to obtain an oilfield water injection fungicide containing a plant fungicide component; Wherein, the vinyl quaternary phosphonium salt comprises the following steps to prepare: Vinylbenzyl chloride and N,N-dimethylformamide are mixed in a mass ratio of 1:10, and a triphenylphosphine / N,N-dimethylformamide mixed solution prepared by mixing triphenylphosphine and N,N-dimethylformamide in a mass ratio of 1:3 is added dropwise at 120°C, the molar ratio of vinylbenzyl chloride to triphenylphosphine is 1.01:1, and the dropping time is 20min. After the dropping is completed, the mixture is reacted at 120°C for 12h. After the reaction is completed, the solvent N,N-dimethylformamide is removed by rotary evaporation at 130°C to obtain a vinyl quaternary phosphonium salt; The modified hydroxyquinoline is prepared by the following steps: Mix hydroxyethyl methacrylate, sodium acetate and p-hydroxyanisole, stir and mix for 1 h in a nitrogen atmosphere at 60°C, add 5-chloromethyl-8-hydroxyquinoline hydrochloride, the mass ratio of hydroxyethyl methacrylate, sodium acetate, p-hydroxyanisole and 5-chloromethyl-8-hydroxyquinoline hydrochloride is 25:1.8:0.12:5, react at 60°C for 6 h, and after the reaction is completed, obtain a reaction product, add 0.1 mol / L ammonia water to neutralize to neutrality, and add 0°C water precipitate 8 times the mass of the reaction product, filter, take the filter cake, add petroleum ether 6 times the mass of the filter cake for recrystallization, and obtain modified hydroxyquinoline.

[0031] Comparative Example 1 This comparative example discloses a method for preparing a fungicide, comprising the following steps: Step (1), mixing a cyclodextrin metal organic framework and a plant-based traditional Chinese medicine extract at a mass ratio of 1:190, loading for 16 hours at a speed of 180 r / min and room temperature in a light-proof environment, and after the loading is completed, centrifuging, filtering, taking the filter cake, and drying at 50° C. for 3 hours to obtain an antibacterial agent / cyclodextrin metal organic framework composite material; Among them, the plant-based Chinese medicine extract is prepared by mixing Polygonum cuspidatum extract, Pomegranate peel extract, Terminalia chebula extract, and ethanol in a mass ratio of 8:1:1:220; Step (2), mixing the antibacterial agent / cyclodextrin metal organic framework composite material with methyl methacrylate at a mass ratio of 1:10, and ultrasonically dispersing for 1.5 hours to obtain modified methyl methacrylate; Modified hydroxyquinoline, tetrahydrofuran, vinyl quaternary phosphonium salt, modified methyl methacrylate, methacrylic acid, and initiator azobisisobutyronitrile are mixed in a mass ratio of 0.8:60:0.8:2.2:1.2:0.05, reacted at 70°C for 8 hours in a nitrogen atmosphere, and after the reaction, the solvent tetrahydrofuran is removed by rotary evaporation at 30°C to obtain a fungicide; Wherein, the vinyl quaternary phosphonium salt comprises the following steps to prepare: Vinylbenzyl chloride and N,N-dimethylformamide are mixed in a mass ratio of 1:8, and a triphenylphosphine / N,N-dimethylformamide mixed solution prepared by mixing triphenylphosphine and N,N-dimethylformamide in a mass ratio of 1:2.8 is added dropwise at 100°C, the molar ratio of vinylbenzyl chloride to triphenylphosphine is 1:1, and the dropping time is 10 minutes. After the dropping is completed, the mixture is reacted at 100°C for 14 hours. After the reaction is completed, the solvent N,N-dimethylformamide is removed by rotary evaporation at 120°C to obtain a vinyl quaternary phosphonium salt; The modified hydroxyquinoline is prepared by the following steps: Mix hydroxyethyl methacrylate, sodium acetate and p-hydroxyanisole, stir and mix for 1.5 h in a nitrogen atmosphere at 50°C, add 5-chloromethyl-8-hydroxyquinoline hydrochloride, the mass ratio of hydroxyethyl methacrylate, sodium acetate, p-hydroxyanisole and 5-chloromethyl-8-hydroxyquinoline hydrochloride is 22:1.7:0.1:5, react at 50°C for 8 h, and after the reaction is completed, obtain a reaction product, add 0.1 mol / L ammonia water to neutralize to neutrality, and add 0°C water precipitate 8 times the mass of the reaction product, filter, take the filter cake, add petroleum ether 5 times the mass of the filter cake for recrystallization, and obtain modified hydroxyquinoline.

[0032] Comparative Example 2 This comparative example discloses a method for preparing a fungicide, comprising the following steps: The cyclodextrin metal organic framework, silver nitrate and ethanol were mixed in a mass ratio of 10:0.8:400, and reacted for 16 hours at a speed of 180 r / min and a temperature of 35° C. in a light-proof environment. After the reaction, the mixture was centrifuged and filtered, and the filter cake was taken and dried at a temperature of 50° C. for 8 hours to obtain a silver-loaded cyclodextrin metal organic framework. The silver-loaded cyclodextrin metal organic framework, the plant-based traditional Chinese medicine extract, and the isothiazolinone-based corrosion inhibitor were mixed in a mass ratio of 1:180:10, and loaded for 16 hours at a speed of 180 r / min and room temperature in a light-proof environment. After the loading was completed, the mixture was centrifuged, filtered, and the filter cake was taken and dried at 50° C. for 3 hours to obtain a fungicide; Among them, the plant-based Chinese medicine extract is prepared by mixing Polygonum cuspidatum extract, Pomegranate peel extract, Terminalia chebula extract, and ethanol in a mass ratio of 8:1:1:220; The isothiazolinone-based corrosion inhibitor is prepared by the following steps: S11, 12-bromodedecanoic acid methyl ester, acetonitrile, and 2-methyl-4-isothiazoline-3-one were mixed and stirred in a mass ratio of 29.3:65:18, and reacted at 80° C. for 10 h. After the reaction was completed, the solvent acetonitrile was removed by rotary evaporation at 60° C. to obtain an intermediate crude product, and acetone of 5 times the mass of the reaction crude product was added for washing, and dried at 50° C. for 8 h to obtain an intermediate product; S12. The intermediate product, ethylenediamine and methanol are mixed in a mass ratio of 20:7:180, and reacted at 70°C for 12 hours. After the reaction, the solvent methanol is removed by rotary evaporation at 30°C to obtain a reaction product, and ether of 5 times the mass of the reaction product is added for extraction. The organic phase is taken and dried at 50°C for 8 hours to obtain an isothiazolinone-based corrosion inhibitor.

[0033] In the above embodiments and comparative examples: cyclodextrin metal organic framework comes from Xi'an Qiyue Biotechnology Co., Ltd., product name γ-cyclodextrin-metal organic framework (γ-CD-MOF); silver nitrate comes from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS number: 7761-88-8; knotweed extract comes from Xi'an Yijun Biotechnology Co., Ltd., specification: alcohol-soluble resveratrol content 98wt%; pomegranate peel extract comes from Shaanxi Fuyubang Biotechnology Co., Ltd., specification: pomegranate peel polyphenol content 60wt%; terminalia chebula extract comes from Shaanxi Mufan Biotechnology Co., Ltd. Company, specifications: alcohol-soluble terminalia tannic acid content 98wt%; 12-bromodecanoic acid methyl ester from Shaoyuan Technology Co., Ltd., CAS number: 26825-95-6; 2-methyl-4-isothiazoline-3-one from Shanghai MacLean Biochemical Technology Co., Ltd., CAS number: 2682-20-4; methyl methacrylate from Shandong Yaojia Chemical Co., Ltd., CAS number: 80-62-6; vinylbenzyl chloride from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS number: 30030-25-2; triphenylphosphine from Alfa Aesar Company, CAS number: 603-35-0; hydroxyethyl methacrylate comes from Shandong Langcheng Chemical Co., Ltd., CAS number: 868-77-9; sodium acetate comes from Shanghai McLean Biochemical Technology Co., Ltd., CAS number: 127-09-3; p-Hydroxyanisole comes from Jiangsu Yuntong New Materials Technology Co., Ltd., CAS number: 150-76-5; 5-chloromethyl-8-hydroxyquinoline hydrochloride comes from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS number: 4053-45-6.

[0034] Test example The performance of the fungicides prepared in the above examples and comparative examples was tested, and the specific test results are shown in Table 1: Table 1 The detection of each index in Table 1 is based on the following standards: the bactericidal rate is determined by referring to SY / T5757-2010 "General Technical Conditions for Bactericides for Oilfield Injection Water"; the corrosion inhibition rate is determined by referring to the static uniform corrosion inhibition rate determination method in SY / T5273-2014 "Performance Indicators and Evaluation Methods for Corrosion Inhibitors for Oilfield Produced Water Treatment"; It can be seen from the test results in Table 1 that the fungicide prepared by the present invention can effectively kill and inhibit the growth of sulfate-reducing bacteria and other bacteria in oilfield reinjection water, and has a certain corrosion inhibition effect.

[0035] The invention prepares a silver-loaded cyclodextrin metal organic framework with excellent antibacterial performance, loads a plant-based Chinese medicine extract with excellent bactericidal and corrosion inhibition performance and an isothiazolinone-based corrosion inhibitor to form an antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material, and loads an acrylate-based resin containing modified hydroxyquinoline and vinyl quaternary phosphonium salt on the composite material through an in-situ polymerization method, thereby effectively improving the structural stability of the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material; and because the modified hydroxyquinoline contains an 8-hydroxyquinoline structure with antibacterial and corrosion inhibition functions, the modified hydroxyquinoline has synergistic antibacterial performance with the vinyl quaternary phosphonium salt and the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material, and further improves the corrosion inhibition effect of the bactericide.

[0036] The cyclodextrin metal organic framework used in Comparative Example 1 is not loaded with silver, and no isothiazolinone-based corrosion inhibitor is added. The silver particles and isothiazolinone-based corrosion inhibitors lack the effect of improving the antibacterial properties of the material. In addition, since the isothiazolinone-based corrosion inhibitor has good corrosion inhibition performance, the bactericidal performance and corrosion inhibition performance of the bactericide prepared in Comparative Example 1 are not as good as those in the embodiment. The bactericide prepared in Comparative Example 2 has no polymerized acrylate-based resin on its surface, and lacks the effect of improving the bactericidal and corrosion-inhibiting properties of the material by the acrylate-based resin containing modified hydroxyquinoline and vinyl quaternary phosphonium salt. Therefore, the bactericidal and corrosion-inhibiting properties of Comparative Example 2 are not as good as those of the embodiment.

[0037] 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 an oilfield water injection fungicide containing a plant fungicide component, characterized in that: The following steps are involved: Step (1), mixing the silver-loaded cyclodextrin metal organic framework, the plant-based Chinese medicine extract, and the isothiazolinone-based corrosion inhibitor, loading, and after loading, centrifuging, filtering, and drying to obtain an antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material; Step (2), mixing the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material with methyl methacrylate, and ultrasonically dispersing the mixture to obtain modified methyl methacrylate; The modified hydroxyquinoline, tetrahydrofuran, vinyl quaternary phosphonium salt, modified methyl methacrylate, methacrylic acid and an initiator are mixed and reacted, and after the reaction is completed, rotary evaporation is performed to obtain an oilfield water injection fungicide containing plant fungicide components.

2. The method for preparing an oilfield water injection fungicide containing a plant fungicide component according to claim 1, characterized in that: In the step (1), the mass ratio of the silver-loaded cyclodextrin metal organic framework, the plant-based Chinese medicine extract, and the isothiazolinone-based corrosion inhibitor is 1:180-200:10-15, and the plant-based Chinese medicine extract is prepared by mixing a polygonum cuspidatum extract, a pomegranate peel extract, a terminalia chebula extract, and ethanol in a mass ratio of 8-10:1:1:200-220; the loading conditions are: in a light-proof environment, at a rotation speed of 180-220 r / min, and at room temperature for 12-16 hours.

3. The method for preparing an oilfield water injection fungicide containing plant fungicide components according to claim 1, characterized in that: The silver-loaded cyclodextrin metal organic framework in step (1) is prepared by the following steps: Mixing a cyclodextrin metal organic framework, silver nitrate and ethanol, reacting, centrifuging, filtering and drying after the reaction is completed to obtain a silver-loaded cyclodextrin metal organic framework; The mass ratio of cyclodextrin metal organic framework, silver nitrate and ethanol is 10:0.8-1:400-500; the reaction conditions are: in a light-proof environment, at a rotation speed of 180-220 r / min and a temperature of 35-37° C., for 12-16 hours.

4. The method for preparing an oilfield water injection fungicide containing plant fungicide components according to claim 1, characterized in that: The isothiazolinone-based corrosion inhibitor in step (1) is prepared by the following steps: S11, mixing 12-bromodeoxyuric acid methyl ester, acetonitrile and 2-methyl-4-isothiazoline-3-one, stirring and reacting, and after the reaction is completed, rotary evaporation, washing and drying are performed to obtain an intermediate product; S12, mixing the intermediate product, ethylenediamine and methanol, reacting, and after the reaction, rotary evaporating, extracting and drying to obtain an isothiazolinone-based corrosion inhibitor.

5. The method for preparing an oilfield water injection fungicide containing plant fungicide components according to claim 4, characterized in that: When preparing the isothiazolinone-based corrosion inhibitor, in S11, the mass ratio of 12-bromodeoxyuric acid methyl ester, acetonitrile, and 2-methyl-4-isothiazolin-3-one is 29.3-30:65-75:18-20; the reaction conditions are: reacting at a temperature of 80-90° C. for 8-10 hours; In S12: the mass ratio of the intermediate product, ethylenediamine and methanol is 20-21:7-8:180-220; the reaction conditions are: react at 70-80°C for 10-12h.

6. The method for preparing an oilfield water injection fungicide containing plant fungicide components according to claim 1, characterized in that: In the step (2), the mass ratio of the antibacterial agent / silver-loaded cyclodextrin metal organic framework composite material to methyl methacrylate is 1:8-10; the mass ratio of modified hydroxyquinoline, tetrahydrofuran, vinyl quaternary phosphonium salt, modified methyl methacrylate, methacrylic acid, and initiator is 0.8-1:60-70:0.8-1:2.2-2.5:1-1.2:0.05-0.06; and the reaction conditions are: reacting in a nitrogen atmosphere at a temperature of 70-80°C for 6-8h.

7. The method for preparing an oilfield water injection fungicide containing plant fungicide components according to claim 1, characterized in that: The vinyl quaternary phosphonium salt in step (2) is prepared by the following steps: Vinylbenzyl chloride and N,N-dimethylformamide are mixed, and a triphenylphosphine / N,N-dimethylformamide mixed solution is added dropwise. After the addition is complete, the mixture is reacted. After the reaction is completed, the mixture is rotary evaporated to obtain a vinyl quaternary phosphonium salt.

8. The method for preparing an oilfield water injection fungicide containing plant fungicide components according to claim 7, characterized in that: When preparing the vinyl quaternary phosphonium salt, the molar ratio of vinyl benzyl chloride to triphenylphosphine is 1-1.01:1; the dripping condition of the triphenylphosphine / N,N-dimethylformamide mixed solution is: dripping at 100-120° C. for 10-20 minutes; the reaction condition is: reacting at 100-120° C. for 12-14 hours.

9. The method for preparing an oilfield water injection fungicide containing plant fungicide components according to claim 1, characterized in that: The modified hydroxyquinoline in step (2) is prepared by the following steps: Mix hydroxyethyl methacrylate, sodium acetate and p-hydroxyanisole, add 5-chloromethyl-8-hydroxyquinoline hydrochloride, react, and purify after the reaction to obtain modified hydroxyquinoline; Among them, the mass ratio of hydroxyethyl methacrylate, sodium acetate, p-hydroxyanisole, and 5-chloromethyl-8-hydroxyquinoline hydrochloride is 22-25:1.7-1.8:0.1-0.12:5; the stirring and mixing conditions are: mixing for 1-1.5 hours at a temperature of 50-60°C in a nitrogen atmosphere; and the reaction conditions are: reacting at a temperature of 50-60°C for 6-8 hours.

10. An oilfield water injection fungicide containing plant fungicide components prepared by the method for preparing an oilfield water injection fungicide containing plant fungicide components according to any one of claims 1 to 9.

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