Polymeric quaternary phosphonium salt fungicide, and preparation method and application thereof

Abstract

The application discloses a kind of polymeric quaternary phosphonium salt fungicides and its preparation method and application the method includes steps: S1, 3, 5-dihydroxyacetophenone, water, organic acid, organic phosphine reaction obtains intermediate product A;S2, brown intermediate product A is reacted in alcohol and halogenated hydrocarbon, and brown viscous product is obtained;S3, brown viscous product is dissolved in ester solvent, filtration is carried out, and the polymeric quaternary phosphonium salt fungicide monomer separated in filtrate is taken;S4, polymeric quaternary phosphonium salt fungicide monomer is added in water, and aqueous solution of potassium persulfate, aqueous solution of sodium bisulfite are sequentially added dropwise, and viscous liquid is obtained;S5, viscous liquid is filtered to obtain light yellow solid, and the light yellow solid is placed in oven and dried overnight, and polymeric quaternary phosphonium salt fungicide is obtained.The polymeric quaternary phosphonium salt fungicide of the application has killing effect on SRB, TGB and IB in oil-containing sewage, and has the advantages of low use concentration and high sterilization efficiency.

Description

Technical Field

[0001] This invention belongs to the field of wastewater treatment technology, specifically a polymeric quaternary phosphonium salt bactericide, its preparation method, and its application. Background Technology

[0002] Currently, oilfield development has entered the middle and late stages. Major oilfields at home and abroad usually use water injection to replenish formation energy and maintain the injection-production balance.

[0003] Oily wastewater, after treatment, is typically injected directly back into the formation. However, this reinjection water contains a large amount of organic matter, which provides a breeding ground for microorganisms, promoting the growth of bacteria such as sulfate-reducing bacteria (SRB), iron bacteria (IB), and saprophytic bacteria (TGB). This bacterial growth causes corrosion, scaling, and damage to injection equipment, pipelines, and metal materials, increasing maintenance costs. Furthermore, sulfate-reducing bacteria (SRB), under the action of hydrogenase, convert sulfate ions into H2S, a colorless, highly toxic acidic gas. The presence of H2S not only exacerbates corrosion of metal equipment but also easily leads to personnel poisoning, affecting the safe operation of the oilfield. Therefore, it is essential to sterilize the reinjection water before it is injected.

[0004] Currently, oilfields use chemical bactericides to sterilize reinjected water. However, as bacteria continue to grow and multiply, they develop resistance to single bactericides, leading to a gradual decrease in sterilization effectiveness, an increase in dosage, and rising costs.

[0005] Chinese invention patent application CN 114805437 A discloses a method for preparing a bactericide for oilfield wastewater. The process involves sequentially adding diethylphosphine, p-hydroxyacetophenone, water, and formic acid to a four-necked flask, stirring and heating under reflux, followed by vacuum distillation to obtain a brown, viscous intermediate. Isobutanol and tetrabromoneopentane are then added to the same four-necked flask, and the mixture is heated under reflux to obtain another brown, viscous substance. Finally, the bactericide is obtained by recrystallization. This bactericide forms four quaternary phosphonium cations by the four carbon atoms of the neopentane group forming four phosphorus atoms connected to larger groups. Although the bactericide molecule contains a large number of quaternary phosphonium cations, its steric hindrance is significant, making it difficult to adsorb onto the negatively charged bacterial surface, thus affecting the bactericidal efficiency and rate.

[0006] Chinese invention patent application CN 114957525 A discloses a method for preparing a bactericide for oilfield wastewater. The process involves adding 2-cyclohexen-1-one, dibutylphosphine, and 1,4-dichloro-2-butene to a nitrogen-protected four-necked flask, refluxing, and then distilling under reduced pressure. Ethyl acetate is then added for recrystallization. Finally, an initiator is added to initiate a polymerization reaction, yielding a pale yellow polymeric bactericide. However, in this method, the phosphorus atom of the bactericide molecule directly forms a chemical bond with the carbon atom in cyclohexanone. This not only fails to reduce the positive charge of the quaternary phosphonium ion but also increases the steric hindrance around the quaternary phosphonium ion, affecting the bactericidal rate. Summary of the Invention

[0007] Objective of the Invention: Existing quaternary phosphonium salt bactericides suffer from significant steric hindrance around the quaternary phosphonium ions, affecting their adsorption capacity to bacterial surfaces and thus their bactericidal efficiency. Furthermore, long-term use of a single bactericide during the bactericidal process can lead to drug resistance, resulting in a significant decrease in bactericidal effect, requiring increasingly higher dosages, and continuously rising costs. To address the shortcomings of the prior art, this invention discloses a polymeric quaternary phosphonium salt bactericide, its preparation method, and its applications.

[0008] Technical solution: A polymeric quaternary phosphonium salt bactericide, the structural formula of which is as follows:

[0009] in:

[0010] n is a positive integer, and n = 100 to 1000.

[0011] A method for preparing the above-mentioned polymeric quaternary phosphonium salt bactericide includes the following steps:

[0012] S1. 3,5-Dihydroxyacetophenone, water and organic acid are added to the reactor in sequence. Nitrogen or inert gas is introduced for protection. Organic phosphine is added dropwise while stirring. After completion, the temperature is raised to at least 40°C and the reaction is carried out for a period of time. The brown intermediate product A is obtained by vacuum distillation.

[0013] S2. In a nitrogen or inert gas atmosphere, add alcohol and haloalkanes to the brown intermediate product A obtained in step S1, adjust the temperature, stir and heat, reflux for a period of time, distill under reduced pressure, and preliminarily purify to obtain a brown viscous product.

[0014] S3. Add an ester solvent to the brown viscous product obtained in step S2, stir and heat until dissolved to obtain a solution, then filter the solution, let the collected filtrate cool naturally until the product precipitates, filter, take the product, dry it to obtain the polyquaternium salt bactericide monomer.

[0015] S4. Add the polyquaternium salt bactericide monomer obtained in step S3 to the reactor, and add an appropriate amount of water as a solvent. Stir and heat to at least 45°C. While stirring, add potassium persulfate aqueous solution dropwise. After reacting for at least 4 hours, heat to at least 70°C and continue reacting for at least 0.5 hours. Add sodium bisulfite aqueous solution and stir for at least 4 hours to obtain a viscous liquid.

[0016] S5. Filter the viscous liquid obtained in step S4 to obtain a light yellow solid, put it in an oven and dry it overnight to obtain a polymeric quaternary phosphonium salt bactericide.

[0017] Polymerized quaternary phosphonium salt bactericide, prepared by any one of the methods described above.

[0018] The aforementioned polymeric quaternary phosphonium salt bactericides are used as bactericides in oil extraction.

[0019] The aforementioned polymeric quaternary phosphonium salt bactericide is used as a bactericide for reinjection water in oil extraction.

[0020] The main technical concept of this invention is as follows: Existing polymeric bactericides have quaternary phosphonium cations linked to two butyl groups and cyclohexyl ketones, while non-polymeric bactericide molecules contain four quaternary phosphonium cations, resulting in significant steric hindrance. The present invention adds 1,3-dihydroxybenzyl and ethyl groups, resulting in a monomer containing two quaternary phosphonium cations, which offers the following advantages:

[0021] 1. Improve the quaternary phosphonium cation linker by replacing the butyl group with an ethyl group that has less steric hindrance;

[0022] 2. Optimize the quaternary phosphonium cation linker group by replacing the cyclohexyl group with a 1,3-dihydroxybenzyl group that has strong electron-withdrawing ability;

[0023] 3. The number of quaternary phosphonium cations is reduced. The polymer monomer contains two quaternary phosphonium cations, which reduces steric hindrance.

[0024] Invention Effects: The polymeric quaternary phosphonium salt bactericide, its preparation method, and its application disclosed in this invention have the following beneficial effects:

[0025] 1. The polymeric quaternary phosphonium salt bactericide synthesized in this invention has a bactericidal effect on SRB, TGB, and IB in oily wastewater, and is effective when the bacterial count reaches 10. 6 When the concentration is 100 mg / L, it can achieve 100% sterilization efficiency against SRB, TGB and IB in wastewater.

[0026] 2. The polymeric quaternary phosphonium salt bactericide of the present invention has a broad spectrum. Compared with existing bactericides, the polymeric quaternary phosphonium salt bactericide of the present invention has the advantages of low concentration and high bactericidal efficiency, and therefore can be widely used in sewage treatment. Detailed Implementation

[0027] The specific embodiments of the present invention are described in detail below.

[0028] The "range" disclosed in this invention is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 10–50 is listed for a specific parameter, it is also expected that ranges of 10–40 and 20–50 are also included. Furthermore, if the minimum range values ​​are 1 and 2, and the maximum range values ​​are 3, 4, and 5, then the following ranges are all expected: 1–3, 1–4, 1–5, 2–3, 2–4, and 2–5. In this application, unless otherwise stated, the numerical range "a–b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0–5" means that all real numbers between "0–5" have been listed herein; "0–5" is merely a shortened representation of these numerical combinations.

[0029] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0030] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0031] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0032] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0033] Unless otherwise specified, the reaction will proceed under normal temperature and pressure conditions.

[0034] Unless otherwise specified, all parts or percentages are by weight or by weight percentage.

[0035] In this invention, all the substances used are known substances that can be purchased or synthesized by known methods.

[0036] In this invention, all the devices or equipment used are conventional devices or equipment known in the art and are readily available.

[0037] Taking 3,5-dihydroxyacetophenone as an example, the reaction equation for the synthetic route of the polymeric quaternary phosphonium salt bactericide of the present invention is as follows:

[0038]

[0039] A polymeric quaternary phosphonium salt bactericide, with the following structural formula:

[0040] in:

[0041] n is a positive integer, and n = 100 to 1000.

[0042] A method for preparing the above-mentioned polymeric quaternary phosphonium salt bactericide includes the following steps:

[0043] S1. 3,5-Dihydroxyacetophenone, water and organic acid are added to the reactor in sequence. Nitrogen or inert gas is introduced for protection. Organic phosphine is added dropwise while stirring. After completion, the temperature is raised to at least 40°C and the reaction is carried out for a period of time. The brown intermediate product A is obtained by vacuum distillation.

[0044] S2. In a nitrogen or inert gas atmosphere, add alcohol and haloalkanes to the brown intermediate product A obtained in step S1, adjust the temperature, stir and heat, reflux for a period of time, distill under reduced pressure, and preliminarily purify to obtain a brown viscous product.

[0045] S3. Add an ester solvent to the brown viscous product obtained in step S2, stir and heat until dissolved to obtain a solution, then filter the solution, let the collected filtrate cool naturally until the product precipitates, filter, take the product, dry it to obtain the polyquaternium salt bactericide monomer.

[0046] S4. Add the polyquaternium salt bactericide monomer obtained in step S3 to the reactor, and add an appropriate amount of water as a solvent. Stir and heat to at least 45°C. While stirring, add potassium persulfate aqueous solution dropwise. After reacting for at least 4 hours, heat to at least 70°C and continue reacting for at least 0.5 hours. Add sodium bisulfite aqueous solution and stir for at least 4 hours to obtain a viscous liquid.

[0047] S5. Filter the viscous liquid obtained in step S4 to obtain a light yellow solid, put it in an oven and dry it overnight to obtain a polymeric quaternary phosphonium salt bactericide.

[0048] Furthermore, the organophosphine mentioned in step S1 is one of dibutylphosphine and diethylphosphine.

[0049] Furthermore, the organic acid mentioned in step S1 is one of formic acid and acetic acid.

[0050] Further, the molar ratio of 3,5-dihydroxyacetophenone to organophosphate in step S1 is 1:

[0051] (1.05~1.1);

[0052] In step S1, the mass ratio of water, organic acid, and organic phosphorus is (5-15):(0.4-0.6):1.

[0053] Furthermore, in step S1, the reaction temperature is 40–50°C, preferably 45–50°C; the reaction time is at least 2 hours, preferably 2–3 hours.

[0054] Furthermore, the alcohol in step S2 is one of ethylene glycol, isobutanol, isopropanol, and ethanol.

[0055] Furthermore, the haloalkane in step S2 is one of 1,4-dibromo-2-butene and 1,4-dichloro-2-butene.

[0056] Furthermore, the mass ratio of the alcohol in step S2 to the 3,5-dihydroxyacetophenone in step S1 is (4-8):1;

[0057] The molar ratio of 3,5-dihydroxyacetophenone in step S1 to the haloalkane in step S2 is 1:(0.55-0.6).

[0058] Furthermore, in step S2, the reflux time is at least 6 hours, preferably 6 to 8 hours.

[0059] Further, in step S3, the ester solvent is one of methyl formate, methyl acetate, and ethyl acetate, preferably ethyl acetate, and / or

[0060] The mass ratio of 3,5-dihydroxyacetophenone in step S1 to the ester solvent in step S3 is 1:(4-10).

[0061] Further, in step S4, the mass concentration of the potassium persulfate aqueous solution is 25% to 30%;

[0062] The concentration of the sodium bisulfite aqueous solution is 15% to 20%;

[0063] The mass ratio of 3,5-dihydroxyacetophenone in step S1 to the potassium persulfate aqueous solution and sodium bisulfite aqueous solution in step S4 is 1:(0.05~0.15):(0.4~0.8);

[0064] The drying temperature of the oven in step S4 is at least 80°C.

[0065] Polymerized quaternary phosphonium salt bactericide, prepared by any one of the methods described above.

[0066] The aforementioned polymeric quaternary phosphonium salt bactericides are used as bactericides in oil extraction.

[0067] The aforementioned polymeric quaternary phosphonium salt bactericide is used as a bactericide for reinjection water in oil extraction.

[0068] In one embodiment:

[0069] A polymeric quaternary phosphonium salt bactericide, with the following structural formula:

[0070] in:

[0071] n is a positive integer, and n = 100.

[0072] A method for preparing the above-mentioned polymeric quaternary phosphonium salt bactericide includes the following steps:

[0073] S1. 3,5-Dihydroxyacetophenone, water and organic acid are added to the reactor in sequence. Nitrogen gas is introduced for protection. Organic phosphine is added dropwise while stirring. After completion, the temperature is raised to 40°C and the reaction is carried out for a period of time. The product is purified by vacuum distillation to obtain brown intermediate product A.

[0074] S2. In a nitrogen atmosphere, alcohol and haloalkanes are added to the brown intermediate product A obtained in step S1. The temperature is adjusted, the mixture is stirred and heated, and the reaction is refluxed for a period of time. The product is then distilled under reduced pressure to obtain a brown viscous product after preliminary purification.

[0075] S3. Add an ester solvent to the brown viscous product obtained in step S2, stir and heat until dissolved to obtain a solution, then filter the solution, let the collected filtrate cool naturally until the product precipitates, filter, take the product, dry it to obtain the polyquaternium salt bactericide monomer.

[0076] S4. Add the polyquaternium salt bactericide monomer obtained in step S3 into the reactor, and add an appropriate amount of water as a solvent. Stir and heat to 45°C. While stirring, add potassium persulfate aqueous solution dropwise. After reacting for 4 hours, heat to 70°C and continue reacting for 0.5 hours. Add sodium bisulfite aqueous solution and stir for 4 hours to obtain a viscous liquid.

[0077] S5. Filter the viscous liquid obtained in step S4 to obtain a light yellow solid, and dry it overnight in an oven at 80°C to obtain a polymeric quaternary phosphonium salt bactericide.

[0078] Furthermore, the organophosphine mentioned in step S1 is dibutylphosphine.

[0079] Furthermore, the organic acid mentioned in step S1 is formic acid.

[0080] Further, the molar ratio of 3,5-dihydroxyacetophenone to organophosphorus in step S1 is 1:1.05; the mass ratio of water, organic acid, and organophosphorus in step S1 is 5:0.4:1.

[0081] Furthermore, in step S1, the reaction temperature is 40°C and the reaction time is 3 hours.

[0082] Furthermore, the alcohol in step S2 is ethylene glycol.

[0083] Furthermore, the haloalkane in step S2 is 1,4-dibromo-2-butene.

[0084] Furthermore, the mass ratio of the alcohol in step S2 to the 3,5-dihydroxyacetophenone in step S1 is 4:1;

[0085] The molar ratio of 3,5-dihydroxyacetophenone in step S1 to the haloalkane in step S2 is 1:0.55.

[0086] Furthermore, in step S2, the reflux time is 6 hours.

[0087] Further, in step S3, the ester solvent is methyl formate, and / or

[0088] The mass ratio of 3,5-dihydroxyacetophenone in step S1 to the ester solvent in step S3 is 1:4.

[0089] Further, in step S4, the mass concentration of the potassium persulfate aqueous solution is 25%;

[0090] The concentration of the sodium bisulfite aqueous solution is 15%;

[0091] The mass ratio of 3,5-dihydroxyacetophenone in step S1 to the potassium persulfate aqueous solution and sodium bisulfite aqueous solution in step S4 is 1:0.05:0.4.

[0092] Polymerized quaternary phosphonium salt bactericide, prepared by any one of the methods described above.

[0093] The aforementioned polymeric quaternary phosphonium salt bactericides are used as bactericides in oil extraction.

[0094] The aforementioned polymeric quaternary phosphonium salt bactericide is used as a bactericide for reinjection water in oil extraction.

[0095] In another embodiment

[0096] A polymeric quaternary phosphonium salt bactericide, with the following structural formula:

[0097] in:

[0098] n is a positive integer, and n = 1000.

[0099] A method for preparing the above-mentioned polymeric quaternary phosphonium salt bactericide includes the following steps:

[0100] S1. 3,5-Dihydroxyacetophenone, water and organic acid are added to the reactor in sequence, argon gas is introduced for protection, and organophosphorus is added dropwise while stirring. After completion, the temperature is raised to 60°C and reacted for a period of time. The product is purified by vacuum distillation to obtain brown intermediate product A.

[0101] S2. In an argon atmosphere, alcohol and haloalkanes are added to the brown intermediate product A obtained in step S1. The temperature is adjusted, the mixture is stirred and heated, and the reaction is refluxed for a period of time. The product is then distilled under reduced pressure to obtain a brown viscous product after preliminary purification.

[0102] S3. Add an ester solvent to the brown viscous product obtained in step S2, stir and heat until dissolved to obtain a solution, then filter the solution, let the collected filtrate cool naturally until the product precipitates, filter, take the product, dry it to obtain the polyquaternium salt bactericide monomer.

[0103] S4. Add the polyquaternium salt bactericide monomer obtained in step S3 into the reactor, and add an appropriate amount of water as a solvent. Stir and heat to 60°C. While stirring, add potassium persulfate aqueous solution dropwise. After reacting for 6 hours, heat to 90°C and continue reacting for 1 hour. Add sodium bisulfite aqueous solution and stir for 6 hours to obtain a viscous liquid.

[0104] S5. Filter the viscous liquid obtained in step S4 to obtain a light yellow solid, and dry it overnight in an oven at 90°C to obtain a polymeric quaternary phosphonium salt bactericide.

[0105] Furthermore, the organophosphine mentioned in step S1 is diethylphosphine.

[0106] Furthermore, the organic acid mentioned in step S1 is acetic acid.

[0107] Further, the molar ratio of 3,5-dihydroxyacetophenone to organophosphorus in step S1 is 1:1.1, and the mass ratio of water, organic acid, and organophosphorus in step S1 is 15:0.6:1.

[0108] Furthermore, in step S1, the reaction temperature is 50°C and the reaction time is 2 hours.

[0109] Furthermore, the alcohol in step S2 is isobutanol.

[0110] Furthermore, the haloalkane in step S2 is 1,4-dichloro-2-butene.

[0111] Furthermore, the mass ratio of the alcohol in step S2 to the 3,5-dihydroxyacetophenone in step S1 is 8:1;

[0112] The molar ratio of 3,5-dihydroxyacetophenone in step S1 to the haloalkane in step S2 is 1:0.6.

[0113] Furthermore, in step S2, the reflux time is 8 hours.

[0114] Further, in step S3, the ester solvent is methyl acetate, and / or

[0115] The mass ratio of 3,5-dihydroxyacetophenone in step S1 to the ester solvent in step S3 is 1:10.

[0116] Further, in step S4, the mass concentration of the potassium persulfate aqueous solution is 30%;

[0117] The concentration of the sodium bisulfite aqueous solution is 20%;

[0118] The mass ratio of 3,5-dihydroxyacetophenone in step S1 to the potassium persulfate aqueous solution and sodium bisulfite aqueous solution in step S4 is 1:0.15:0.8.

[0119] Polymerized quaternary phosphonium salt bactericide, prepared by any one of the methods described above.

[0120] The aforementioned polymeric quaternary phosphonium salt bactericides are used as bactericides in oil extraction.

[0121] The aforementioned polymeric quaternary phosphonium salt bactericide is used as a bactericide for reinjection water in oil extraction.

[0122] In yet another embodiment

[0123] A polymeric quaternary phosphonium salt bactericide, with the following structural formula:

[0124] in:

[0125] n is a positive integer, and n = 600.

[0126] A method for preparing the above-mentioned polymeric quaternary phosphonium salt bactericide includes the following steps:

[0127] S1. 3,5-Dihydroxyacetophenone, water and organic acid are added to the reactor in sequence, helium gas is introduced for protection, and organophosphorus is added dropwise while stirring. After completion, the temperature is raised to 42°C and reacted for a period of time. The product is purified by vacuum distillation to obtain brown intermediate product A.

[0128] S2. In a helium atmosphere, alcohol and haloalkanes are added to the brown intermediate product A obtained in step S1. The temperature is adjusted, the mixture is stirred and heated, and the reaction is refluxed for a period of time. The product is then distilled under reduced pressure to obtain a brown viscous product after preliminary purification.

[0129] S3. Add an ester solvent to the brown viscous product obtained in step S2, stir and heat until dissolved to obtain a solution, then filter the solution, let the collected filtrate cool naturally until the product precipitates, filter, take the product, dry it to obtain the polyquaternium salt bactericide monomer.

[0130] S4. Add the polyquaternium salt bactericide monomer obtained in step S3 into the reactor, and add an appropriate amount of water as a solvent. Stir and heat to 46°C. While stirring, add potassium persulfate aqueous solution dropwise. After reacting for 4.5 hours, heat to 72°C and continue reacting for 0.6 hours. Add sodium bisulfite aqueous solution and stir for 4.5 hours to obtain a viscous liquid.

[0131] S5. Filter the viscous liquid obtained in step S4 to obtain a light yellow solid, and dry it overnight in an oven at 85°C to obtain a polymeric quaternary phosphonium salt bactericide.

[0132] Furthermore, the organophosphine mentioned in step S1 is dibutylphosphine.

[0133] Furthermore, the organic acid mentioned in step S1 is acetic acid.

[0134] Further, the molar ratio of 3,5-dihydroxyacetophenone to organophosphorus in step S1 is 1:1.08; the mass ratio of water, organic acid, and organophosphorus in step S1 is 10:0.5:1.

[0135] Furthermore, in step S1, the reaction temperature is 45°C and the reaction time is 2.5 hours.

[0136] Further, the alcohol in step S2 is isopropanol. In another embodiment, the alcohol in step S2 is ethanol.

[0137] Furthermore, the haloalkane in step S2 is 1,4-dibromo-2-butene.

[0138] Furthermore, the mass ratio of the alcohol in step S2 to the 3,5-dihydroxyacetophenone in step S1 is 6:1;

[0139] The molar ratio of 3,5-dihydroxyacetophenone in step S1 to the haloalkane in step S2 is 10.58.

[0140] Furthermore, in step S2, the reflux time is 7 hours.

[0141] Further, in step S3, the ester solvent is ethyl acetate, and / or

[0142] The mass ratio of 3,5-dihydroxyacetophenone in step S1 to the ester solvent in step S3 is 1:5.

[0143] Further, in step S4, the mass concentration of the potassium persulfate aqueous solution is 27%;

[0144] The concentration of the sodium bisulfite aqueous solution is 18%;

[0145] The mass ratio of 3,5-dihydroxyacetophenone in step S1 to the potassium persulfate aqueous solution and sodium bisulfite aqueous solution in step S4 is 1:0.1:0.6.

[0146] Polymerized quaternary phosphonium salt bactericide, prepared by any one of the methods described above.

[0147] The aforementioned polymeric quaternary phosphonium salt bactericides are used as bactericides in oil extraction.

[0148] The aforementioned polymeric quaternary phosphonium salt bactericide is used as a bactericide for reinjection water in oil extraction.

[0149] Example 1

[0150] A method for preparing polymeric quaternary phosphonium salt bactericides includes the following steps:

[0151] (1) 15.20 g (0.1 mol) of 3,5-dihydroxyacetophenone, 75.68 g of water and 3.78 g of formic acid were added to a four-necked flask in sequence, and nitrogen gas was introduced for protection. 9.46 g (0.105 mol) of diethylphosphine was added dropwise while stirring. Finally, the temperature was raised to 50 °C and the reaction was carried out for 6 hours. The product was purified by vacuum distillation to obtain a brown intermediate product.

[0152] (2) In a nitrogen atmosphere, 60.80 g of ethylene glycol and 11.76 g (0.055 mol) of 1,4-dibromo-2-butene were added to the above intermediate product A. The temperature was adjusted, the mixture was stirred and heated, and the mixture was refluxed for 6 hours. The product was then purified by vacuum distillation to obtain a brown viscous product.

[0153] (3) Add 60.80g of ethyl acetate solvent to the above crude product, stir and heat until dissolved, filter directly at a high temperature, cool the collected filtrate naturally until the product precipitates, filter and dry, and the product obtained is the polyquaternium salt bactericide monomer.

[0154] (4) Add the polyquaternium salt bactericide monomer obtained in (3) to a clean three-necked flask, add water until dissolved, stir and heat to 45°C, add 0.59g of potassium persulfate initiator dropwise while stirring, react for 4 hours and then heat to 70°C, continue to react for 0.5 hours, add 6.08g of 15wt% sodium bisulfite solution, stir for 4 hours to obtain a viscous liquid;

[0155] (5) The viscous liquid obtained above was filtered to obtain a light yellow solid, which was then dried overnight in an oven at 80°C to obtain polymeric quaternary phosphonium salt bactericide M1.

[0156] Example 2

[0157] A method for preparing polymeric quaternary phosphonium salt bactericides includes the following steps:

[0158] (1) 15.20 g (0.1 mol) of 3,5-dihydroxyacetophenone, 79.28 g of water and 4.96 g of formic acid were added to a four-necked flask in sequence, nitrogen gas was introduced for protection, and 9.91 g (0.11 mol) of diethylphosphine was added dropwise while stirring. Finally, the temperature was raised to 46 °C and the reaction was carried out for 6 hours. The product was purified by vacuum distillation to obtain a brown intermediate product.

[0159] (2) In a nitrogen atmosphere, 60.80 g of ethylene glycol and 11.98 g (0.06 mol) of 1,4-dibromo-2-butene were added to the above intermediate product A. The temperature was adjusted, the mixture was stirred and heated, and the mixture was refluxed for 6 hours. The product was then purified by vacuum distillation to obtain a brown viscous product.

[0160] (3) Add 68.40g of ethyl acetate solvent to the above crude product, stir and heat until dissolved, filter directly at a high temperature, cool the collected filtrate naturally until the product precipitates, filter and dry, and the product obtained is the polyquaternium salt bactericide monomer.

[0161] (4) Add the polyquaternium salt bactericide monomer obtained in (3) to a clean three-necked flask, add water until dissolved, stir and heat to 45°C, add 0.83g of potassium persulfate initiator dropwise while stirring, react for 4 hours and then heat to 70°C, continue to react for 0.5 hours, add 7.60g of 15wt% sodium bisulfite solution, stir for 4 hours to obtain a viscous liquid;

[0162] (5) The viscous liquid obtained above was filtered to obtain a light yellow solid, which was then dried overnight in an oven at 80°C to obtain polymeric quaternary phosphonium salt bactericide M2.

[0163] Example 3

[0164] A method for preparing polymeric quaternary phosphonium salt bactericides includes the following steps:

[0165] (1) 15.20 g (0.1 mol) of 3,5-dihydroxyacetophenone, 85.14 g of water and 5.68 g of formic acid were added to a four-necked flask in sequence, and nitrogen gas was introduced for protection. 9.46 g (0.105 mol) of diethylphosphine was added dropwise while stirring. Finally, the temperature was raised to 45 °C and the reaction was carried out for 6 hours. The product was purified by vacuum distillation to obtain a brown intermediate product.

[0166] (2) In a nitrogen atmosphere, 76.00 g of ethylene glycol and 11.98 g (0.06 mol) of 1,4-dibromo-2-butene were added to the above intermediate product A. The temperature was adjusted, the mixture was stirred and heated, and the mixture was refluxed for 7 hours. The product was then purified by vacuum distillation to obtain a brown viscous product.

[0167] (3) Add 68.40g of ethyl acetate solvent to the above crude product, stir and heat until dissolved, filter directly at a high temperature, cool the collected filtrate naturally until the product precipitates, filter and dry, and the product obtained is the polyquaternium salt bactericide monomer.

[0168] (4) Add the polyquaternium salt bactericide monomer obtained in (3) to a clean three-necked flask, add water until dissolved, stir and heat to 45°C, add 0.96g of potassium persulfate initiator dropwise while stirring, react for 4 hours and then heat to 70°C, continue to react for 0.5 hours, add 9.12g of 15wt% sodium bisulfite solution, stir for 4 hours to obtain a viscous liquid;

[0169] (5) The viscous liquid obtained above was filtered to obtain a light yellow solid, which was then dried overnight in an oven at 80°C to obtain polymeric quaternary phosphonium salt bactericide M3.

[0170] Example 4

[0171] A method for preparing polymeric quaternary phosphonium salt bactericides includes the following steps:

[0172] (1) 15.20 g (0.1 mol) of 3,5-dihydroxyacetophenone, 89.19 g of water and 5.95 g of formic acid were added to a four-necked flask in sequence, nitrogen gas was introduced for protection, and 9.91 g (0.11 mol) of diethylphosphine was added dropwise while stirring. Finally, the temperature was raised to 48 °C and the reaction was carried out for 6 hours. The product was purified by vacuum distillation to obtain a brown intermediate product.

[0173] (2) In a nitrogen atmosphere, 76.00 g of ethylene glycol and 11.76 g (0.055 mol) of 1,4-dibromo-2-butene were added to the above intermediate product A. The temperature was adjusted, the mixture was stirred and heated, and the mixture was refluxed for 8 hours. The product was then purified by vacuum distillation to obtain a brown viscous product.

[0174] (3) Add 76.00g of ethyl acetate solvent to the above crude product, stir and heat until dissolved, filter directly at a high temperature, cool the collected filtrate naturally until the product precipitates, filter and dry, and the product obtained is the polyquaternium salt bactericide monomer.

[0175] (4) Add the polyquaternium salt bactericide monomer obtained in (3) to a clean three-necked flask, add water until dissolved, stir and heat to 45°C, add 1.06g of potassium persulfate initiator dropwise while stirring, react for 4 hours and then heat to 70°C, continue to react for 0.5 hours, add 10.64g of 15wt% sodium bisulfite solution, stir for 4 hours to obtain a viscous liquid;

[0176] (5) The viscous liquid obtained above was filtered to obtain a light yellow solid, which was then dried overnight in an oven at 80°C to obtain polymeric quaternary phosphonium salt bactericide M4.

[0177] Example 5

[0178] A method for preparing polymeric quaternary phosphonium salt bactericides includes the following steps:

[0179] (1) 15.98 g (0.105 mol) of 3,5-dihydroxyacetophenone, 85.14 g of water and 5.68 g of formic acid were added to a four-necked flask in sequence, and nitrogen gas was introduced for protection. 9.46 g (0.105 mol) of diethylphosphine was added dropwise while stirring. Finally, the temperature was raised to 50 °C and the reaction was carried out for 8 hours. The product was purified by vacuum distillation to obtain a brown intermediate product.

[0180] (2) In a nitrogen atmosphere, 63.92 g of ethylene glycol and 11.98 g (0.06 mol) of 1,4-dibromo-2-butene were added to the above intermediate product A. The temperature was adjusted, the mixture was stirred and heated, and the mixture was refluxed for 7 hours. The product was then purified by vacuum distillation to obtain a brown viscous product.

[0181] (3) Add 68.40g of ethyl acetate solvent to the above crude product, stir and heat until dissolved, filter directly at a high temperature, cool the collected filtrate naturally until the product precipitates, filter and dry, and the product obtained is the polyquaternium salt bactericide monomer.

[0182] (4) Add the polyquaternium salt bactericide monomer obtained in (3) to a clean three-necked flask, add water until dissolved, stir and heat to 45°C, add 1.12g of potassium persulfate initiator dropwise while stirring, react for 4 hours and then heat to 70°C, continue to react for 0.5 hours, add 12.78g of 15wt% sodium bisulfite solution, stir for 4 hours to obtain a viscous liquid;

[0183] (5) The viscous liquid obtained above was filtered to obtain a light yellow solid, which was then dried overnight in an oven at 80°C to obtain polymeric quaternary phosphonium salt bactericide M5.

[0184] Example 6

[0185] A method for preparing polymeric quaternary phosphonium salt bactericides includes the following steps:

[0186] (1) 15.98 g (0.105 mol) of 3,5-dihydroxyacetophenone, 99.10 g of water and 4.96 g of formic acid were added to a four-necked flask in sequence, and nitrogen gas was introduced for protection. 9.91 g (0.11 mol) of diethylphosphine was added dropwise while stirring. Finally, the temperature was raised to 50 °C and the reaction was carried out for 3 hours. The product was purified by vacuum distillation to obtain a brown intermediate product.

[0187] (2) In a nitrogen atmosphere, 79.90 g of ethylene glycol and 11.76 g (0.055 mol) of 1,4-dibromo-2-butene were added to the above intermediate product A. The temperature was adjusted, the mixture was stirred and heated, and the mixture was refluxed for 8 hours. The product was then purified by vacuum distillation to obtain a brown viscous product.

[0188] (3) Add 63.92g of ethyl acetate solvent to the above crude product, stir and heat until dissolved, filter directly at a high temperature, cool the collected filtrate naturally until the product precipitates, filter and dry, and the product obtained is the polyquaternium salt bactericide monomer.

[0189] (4) Add the polyquaternium salt bactericide monomer obtained in (3) to a clean three-necked flask, add water until dissolved, stir and heat to 45°C, add 0.94g of potassium persulfate initiator dropwise while stirring, react for 4 hours and then heat to 70°C, continue to react for 0.5 hours, add 11.19g of 15wt% sodium bisulfite solution, stir for 4 hours to obtain a viscous liquid;

[0190] (5) The viscous liquid obtained above was filtered to obtain a light yellow solid, which was then dried overnight in an oven at 80°C to obtain polymeric quaternary phosphonium salt bactericide M6.

[0191] bactericidal performance verification experiment

[0192] 1. Testing Method

[0193] In three narrow-mouthed flasks, 100 ml of well-produced fluid containing sulfate-reducing bacteria (SRB), saprophytic bacteria (TGB), and iron bacteria (IB) were added respectively, along with the corresponding bacterial culture medium. The flasks were incubated at 55°C until the bacterial count reached 10⁻⁶. 6When the bacterial count was 1 / mL, different concentrations of bactericide were added to the cultured liquid, shaken well, and placed in an oven at 55℃ for 1 hour for sterilization. Finally, the MPN detection method was used to detect the number of remaining bacteria and calculate the sterilization efficiency.

[0194] 2. Bactericidal efficiency of sulfate-reducing bacteria (SRB)

[0195] Table 1. SRB sterilization results (sterilization rate, %)

[0196] Concentration, mg / L 50 75 100 125 150 M1 94.2 96.0 100 100 100 M2 94.0 95.8 100 100 100 M3 93.6 96.0 100 100 100 M4 95.2 96.5 100 100 100 M5 96.2 97.0 100 100 100 M6 94.5 98.5 100 100 100 1227 30 44.5 58.3 68.9 75.6

[0197] As can be seen from Table 1, the polymeric quaternary phosphonium salt bactericides M1-M6 of the present invention achieve a bacterial count of 10. 6 When the concentration is 75 mg / L, the bactericidal rate against SRB reaches over 95.8%; at a concentration of 100 mg / L, the bactericidal rate against SRB reaches 100%; while the existing bactericide 1227 only achieves a bactericidal efficiency of 75.6% at a concentration of 150 mg / L. Compared with existing bactericides, the polymeric quaternary phosphonium salt bactericide of this invention has a better bactericidal effect against SRB.

[0198] 3. Sterilization efficiency of saprophytic bacteria (TGB)

[0199] Table 2. TGB sterilization results (sterilization rate, %)

[0200] Concentration, mg / L 50 75 100 125 150 M1 93.6 97.0 100 100 100 M2 94.0 95.6 100 100 100 M3 94.5 96.0 100 100 100 M4 95.5 96.5 100 100 100 M5 93.5 97.5 100 100 100 M6 93.0 96.8 100 100 100 1227 30 56.8 65.6 74.5 82.5

[0201] As can be seen from Table 2, the bacterial count in M1-M6 of this invention reaches 10. 6 At a concentration of 75 mg / L, the bactericidal rate against TGB reaches 96.0%; at a concentration of 100 mg / L, the bactericidal rate against SRB reaches 100%; while the existing bactericide 1227 only achieves a bactericidal efficiency of 82.5% at a concentration of 150 mg / L. Compared with the existing bactericide 1227, the polymeric quaternary phosphonium salt bactericide of the present invention has a better bactericidal effect against TGB.

[0202] 4. Sterilization efficiency of iron bacteria (IB)

[0203] Table 3. IB sterilization results (sterilization rate, %)

[0204] Concentration, mg / L 50 75 100 125 150 M1 92.5 95.0 100 100 100 M2 93.6 96.0 100 100 100 M3 94.5 95.9 100 100 100 M4 93.8 97.8 100 100 100 M5 95.0 98.0 100 100 100 M6 95.5 97.5 100 100 100 1227 35 58 69.5 75.8 85.6

[0205] As can be seen from Table 3, the bacterial count in M1-M6 of this invention reaches 10. 6When the concentration is 75 mg / L, the bactericidal rate against IB reaches 95.0%; when the concentration is 100 mg / L, the bactericidal rate against IB reaches 100%; while the existing bactericide 1227 only achieves a bactericidal efficiency of 85.6% at a concentration of 150 mg / L. Compared with the existing bactericide 1227, the polymeric quaternary phosphonium salt bactericide of the present invention has a better bactericidal effect against IB.

[0206] The embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments, and various changes can be made within the scope of knowledge possessed by those skilled in the art without departing from the spirit of the present invention.

Claims

1. A polymeric quaternary phosphonium salt bactericide, characterized in that, Its structural formula is as follows: in: n is a positive integer, and n = 100 to 1000.

2. A method for preparing the polymeric quaternary phosphonium salt bactericide according to claim 1, characterized in that, Includes the following steps: S1. 3,5-Dihydroxyacetophenone, water and organic acid are added to the reactor in sequence. Nitrogen or inert gas is introduced for protection. Organic phosphine is added dropwise while stirring. After completion, the temperature is raised to at least 40°C and the reaction is carried out for a period of time. The brown intermediate product A is obtained by vacuum distillation. S2. In a nitrogen or inert gas atmosphere, add alcohol and haloalkanes to the brown intermediate product A obtained in step S1, adjust the temperature, stir and heat, reflux for a period of time, distill under reduced pressure, and preliminarily purify to obtain a brown viscous product. S3. Add an ester solvent to the brown viscous product obtained in step S2, stir and heat until dissolved to obtain a solution, then filter the solution, let the collected filtrate cool naturally until the product precipitates, filter, take the product, dry it to obtain the polyquaternium salt bactericide monomer. S4. Add the polyquaternium salt bactericide monomer obtained in step S3 to the reactor, and add an appropriate amount of water as a solvent. Stir and heat to at least 45°C. While stirring, add potassium persulfate aqueous solution dropwise. After reacting for at least 4 hours, heat to at least 70°C and continue reacting for at least 0.5 hours. Add sodium bisulfite aqueous solution and stir for at least 4 hours to obtain a viscous liquid. S5. Filter the viscous liquid obtained in step S4 to obtain a light yellow solid, put it in an oven and dry it overnight to obtain a polymeric quaternary phosphonium salt bactericide.

3. The preparation method of the polymeric quaternary phosphonium salt bactericide as described in claim 2, characterized in that, The organophosphine mentioned in step S1 is one of dibutylphosphine and diethylphosphine, and / or The organic acid mentioned in step S1 is one of formic acid and acetic acid, and / or The molar ratio of 3,5-dihydroxyacetophenone to organophosphate in step S1 is 1:(1.05-1.1), and / or In step S1, the mass ratio of water, organic acid, and organic phosphorus is (5-15):(0.4-0.6):1, and / or In step S1, the reaction temperature is 40-50°C, preferably 45-50°C; the reaction time is at least 2 hours, preferably 2-3 hours.

4. The preparation method of the polymeric quaternary phosphonium salt bactericide as described in claim 2, characterized in that, The alcohol in step S2 is one of ethylene glycol, isobutanol, isopropanol, ethanol, and / or The haloalkane in step S2 is one of 1,4-dibromo-2-butene, 1,4-dichloro-2-butene, and / or The mass ratio of the alcohol in step S2 to the 3,5-dihydroxyacetophenone in step S1 is (4-8):1, and / or The molar ratio of 3,5-dihydroxyacetophenone in step S1 to the haloalkane in step S2 is 1:(0.55-0.6).

5. The preparation method of a polymeric quaternary phosphonium salt bactericide as described in claim 2, characterized in that, In step S2, the reflux time is at least 6 hours, preferably 6 to 8 hours, and / or In step S3, the ester solvent is one of methyl formate, methyl acetate, and ethyl acetate, preferably ethyl acetate, and / or The mass ratio of 3,5-dihydroxyacetophenone in step S1 to the ester solvent in step S3 is 1:(4-10).

6. The method for preparing a polymeric quaternary phosphonium salt bactericide as described in claim 2, characterized in that, In step S4, the mass concentration of the potassium persulfate aqueous solution is 25%–30%, and / or The concentration of the sodium bisulfite aqueous solution is 15% to 20%.

7. The method for preparing a polymeric quaternary phosphonium salt bactericide as described in claim 2, characterized in that, The mass ratio of 3,5-dihydroxyacetophenone in step S1 to the potassium persulfate aqueous solution and sodium bisulfite aqueous solution in step S4 is 1:(0.05-0.15):(0.4-0.8), and / or The drying temperature of the oven in step S4 is at least 80°C.

8. A polymeric quaternary phosphonium salt bactericide, characterized in that, Prepared by the method described in any one of claims 2-7.

9. The application of the polymeric quaternary phosphonium salt bactericide according to claim 1 or 8 as a bactericide in oil extraction.

10. The application of the polymeric quaternary phosphonium salt bactericide according to claim 1 or 8 as a bactericide for reinjection water in oil extraction.

Images