CN114773504B - Fluorine-containing macromolecular quaternary ammonium salt with two-block structure, and preparation method and application thereof - Google Patents
Fluorine-containing macromolecular quaternary ammonium salt with two-block structure, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of sterilization, and discloses a fluorine-containing macromolecular quaternary ammonium salt with a two-block structure, and a preparation method and application thereof. The fluorine-containing macromolecular quaternary ammonium salt with a two-block structure and a structural general formula shown in formula 1:wherein m and n are both positive integers, and m: n= (14-22): (6-32). The fluorine-containing macromolecular quaternary ammonium salt with the two-block structure has good antibacterial effect, particularly has the effect of inhibiting FOC4 spores in soil, reduces the influence on the diversity of soil microorganisms, and is beneficial to preventing and treating banana wilt.
Description
Technical Field
The invention belongs to the technical field of sterilization, and particularly relates to a fluorine-containing macromolecular quaternary ammonium salt with a two-block structure, and a preparation method and application thereof.
Background
The pathogenic bacteria of the banana vascular wilt are Fusarium oxysporum Gouba specialization Fusarium oxysporium f.sp.cube (FOC for short), physiological species are more differentiated, and the No. 4 species (FOC 4 for short) have the greatest harm and the greatest distribution, and become one of the biggest diseases endangering banana planting industry worldwide. The pathogenic bacteria have strong saprophytic capability and can survive in soil for a long time in the form of dormant spores, and the occurrence of banana vascular wilt is positively related to the quantity of pathogenic bacteria FOC4 in the soil, so that reducing the quantity of pathogenic bacteria in the soil is an important method for preventing and treating banana vascular wilt.
The chemical prevention and treatment in the prior art mainly comprises two types of methods: one type is to use chemical agents to inhibit the number of pathogenic bacteria in the soil. Although some small molecular medicines such as prochloraz, propiconazole, thiophanate methyl, pentachloronitrobenzene and the like screened on the basis of indoor toxicity measurement and potting experiments at present have certain control effects on banana vascular wilt, the control effects in practice are poor. The other type can be called as 'soil disinfection', namely, a physical, chemical or biological method is adopted to kill microorganisms in soil, such as soil heating, soil fumigation and the like, wherein micromolecular chemical fumigation represented by dazomet (tetrahydrochysene-3, 5-dimethyl-2H-1, 3, 5-thiadiazine-2-thione), lime nitrogen (calcium cyanamide), chlorine dioxide and the like is the main method for field control at present; the method completely damages the microbial community structure in the soil, so that new organic matters are required to be introduced after the treatment to restore the soil, which is not beneficial to the stability of a soil ecological system. Biological control, crop rotation and the like are difficult to effectively implement on a large scale due to high economic cost, incapability of continuous planting, limited economic benefit and the like. Thus, there is currently no economically viable method for effectively inhibiting FOC4 in soil while maintaining as much as possible microbial diversity in the soil.
Therefore, there is a need to provide a novel bactericidal substance which has a good killing effect on FOC4 in soil and does not damage the soil microbial ecosystem, thereby being beneficial to the control of banana wilt.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure, the preparation method and the application thereof are provided, and the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure can have a good inhibition effect on the activity of FOC4 spores in soil, reduce the influence on the diversity of soil microorganisms and are beneficial to the control of banana wilt.
In a first aspect, the present invention provides a fluorine-containing macromolecular quaternary ammonium salt having a two-block structure.
Specifically, the fluorine-containing macromolecular quaternary ammonium salt with a two-block structure and a structural general formula shown in formula 1:
wherein m and n are both positive integers, and m: n= (14-22): (6-32).
Further preferably, the m: n=18: (6-30).
Preferably, m is a positive integer between 14 and 22, and n is a positive integer between 6 and 32.
Preferably, m is an even number between 14 and 22, and n is an even number between 6 and 32.
Preferably, m is 18 and n is 6, 12, 18 or 30.
B in formula 1 represents that the repeating units marked m and n are of a two-block structure.
Preferably, the molecular weight of the fluorine-containing macromolecular quaternary ammonium salt with a two-block structure is 5-20kDa, preferably 5-12kDa.
In a second aspect, the present invention provides a method for preparing a fluorine-containing macromolecular quaternary ammonium salt having a two-block structure.
Specifically, the preparation method of the fluorine-containing macromolecular quaternary ammonium salt with a two-block structure comprises the following steps:
(1) Mixing trifluoroethyl methacrylate, bromoester, a catalyst, an auxiliary agent and an organic solvent, reacting for the first time in an inert gas atmosphere, adding dimethylaminoethyl methacrylate, and reacting for the second time to obtain an intermediate product;
(2) Mixing the intermediate product prepared in the step (1), benzyl chloride and an organic solvent, and reacting in an inert gas atmosphere to prepare the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure.
Preferably, in step (1), the catalyst is a cuprous salt; further preferably, the catalyst is a cuprous salt formed by halogen and cuprous; more preferably, the catalyst is CuBr.
Preferably, the bromoester in step (1) is ethyl 2-bromoisobutyrate (abbreviated as EtBriB).
Preferably, in the step (1), the auxiliary agent includes N, N', N "-pentamethyldivinyl triamine (abbreviated as PMDETA).
Preferably, in step (1), the inert gas includes nitrogen or a rare gas.
Preferably, in step (1), after the second reaction is performed for a period of time, the reaction is stopped when the second reaction is exposed to air. The prepared intermediate product can be separated and purified and is light yellow transparent oily liquid.
Preferably, the separation and purification process of the intermediate product is as follows: performing rotary evaporation treatment on the mixture formed after the reaction to remove most of organic solvent, then adding acetone solvent, then adding neutral alumina, stirring until the solution turns from green to colorless, then filtering out powder, and finally performing rotary evaporation on the solvent and unreacted substances (monomers) to obtain a purified intermediate product; or removing most of organic solvent by rotary evaporation, dissolving the reacted system by acetone, filtering by a diaphragm pump to remove CuBr in the reacted system by a neutral alumina chromatographic column, and removing unreacted substances (monomers or auxiliaries) by rotary evaporation of the obtained eluent at 70 ℃ to obtain an intermediate product.
Preferably, in step (1), the organic solvent is toluene and/or ethanol.
Preferably, in the step (1), the volume of the organic solvent is 1 to 10 times, preferably 2 to 8 times of the total volume of the trifluoroethyl methacrylate and the bromoester.
Preferably, in step (1), the catalyst is pretreated and washed 3-10 times with acetic acid and methanol.
Preferably, in the step (1), the molar ratio of the bromoester, the catalyst and the auxiliary agent is 1: (0.8-2): (0.8-2); preferably 1:1.5:1.5.
preferably, in the step (1), the temperature of the first reaction is 45-55 ℃ and the reaction time is 1-10 hours; preferably, the temperature of the reaction is 48-50 ℃ and the reaction time is 2-3 hours.
Preferably, in the step (1), the temperature of the second reaction is 45-55 ℃, and the reaction time is 4-8 hours; preferably, the temperature of the reaction is 48-50 ℃ and the reaction time is 4-8 hours.
Preferably, in the step (1), the mass ratio of the trifluoroethyl methacrylate to the dimethylaminoethyl methacrylate is 1-5:3. the trifluoroethyl methacrylate and the dimethylaminoethyl methacrylate are subjected to reduced pressure distillation before use so as to remove polymerization inhibitor impurities.
Preferably, in step (2), the mass of the organic solvent is 2 to 5 times, preferably 3 to 4 times the mass of the intermediate product obtained in step (1).
Preferably, in the step (2), the temperature of the reaction is 45-55 ℃ and the reaction time is 20-50 hours; preferably, the temperature of the reaction is 48-50 ℃ and the reaction time is 24-48 hours.
Preferably, in the step (2), the molar ratio of the intermediate product prepared in the step (1) to benzyl chloride is 1 (3-8); preferably 1:5.
preferably, in the step (2), after the reaction is finished, the product is purified, and the specific process of purification is as follows: distilling off most of the solvent under reduced pressure, adding a large amount of anhydrous diethyl ether to precipitate out fluorine-containing macromolecular quaternary ammonium salt with a two-block structure, pouring out supernatant, repeating for 2-5 times, and then putting into a vacuum oven at 40-50 ℃ for drying to obtain the purified fluorine-containing macromolecular quaternary ammonium salt with a two-block structure.
The molecular weight of the product can be controlled by controlling the amount of each reaction raw material.
In a third aspect, the invention provides the use of a fluorine-containing macromolecular quaternary ammonium salt having a two-block structure.
The invention relates to an application of fluorine-containing macromolecular quaternary ammonium salt with a two-block structure in preventing and treating banana vascular wilt.
Preferably, the use is for inhibiting FOC 4.
An antibacterial agent comprising the fluorine-containing macromolecular quaternary ammonium salt having a two-block structure described above.
Compared with the prior art, the invention has the following beneficial effects:
(1) The fluorine-containing macromolecular quaternary ammonium salt with the two-block structure has good antibacterial effect, particularly has the effect of inhibiting FOC4 spores in soil, reduces the influence on the diversity of soil microorganisms, and is beneficial to preventing and treating banana wilt. The fluorine-containing macromolecular quaternary ammonium salt with the two-block structure can be effectively adsorbed in soil and is not easy to migrate, so that FOC4 spores in the soil can be effectively inhibited for a long time.
(2) The preparation method disclosed by the invention has the advantages that the process is simple and convenient, two steps are taken, no byproducts are generated in the reaction process, pure products can be efficiently and conveniently obtained, in addition, the atom transfer active free radical polymerization is adopted in the synthesis process, the structure and the molecular weight of the products can be controlled through the feeding sequence and the feeding ratio of each reaction, and the controllability of the prepared products is strong.
Drawings
FIG. 1 is an infrared spectrum of the intermediate and product obtained in example 1 and comparative example 1 of the present invention;
FIG. 2 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the intermediate product obtained in example 1 of the present invention;
FIG. 3 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product obtained in example 1 of the present invention;
FIG. 4 is a graph showing critical micelle concentration of the products prepared in examples 1 to 4 and comparative example 1 according to the present invention;
FIG. 5 is a Zeta potential diagram of the products of examples 1-4, comparative example 1, according to the present invention;
FIG. 6 is a schematic diagram showing particle size distribution of the products obtained in examples 1 to 4 and comparative example 1 according to the present invention;
FIG. 7 is a graph showing the antibacterial effect of the products of examples 1 to 4 and comparative example 1 according to the present invention;
FIG. 8 is a graph showing the saturated adsorption amount of the products prepared in examples 1 to 4 and comparative example 1 in soil;
FIG. 9 is a graph showing migration ability in soil of the products of examples 1 to 4 and comparative example 1 according to the present invention;
FIG. 10 shows the effect of the products of example 1 and comparative example 1 of the present invention on the diversity of soil microorganisms.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The fluorine-containing macromolecular quaternary ammonium salt with a two-block structure and a structural general formula shown in formula 1:
wherein m is 18, and n is 6, 12, 18 or 30.
B in formula 1 represents that the repeating units marked m and n are of a two-block structure.
The molecular weight of the fluorine-containing macromolecular quaternary ammonium salt with a two-block structure is 5-20kDa
The preparation method of the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure comprises the following steps:
(1) Mixing trifluoroethyl methacrylate, bromoester, a catalyst, an auxiliary agent and an organic solvent, reacting for the first time in an inert gas (nitrogen) atmosphere, adding dimethylaminoethyl methacrylate, and reacting for the second time to obtain an intermediate product;
(2) Mixing the intermediate product prepared in the step (1), benzyl chloride and an organic solvent, and reacting in an inert gas atmosphere to prepare the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure.
In the step (1), the catalyst is CuBr; the bromoester is ethyl 2-bromoisobutyrate (EtBriB); the auxiliary agent comprises N, N, N' -pentamethyldivinyl triamine (PMDETA for short); the inert gas is nitrogen; the prepared intermediate product can be separated and purified and is light yellow transparent oily liquid.
In the step (1), the temperature of the first reaction is 45-55 ℃, and the reaction time is 1-10 hours; the temperature of the second reaction is 45-55 ℃, and the reaction time is 4-8 hours.
In the step (2), the temperature of the reaction is 45-55 ℃ and the reaction time is 20-50 hours.
The equation for the above reaction is shown below:
comparative example 1: preparation of fluorine-containing quaternary ammonium salt product
The preparation of the fluorine-containing quaternary ammonium salt product comprises the following steps:
(1) 1.08g of CuBr is weighed into a 250mL eggplant-shaped bottle with stirring magnet, 40g of toluene and 40g of ethanol are added into an organic solvent, 1.3g of N, N' -pentamethyldivinyl triamine (PMDETA) and 0.975g of ethyl 2-bromoisobutyrate (EtBrib) are added into a reaction system, nitrogen is filled into the reaction system for three times, the reaction system is placed into an oil bath pot at 50 ℃ for stirring, then 15g of dimethylaminoethyl methacrylate (marked as DMAEMA) is added, the reaction is carried out for 5 hours at 50 ℃, the reaction is exposed to air for stopping the reaction, most of the organic solvent is removed by spin evaporation, 100mL of acetone is used for dissolving the reacted system, the obtained eluent is subjected to spin evaporation at 70 ℃ to remove unreacted substances (marked as MAEMA, and is abbreviated as D) through a neutral alumina chromatographic column, and an intermediate product is obtained 3 )；
(2) 10g of D obtained in step (1) are reacted with 3 Dissolving in 40g toluene/ethanol (mass ratio of 1:1) mixed organic solvent, loading into 150mL eggplant-shaped bottle with stirring magnet, flushing nitrogen gas into the reaction system for three times, placing into 50 ℃ oil bath, injecting 2.11g benzyl chloride into the reaction system, keeping the temperature for 24 hours, removing most toluene and ethanol organic solvent in the reacted system by rotary evaporation at 70 ℃, adding 100mL diethyl ether after rotary evaporation, precipitating the final product from toluene/ethanol organic solvent by utilizing solubility difference to obtain yellow flocculent product, repeatedly washing the product with diethyl ether for three times, filtering, placing into 60 ℃ vacuum oven, and drying for 48 hours to obtain fluorine-containing quaternary ammonium salt product (named as PDMAEMA-BC for short as Q) 5 )。
The reaction equation for the fluoroquaternary product of comparative example 1 is as follows:
example 1: preparation of fluorine-containing macromolecular quaternary ammonium salt with two-block structure
A fluorine-containing macromolecular quaternary ammonium salt with a two-block structure and a structural formula shown in formula 1:
wherein m is 18 and n is 6.
The preparation method of the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure comprises the following steps:
(1) 1.08g of CuBr is weighed into a 250mL eggplant-shaped bottle with a stirring magnet, 40g of toluene and 40g of ethanol are added into an organic solvent, 1.3g of N, N' -pentamethyldivinyl triamine (PMDETA) and 0.975g of ethyl 2-bromoisobutyrate (EtBrib) are added into a reaction system, nitrogen is filled into the reaction system for three times, the reaction system is placed under an oil bath kettle at 50 ℃ for stirring, then 5g of trifluoroethyl methacrylate (marked as DMAEMA) is added, after the first reaction at 50 ℃ for 2.5 hours, 15g of dimethylaminoethyl methacrylate (marked as DMAEMA) is added, after the second reaction at 50 ℃ for 4 hours, the reaction is exposed to air for stopping the reaction, most of the organic solvent is removed by rotary evaporation, the obtained eluent is filtered by a diaphragm pump to make the eluent pass through a neutral alumina chromatographic column to remove the steamed Br in the reaction system after the reaction at 70 ℃ after the reaction, unreacted substances (marked as monomer or auxiliary agent) are removed, and an intermediate product (F is obtained 1 -b-D 3 )；
(2) Dissolving 10g of the intermediate product prepared in the step (1) in 40g of toluene/ethanol (the mass ratio is 1:1) mixed organic solvent, filling the mixture into a 150mL eggplant-shaped bottle with a stirring magnet, flushing and sucking nitrogen for three times in a reaction system, placing the reaction system in an oil bath pot at 50 ℃, injecting 2.11g of benzyl chloride into the reaction system, carrying out heat preservation reaction for 24 hours, removing most of toluene and ethanol organic solvent in the reacted system by rotary evaporation at 70 ℃, and carrying out rotary evaporation to form a knotAdding 100mL of diethyl ether after bundling, precipitating the final product from toluene/ethanol organic solvent by utilizing solubility difference to obtain yellow flocculent product, repeatedly washing the product with diethyl ether for three times, filtering, and drying in a vacuum oven at 60 ℃ for 48 hours to obtain fluorine-containing macromolecular quaternary ammonium salt (PFDMS-PDMAEMA-BC, abbreviated as F) with two-block structure 1 -b-Q 5 )。
FIG. 1 is an infrared spectrum of the intermediate and product obtained in example 1 and comparative example 1 of the present invention; FIG. 2 shows the nuclear magnetic resonance hydrogen spectrum of the intermediate product obtained in example 1 of the present invention (for clarity of illustration in FIG. 2, intermediate F is shown 1 -b-D 3 A, b, a ', b', c, d, e, f in fig. 2 are labels for hydrogen in different positions); FIG. 2 shows the result of intermediate F 1 -b-D 3 Placed in CDCl 3 Measured in deuterated chloroform. FIG. 3 shows the nuclear magnetic resonance hydrogen spectrum of the product obtained in example 1 of the present invention (for clarity of illustration in FIG. 3, product F is shown 1 -b-Q 5 A, b, a ', b', c, d, e, f, g, h in fig. 3 are labels for hydrogen in different positions); FIG. 3 shows the result of converting the product F 1 -b-Q 5 Measured in deuterated methanol (the expression of b for hydrogen in different positions in fig. 2-3 means different from b in the structural formula of the prepared intermediate or product, the expression of b for hydrogen in different positions means hydrogen in different positions, and the expression of b in the structural formula of the intermediate or product means that the repeating units representing the m and n marks are in a two-block structure).
From the results shown in FIGS. 1 to 3, it can be seen that the structural formula of the product obtained in this example 1 is shown in formula 1.
Example 2: preparation of fluorine-containing macromolecular quaternary ammonium salt with two-block structure
A fluorine-containing macromolecular quaternary ammonium salt with a two-block structure and a structural formula shown in formula 1:
wherein m is 18 and n is 12.
Example 2 differs from example 1 in that 10g of trifluoroethyl methacrylate (noted DMAMMA) was added in example 2, the time for the first reaction was 4 hours, and the rest of the procedure was the same as in example 1. Obtain the fluorine-containing macromolecular quaternary ammonium salt (F for short) with a two-block structure 2 -b-Q 5 )。
Example 3: preparation of fluorine-containing macromolecular quaternary ammonium salt with two-block structure
A fluorine-containing macromolecular quaternary ammonium salt with a two-block structure and a structural formula shown in formula 1:
wherein m is 18 and n is 18.
Example 3 differs from example 1 in that example 3 was charged with 15g of trifluoroethyl methacrylate (noted DMAMMA), the time for the first reaction was 6 hours, and the rest of the procedure was the same as in example 1. Obtain the fluorine-containing macromolecular quaternary ammonium salt (F for short) with a two-block structure 3 -b-Q 5 )。
Example 4: preparation of fluorine-containing macromolecular quaternary ammonium salt with two-block structure
A fluorine-containing macromolecular quaternary ammonium salt with a two-block structure and a structural formula shown in formula 1:
wherein m is 18 and n is 30.
Example 4 differs from example 1 in that example 4 was charged with 25g of trifluoroethyl methacrylate (noted DMAMMA), the time for the first reaction was 10 hours, and the rest of the procedure was the same as in example 1. Obtain the fluorine-containing macromolecular quaternary ammonium salt (F for short) with a two-block structure 5 -b-Q 5 )。
Product performance test
1. Critical micelle concentration, zeta potential (electrokinetic potential), particle size distribution, migration ability in soil Performance test of the products prepared in examples, comparative examples
FIG. 4 is a graph showing critical micelle concentration of the products prepared in examples 1 to 4 and comparative example 1 according to the present invention; FIG. 5 is a Zeta potential diagram of the products of examples 1-4, comparative example 1, according to the present invention; FIG. 6 is a schematic diagram showing particle size distribution of the products obtained in examples 1 to 4 and comparative example 1 according to the present invention.
The products prepared in examples 1-4 in FIG. 4 all showed a tendency of gradually decreasing critical micelle concentration with increasing hydrophobicity.
The results of FIG. 5 illustrate that the Zeta potential of the products prepared in examples 1-4 increases with increasing hydrophobicity, and the Zeta potential of the micelles formed increases and the kinetic stability of the micelles increases.
FIG. 6 the particle size of the products of examples 1-4 is larger than that of the product of comparative example 1, and the particle size of the products of examples increases as the hydrophobic segment increases and the molecular weight increases.
2. Antibacterial effect test
The inhibition of the four bacteria/fungi by the products prepared in the examples was evaluated with reference to dodecyldimethylbenzyl ammonium chloride (benzalkonium chloride, noted BC), with escherichia coli (e.coli) as representative of gram-negative bacteria, staphylococcus albus (s.albus) as representative of gram-positive bacteria, candida albicans (c.album) as representative of pathogenic fungi, and fusarium oxysporum copal specialization type No. 4 physiological race (FOC 4) as representative of plant pathogenic fungi. The bacteriostasis experiment is briefly described as follows:
diluting the bacterial or fungal suspension in culture to 10 5 The CFU/mL concentration was then mixed with 100 μl of the bacterial or fungal suspension and 100 μl of the solution of the fluorine-containing macromolecular quaternary ammonium salt having a two-block structure prepared in the example with different concentrations, respectively, and the solution of the product prepared in comparative example 1 was transferred onto a 96-well plate. In addition, a medium was used as a control instead of the fluorine-containing macromolecular quaternary ammonium salt solution having a two-block structure, and then a 96-well plate was cultured at 28℃or 37℃for a suitable number of days, and then 10. Mu.L of a mass concentration per well was added to the 96-well plateA5% solution of 2,3, 5-triphenyltetrazolium chloride (TTC) was incubated at an appropriate temperature in the dark for 2 hours. The Minimum Inhibitory Concentration (MIC) value is the lowest concentration at which no bacterial or fungal growth is visible, i.e. the lowest concentration at which TTC is not stained red. 100. Mu.L of the mixture in 96-well plates at or above MIC values was then transferred to medium for 48 hours. The Minimum Fungicidal Concentration (MFC) or Minimum Bactericidal Concentration (MBC) value is then the lowest concentration at which less than 5 colony formations were observed, and the results are shown in fig. 7.
FIG. 7 is a graph showing the antibacterial effect of the products of examples 1 to 4 and comparative example 1 according to the present invention; as can be seen from FIG. 7 (the ordinate in FIG. 7 represents MIC or MFC (or MBC) values for the bacteria or fungi of the corresponding examples 1 to 4, comparative example 1), the products (F) obtained in the examples 1 to 4 of the present invention 1 -b-Q 5 、F 2 -b-Q 5 、F 3 -b-Q 5 、F 5 -b-Q 5 ) Has good inhibiting effect on Escherichia coli (E.coli), staphylococcus (S.albus), candida albicans (C.albicans) and FOC 4. Wherein F is 1 -b-Q 5 The minimum inhibitory concentration for FOC4 was comparable to Benzalkonium Chloride (BC), indicating F 1 -b-Q 5 Has good inhibition effect on FOC 4.
3. Test of interaction characteristics with soil
Adsorption performance test: the products obtained in examples 1-4 and comparative example 1, BC (benzalkonium chloride) and 0.01mol/L CaCl, respectively 2 Preparing 400mg/L of solution respectively, taking 100mL of solution into 250mL conical flasks, adding 1g of sterilized soil, sealing with a rubber plug, placing into a constant temperature shaking incubator, shaking at 25deg.C and 200r/min, placing into the constant temperature shaking incubator, starting at 0, taking 1mL of upper turbid liquid at 1.5, 2,3,5, 10, 15, 20, 30, 40, 60, 80, 100, 120, 160, 210, 300, 600 and 720min respectively, adding 1mL of deionized water at the same time, centrifuging in a 8000r/min centrifuge for 3min after the solution taking is completed, measuring absorbance of supernatant liquid by using an ultraviolet spectrophotometer, and calculating adsorption content of the products prepared in examples 1-4 in the soil according to standard curves and formulas, wherein the result is shown in FIG. 8.
FIG. 8 is a graph showing the saturated adsorption amount of the products prepared in examples 1 to 4 and comparative example 1 in soil; as can be seen from FIG. 8, the products prepared in examples 1-4 of the present invention are easy to adsorb in soil, and the saturated adsorption amount in soil increases with the increase of hydrophobicity (fluorine-containing structure corresponds to hydrophobicity), the molecular weight increases, and the molecular chain growth shows a continuous trend.
Migration performance test: the products prepared in examples 1-4 and BC (benzalkonium chloride) were prepared as 400mg/mL solutions, 100mL were added dropwise to leaching devices of different column thicknesses at a certain leaching rate (1-2 drops/second, corresponding to actual heavy rain level), deionized water was continuously added dropwise at the same rate after the solution was added dropwise, the leaching conditions were observed, column leaches were collected once every 100mL until 500mL was collected, 1mL of each solution was centrifuged at 5000r/min for 5 minutes after the collection of the leaches was completed, and the solution concentration was calculated by measuring absorbance with an ultraviolet spectrophotometer, as shown in FIG. 9.
The ordinate in fig. 9 is "percentage of leaching quaternary ammonium salt", the products prepared in examples and comparative examples are quaternary ammonium salts, and for simplicity of description, the ordinate is labeled "percentage of leaching quaternary ammonium salt", which indicates that the products prepared in examples 1 to 4 have poor migration ability in soil and are not easy to be leached by rainwater.
4. Toxicity test on zebra fish
Acute oral toxicity test of fish: refer to GB/T31270.12-2014 chemical pesticide environmental safety evaluation Experimental guidelines-part 12: acute toxicity test of fish, zebra fish experiments are carried out by adopting a semi-static test method, and the products (which can be called drugs to be tested) prepared in examples 1-4 and comparative example 1 and benzalkonium chloride have acute toxicity to zebra fish in aqueous solution, and the specific experimental operation steps are as follows: the method comprises the steps of determining the approximate toxicity concentration range of the drug to the zebra fish through a pre-experiment, accurately setting a series of gradient concentrations of the drug according to a certain interval, placing 7 zebra fish in each group of concentration gradients, changing the liquid medicine every day, recording the growth condition of the zebra fish at 96h under other experimental conditions which are the same as the domestication environment, and calculating the toxicity level (LC 50 ) The results are shown in Table 1.
Environmental toxicity test of drug-containing soil: 10g of fresh experimental soil, the products (which can be called as medicines to be detected) prepared in examples 1-4 and comparative example 1 and benzalkonium chloride are respectively prepared into 1000mL of medicine-containing soil suspension, a group of medicine-free soil suspension control groups are simultaneously arranged, the mixture is stirred by a glass rod and then is left for 12 hours, 7 zebra fish are put into each group of soil suspension after the upper layer of the solution is clear, the new soil suspension is replaced every day, other experimental conditions are the same as those of a domestication environment, the growth condition of the zebra fish is recorded when 96 hours, and the toxicity level of the medicines to the zebra fish after the medicines are adsorbed by the soil is calculated, wherein the result is shown in table 1.
Toxicity test of leaching solution of drug-containing soil: the experimental soil, the products (which can be called as medicines to be tested) prepared in examples 1-4 and comparative example 1 and benzalkonium chloride are stirred and mixed uniformly and then filled into a soil column, deionized water is dripped into a soil column leaching device according to a certain leaching speed, medicines in the soil column are washed to simulate the scouring condition of rainwater on the medicines in the soil in reality, leaching conditions of the soil column are observed, leaching liquid medicine of 100mg/L, 50mg/L, 20mg/L and 10mg/L is collected, then zebra fish toxicity experiments are carried out, and the influence of the medicines on the toxicity of the zebra fish along with the infiltration of the rainwater into underground water in actual production application is simulated, wherein the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the products prepared in examples 1-4 of the present invention exhibited low toxicity characteristics after interaction with soil.
4. Impact test on soil microbial diversity
1g of fresh soil and the products prepared in the example 1 and the comparative example 1 and Benzalkonium Chloride (BC) medicines are weighed and put into a sterile centrifuge tube, a certain amount of sterile water is added to enable the water-soil mass ratio of a soil solution system to be 1:1, a group of deionized water control groups (CK) is arranged, the prepared soil solution system is placed into a constant temperature shake incubator to be cultured at 28 ℃ and 200rpm for shake culture for 2 days, 0.5mL of the upper solution is placed into a 1mL centrifuge tube to be centrifuged for 3 minutes after the culture is completed, and then a series of dilutions are carried out on the supernatant. 100 mu L of the diluted culture solution is respectively taken by a pipetting gun and coated on a prepared Bengalia red culture medium, a beef extract peptone culture medium and a modified Gao's culture medium to be used for culturing fungi, bacteria and actinomycetes in soil respectively, the culture medium is placed in a constant temperature incubator at 28 ℃ for a certain period of time, colonies of the fungi, bacteria and actinomycetes growing in the flat culture medium are counted, and the colony numbers in the soil system without adding the products prepared in example 1 and comparative example 1 are compared, so that the influence of the products prepared in example 1 and comparative example 1 on microorganisms in the soil system is evaluated.
FIG. 10 is a graph showing the effect of the products of example 1 and comparative example 1 of the present invention on the diversity of soil microorganisms; the effects of the products of example 1 and comparative example 1 and benzalkonium chloride on the number of bacteria, actinomycetes and fungi are shown in FIG. 10 (a), (b) and (c), respectively. As can be seen from fig. 10, benzalkonium Chloride (BC) completely inhibited and killed the microorganisms in the soil almost indiscriminately, while the product prepared in example 1 of the present invention had less effect on the abundance of typical microbial communities in the soil, wherein the abundance of fungal communities decreased and the abundance of bacterial and actinomycete communities increased, suggesting that the soil to which the product prepared in example 1 was applied was more favorable for banana plant planting.
5. Potting test
In the potting test process, sterile non-drug, sterile drug test groups are set, and 5 repeated groups are repeated under each concentration, and the specific operation is as follows: adding 10g matrix soil into 100 experimental soil samples, mixing 90 parts of the experimental soil samples with a certain concentration of the solution of the product (which can be called medicine) prepared in comparative example 1 and example 1, stirring, filling into a container with an upper caliber of 12cm and a lower caliber of 10cm, and height10 parts of each concentration component (5 pots were inoculated for each concentration when FOC4 was inoculated later) was placed in an experimental flowerpot of 10cm, and the remaining 10 groups of experimental soil samples were uniformly mixed with 150mL of deionized water to prepare a control group (designated CK) containing no drug. Transplanting banana seedlings with consistent root systems and leaves growing to the prepared potting soil environment, culturing for 14 days, and inoculating 2X 10 by taking 5 pots respectively under each concentration gradient of a bacterial non-drug group and a bacterial drug group after the banana seedlings adapt to the growing environment 6 FOC4 spore fungus suspension per gram of soil was continuously cultured for a certain number of days and the infection of banana seedlings was counted, and the results are shown in Table 2.
TABLE 2
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Table 2 shows the effect of the products of comparative example 1 and example 1 on banana seedling growth parameters, EC 50s Represents the drug concentration at which the product of comparative example 1, example 1 inhibited FOC4 in the soil to 50%. The results in Table 2 show that: under the experimental condition of not inoculating FOC4, the products prepared in comparative example 1 and example 1 have little influence on banana seedling growth; after inoculating FOC4, the product prepared in example 1 greatly reduces the concentration of FOC4 in soil through interaction with bacteria in the soil, the disease condition of banana seedlings is improved, and the banana seedlings grow obviously along with the increase of the content of applied medicines, when the application amount of the product prepared in example 1 reaches 4 times EC 50s I.e. about 1.2mg/g soil, the disease index of banana seedlings is reduced to a first level (the disease degree is about 11%), which shows that the product prepared in the example 1 has positive control effect in the banana wilt disease control process.
Claims (3)
1. The application of the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure in preventing and treating banana vascular wilt is characterized in that the preparation method of the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure comprises the following steps:
(1) Mixing dimethylaminoethyl methacrylate, ethyl 2-bromoisobutyrate, a catalyst, an auxiliary agent and an organic solvent, carrying out a first reaction in an inert gas atmosphere, adding trifluoroethyl methacrylate, and carrying out a second reaction to obtain an intermediate product;
(2) Mixing the intermediate product prepared in the step (1), benzyl chloride and an organic solvent, and reacting in an inert gas atmosphere to prepare the fluorine-containing macromolecular quaternary ammonium salt with the two-block structure;
in the step (1), the mass ratio of the trifluoroethyl methacrylate to the dimethylaminoethyl methacrylate is 1-5:3.
2. the method according to claim 1, wherein in the step (1), the temperature of the first reaction is 45 to 55℃and the reaction time is 1 to 10 hours.
3. The process according to claim 1, wherein in step (1), the temperature of the second reaction is 45 to 55℃and the reaction time is 4 to 8 hours.
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