CN114957542B - Fluorine-containing macromolecular quaternary ammonium salt with random structure, and preparation method and application thereof - Google Patents
Fluorine-containing macromolecular quaternary ammonium salt with random structure, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114957542B CN114957542B CN202210337162.9A CN202210337162A CN114957542B CN 114957542 B CN114957542 B CN 114957542B CN 202210337162 A CN202210337162 A CN 202210337162A CN 114957542 B CN114957542 B CN 114957542B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- quaternary ammonium
- ammonium salt
- random structure
- soil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- General Chemical & Material Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of sterilization, and discloses a fluorine-containing macromolecular quaternary ammonium salt with a random structure, and a preparation method and application thereof. The fluorine-containing macromolecular quaternary ammonium salt with a random structure and a structural general formula shown in the formula 1:wherein m and n are both positive integers, and m: n= (14-22): (4-36). The fluorine-containing macromolecular quaternary ammonium salt with a random structure has good antibacterial effect, particularly has an inhibition effect on FOC4 spores in soil, reduces the influence on the diversity of soil microorganisms, and provides a foundation for the practical application of fluorine-containing alkyl macromolecular quaternary ammonium salt in the chemical control of plant fungal diseases such as banana wilt and the like.
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 random structure, and a preparation method and application thereof.
Background
Banana vascular bundle is destroyed to cause the death of plants, the pathogenic bacteria of the banana vascular bundle is Fusarium oxysporum Gouba specialization Fusarium oxysporium f.sp.cube (FOC for short), physiological species are more differentiated, and the damage of No. 4 species (FOC 4 for short) is the largest, the distribution is the widest, and the banana vascular bundle has become one of the largest diseases which damage the banana planting industry worldwide. Because the pathogenic bacteria have strong saprophytic capability and can survive in soil for a long time in the form of dormant spores, the occurrence of banana vascular wilt is positively correlated with the quantity of pathogenic bacteria FOC4 in the soil to a certain extent, and therefore, reducing the quantity of pathogenic bacteria in the soil is an important method for preventing and treating banana vascular wilt.
In practice, two main methods are used for chemical control: 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 new bactericidal substance which has good killing effect on FOC4 in soil and does not damage the soil microbial ecosystem, thereby having important significance for preventing and treating 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 random structure, the preparation method and the application thereof are provided, the fluorine-containing macromolecular quaternary ammonium salt with the random 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 provide a foundation for the practical application of the fluorine-containing macromolecular quaternary ammonium salt in the chemical control of plant fungal diseases such as banana wilt and the like.
The invention is characterized in that: according to the invention, the fluorine-containing alkyl is introduced into the quaternary ammonium salt, so that on one hand, the quaternary ammonium salt has lower surface tension and excellent water-soluble stability, and on the other hand, the fluorine-containing chain segment is introduced into the quaternary ammonium salt, so that the hydrophilic-hydrophobic structure and the proportion can be changed, the antibacterial activity of the quaternary ammonium salt can be improved, the inhibition effect of the fluorine-containing alkyl macromolecular quaternary ammonium salt on FOC4 spores in soil can be improved, the influence on the diversity of soil microorganisms can be reduced, and a foundation is provided for the practical application of the fluorine-containing alkyl macromolecular quaternary ammonium salt in the chemical control of plant fungal diseases such as banana wilt and the like.
In a first aspect the present invention provides a fluorine-containing macromolecular quaternary ammonium salt having a random structure.
Specifically, the fluorine-containing macromolecular quaternary ammonium salt with a random structure and a structural general formula shown in formula 1:
wherein m and n are both positive integers, and m: n= (14-22): (4-36).
Further preferably, the m: n=18: (4-36); preferably 18: (6-30).
Preferably, m is a positive integer between 14 and 22, and n is a positive integer between 4 and 36.
Preferably, m is an even number between 14 and 22, and n is an even number between 4 and 36.
Preferably, m is 18 and n is 6, 12, 18 or 30.
Preferably, the molecular weight of the fluorine-containing macromolecular quaternary ammonium salt with a random structure is 5-20kDa, preferably 5-12kDa.
In a second aspect, the present invention provides a process for preparing a fluorine-containing macromolecular quaternary ammonium salt having a random structure.
Specifically, the preparation method of the fluorine-containing macromolecular quaternary ammonium salt with a random structure comprises the following steps:
(1) Trifluoroethyl methacrylate, dimethylaminoethyl methacrylate, bromoester, a catalyst, an auxiliary agent and an organic solvent are mixed and reacted in an inert gas atmosphere to prepare 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 a random 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), the reaction is stopped after the reaction is performed for a period of time and then 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 amount of the organic solvent is 3-10 times, preferably 4-8 times of the total volume of the trifluoroethyl methacrylate, the dimethylaminoethyl 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 reaction is 45-55 ℃ and the reaction time is 5-14 hours; preferably, the temperature of the reaction is 48-50 ℃ and the reaction time is 5-14 hours.
Preferably, in step (1), the trifluoroethyl methacrylate and dimethylaminoethyl methacrylate are distilled under reduced pressure before use to remove 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 random structure, pouring out supernatant, repeating for 2-5 times, and then placing into a vacuum oven at 40-50 ℃ for drying to obtain the purified fluorine-containing macromolecular quaternary ammonium salt with random 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 random structure.
The invention relates to an application of fluorine-containing macromolecular quaternary ammonium salt with a random 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 random structure described above.
Compared with the prior art, the invention has the following beneficial effects:
(1) The fluorine-containing macromolecular quaternary ammonium salt with a random 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 provides a basis for the practical application of fluorine-containing macromolecular quaternary ammonium salt in the chemical control of plant fungal diseases such as banana wilt and the like. The fluorine-containing macromolecular quaternary ammonium salt with the random 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 random structure and a structural general formula shown in the formula 1:
wherein m is 18, n is 6, 12, 18 or 30.
The molecular weight of the fluorine-containing macromolecular quaternary ammonium salt with a random structure is 5-20kDa.
The preparation method of the fluorine-containing macromolecular quaternary ammonium salt with the random structure comprises the following steps:
(1) Trifluoroethyl methacrylate, dimethylaminoethyl methacrylate, bromoester, a catalyst, an auxiliary agent and an organic solvent are mixed and reacted in an inert gas atmosphere to prepare 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 (nitrogen) atmosphere to prepare the fluorine-containing macromolecular quaternary ammonium salt with a random 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 reaction is 45-55 ℃, and the reaction time is 5-14 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 ℃ after the reaction by a diaphragm pump filtration, unreacted substances (marked as MAEMA, the monomer or the auxiliary agent) are removed, and an intermediate product (marked as MAEMA, which is abbreviated as D) 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 random structure
The fluorine-containing macromolecular quaternary ammonium salt with a random structure and shown in the structural formula 1:
wherein m is 18 and n is 6.
The preparation method of the fluorine-containing macromolecular quaternary ammonium salt with the random 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 to mix the organic solvent, 1.3g of N, N' -pentamethyldivinyl triamine (PMDETA) and 0.975g of ethyl 2-bromoisobutyrate (EtBrib) are added to the reaction system, the reaction system is filled with nitrogen three times and stirred in an oil bath pot at 50 ℃, then 5g of trifluoroethyl methacrylate (marked as DMAMMA) and 15g of dimethylaminoethyl methacrylate (marked as DMAEMA) are added, the reaction is stopped by exposing to air after 6.5 hours at 50 ℃, most of the organic solvent is removed by rotary evaporation, the system after the reaction is dissolved by 100mL of acetone, the CuBr in the system after the reaction is removed by a neutral alumina chromatographic column through membrane filtration, the obtained eluent is rotary evaporated at 70 ℃ to remove unreacted substances (marked as monomers or auxiliaries), and an intermediate product (marked as F) is obtained 1 -co-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 stirring magneton, flushing and sucking nitrogen for three times in a reaction system, placing the mixture into 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 ℃, adding 100mL of diethyl ether after the rotary evaporation, and precipitating the final product from the toluene/ethanol organic solvent by utilizing the solubility differenceObtaining yellow flocculent product, repeatedly washing the product with diethyl ether for three times, filtering, and drying in vacuum oven at 60deg.C for 48 hr to obtain fluorine-containing macromolecular quaternary ammonium salt (PFDMS-PDMAEMA-BC, abbreviated as F) with random structure 1 -co-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 -co-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 -co-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 -co-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 -co-Q 5 Measured in deuterated methanol.
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 random structure
The fluorine-containing macromolecular quaternary ammonium salt with a random structure and shown in the structural formula 1:
wherein m is 18 and n is 12.
Example 2 differs from example 1 in that 10g of trifluoroethyl methacrylate (denoted as DMAMMA) and 15g of dimethylaminoethyl methacrylate (denoted as DMAEMA) were added in example 2, the reaction time in step (1) was 8 hours, and the rest of the procedure was the same as in example 1. Obtaining fluorine-containing macromolecular quaternary ammonium salt (F for short) with random structure 2 -co-Q 5 )。
Example 3: preparation of fluorine-containing macromolecular quaternary ammonium salt with random structure
The fluorine-containing macromolecular quaternary ammonium salt with a random structure and shown in the structural 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 (denoted as DMAMMA), 15g of dimethylaminoethyl methacrylate (denoted as DMAEMA), the reaction time in step (1) was 10 hours, and the rest of the procedure was the same as in example 1. Obtaining fluorine-containing macromolecular quaternary ammonium salt (F for short) with random structure 3 -co-Q 5 )。
Example 4: preparation of fluorine-containing macromolecular quaternary ammonium salt with random structure
The fluorine-containing macromolecular quaternary ammonium salt with a random structure and shown in the structural formula 1:
wherein m is 18 and n is 30.
Example 3 differs from example 1 in that example 3 was charged with 25g of trifluoroethyl methacrylate (denoted as DMAMMA), 15g of dimethylaminoethyl methacrylate (denoted as DMAEMA), the reaction time in step (1) was 14 hours, and the rest of the procedure was the same as in example 1. Obtaining fluorine-containing macromolecular quaternary ammonium salt (F for short) with random structure 5 -co-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 1-4 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 synthesized in the examples was evaluated with reference to dodecyldimethylbenzyl ammonium chloride (benzalkonium chloride, noted BC), escherichia coli (e.coli) as a gram-negative bacterial representative, staphylococcus albus(s) as a gram-positive bacterial representative, candida albicans (c.album) as a pathogenic fungus representative, fusarium oxysporum copal specialization type No. 4 physiological race (FOC 4) as a representative of plant pathogenic fungi. The bacteriostasis experiment is briefly described as follows:
the bacterial or fungal suspension cultivated in the medium is diluted to 10 5 The CFU/mL concentration was then mixed with 100. Mu.L of the bacterial or fungal suspension and 100. Mu.L of the solution of the random-structured fluorine-containing macromolecular quaternary ammonium salt prepared in the example, the solution of the product prepared in comparative example 1, respectively, and transferred to 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 random structure, and then a 96-well plate was cultured at 28 ℃ (fungi) or 37 ℃ (bacteria) for a suitable number of days, and then 10 μl of a 5% by mass 2,3, 5-triphenyltetrazolium chloride (TTC) solution was added to each well of the 96-well plate, and cultured at a suitable temperature in the absence of light 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. Then the cells are placed in 96-well plates at or above MIC valuesIs transferred to a 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 -co-Q 5 、F 2 -co-Q 5 、F 3 -co-Q 5 、F 5 -co-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 -co-Q 5 The minimum inhibitory concentration for FOC4 was comparable to Benzalkonium Chloride (BC), indicating F 1 -co-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 tested) prepared in metering 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 soil suspension control groups are stirred by a glass rod and then are stood for 12 hours, 7 zebra fish are placed in 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 results are 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 and comparative example 1 of the present invention exhibited low toxicity characteristics after interacting 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: 10g of matrix soil is added into 100 experimental soil samples, 90 parts of the matrix soil samples are taken and mixed with the product (which can be called a medicine) solution prepared in comparative example 1 and example 1 with a certain concentration, the mixture is uniformly stirred and then filled into an experimental flowerpot with an upper caliber of 12cm, a lower caliber of 10cm and a height of 10cm, 10 parts of each concentration component (each concentration is inoculated with 5 pots when FOC4 is inoculated subsequently) are respectively filled into the experimental flowerpot, and the rest 10 groups of experimental soil samples are uniformly mixed with 150mL of deionized water to be set as a control group (which is called CK) without the medicine. Selecting root system and leaf growth conditionTransplanting banana seedlings to the prepared potting soil environment, culturing for 14 days, inoculating 5 pots of banana seedlings to 2×10 seedlings under each concentration gradient of the bacteria-free and bacteria-free groups after the banana seedlings adapt to the growth 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
/>
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 (8)
1. The application of the fluorine-containing macromolecular quaternary ammonium salt with a random structure in preventing and treating banana vascular wilt is characterized in that the structural general formula of the fluorine-containing macromolecular quaternary ammonium salt with a random structure is shown in formula 1:
wherein m and n are both positive integers, and m: n= (14-22): (4-36).
2. The use according to claim 1, wherein m: n = 18: (4-36).
3. The use according to claim 1, wherein m is a positive integer between 14 and 22 and n is a positive integer between 4 and 36.
4. The use according to claim 1, wherein m is 18 and n is 6, 12, 18 or 30.
5. The use according to claim 1, wherein the molecular weight of the fluorine-containing macromolecular quaternary ammonium salt having a random structure is 5-20kDa.
6. The use according to any one of claims 1 to 5, characterized in that the process for the preparation of the fluorine-containing macromolecular quaternary ammonium salt having a random structure comprises the following steps:
(1) Trifluoroethyl methacrylate, dimethylaminoethyl methacrylate, bromoester, a catalyst, an auxiliary agent and an organic solvent are mixed and reacted in an inert gas atmosphere to prepare 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 a random structure.
7. The use according to claim 6, wherein in step (1), the catalyst is a cuprous salt; the bromo ester is ethyl 2-bromoisobutyrate; the auxiliary agent comprises N, N, N' -pentamethyldivinyl triamine.
8. The use according to claim 6, wherein in step (1), the temperature of the reaction is 45-55 ℃ and the time of the reaction is 5-14 hours; in the step (2), the temperature of the reaction is 45-55 ℃ and the reaction time is 20-50 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210337162.9A CN114957542B (en) | 2022-03-31 | 2022-03-31 | Fluorine-containing macromolecular quaternary ammonium salt with random structure, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210337162.9A CN114957542B (en) | 2022-03-31 | 2022-03-31 | Fluorine-containing macromolecular quaternary ammonium salt with random structure, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114957542A CN114957542A (en) | 2022-08-30 |
| CN114957542B true CN114957542B (en) | 2023-09-26 |
Family
ID=82976576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210337162.9A Active CN114957542B (en) | 2022-03-31 | 2022-03-31 | Fluorine-containing macromolecular quaternary ammonium salt with random structure, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114957542B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06239941A (en) * | 1993-02-15 | 1994-08-30 | Shikishima Boseki Kk | Antimicrobial polymer |
| CN102122720A (en) * | 2011-01-25 | 2011-07-13 | 厦门大学 | Fluorine-containing acrylate polymer anion exchange membrane and preparation method thereof |
| JP2017214346A (en) * | 2015-09-30 | 2017-12-07 | 株式会社日本触媒 | Antibacterial agent |
| CN108384293A (en) * | 2018-03-22 | 2018-08-10 | 天津大学 | A kind of antifog/anti-fog coatings and preparation method thereof based on cationic polyelectrolyte copolymer |
| CN113444211A (en) * | 2021-06-11 | 2021-09-28 | 湖北大学 | Preparation method and application of PISA-based antibacterial polymer nanoparticles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090256102A1 (en) * | 2005-07-14 | 2009-10-15 | Daikin Industries, Ltd. | Fluoropolymer and soil remover |
-
2022
- 2022-03-31 CN CN202210337162.9A patent/CN114957542B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06239941A (en) * | 1993-02-15 | 1994-08-30 | Shikishima Boseki Kk | Antimicrobial polymer |
| CN102122720A (en) * | 2011-01-25 | 2011-07-13 | 厦门大学 | Fluorine-containing acrylate polymer anion exchange membrane and preparation method thereof |
| JP2017214346A (en) * | 2015-09-30 | 2017-12-07 | 株式会社日本触媒 | Antibacterial agent |
| CN108384293A (en) * | 2018-03-22 | 2018-08-10 | 天津大学 | A kind of antifog/anti-fog coatings and preparation method thereof based on cationic polyelectrolyte copolymer |
| CN113444211A (en) * | 2021-06-11 | 2021-09-28 | 湖北大学 | Preparation method and application of PISA-based antibacterial polymer nanoparticles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114957542A (en) | 2022-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106588772B (en) | Heavy turpentine longifolene derivative and preparation and application thereof | |
| CN104498399B (en) | Rhodopseudomonas palustris bacterial strain, biocontrol agent and its preparation method and application | |
| CN104403978B (en) | Rhodopseudomonas palustris bacterial strain, the preparation method of microbial inoculum and microbial inoculum, extracellular protein and its extracting method and application | |
| CN108642018B (en) | Lytic bacteriophage capable of preventing and controlling tomato bacterial wilt and application thereof | |
| DE3639504A1 (en) | PEST CONTROL AND PLANT TREATMENT AGENTS | |
| CN108641087B (en) | Diblock macromolecular quaternary ammonium salt containing polysiloxane chain segment and preparation method and application thereof | |
| CN106834130A (en) | One plant of Strain of Beauveria bassiana and its application to grub larva highly pathogenicity | |
| CN106750056A (en) | A kind of triclosan amphipathic nature polyalcohol nano-particle and its preparation method and antibacterial applications | |
| CN110437374A (en) | A kind of amphipathic cationic polymer of quaternary ammonium salt and its application | |
| CN104357338A (en) | Fermentation method and applications of paecilomyce lilacinus microsclerotia | |
| CN110724260B (en) | Super-hydrophilic main chain type quaternary ammonium salt and preparation method and application thereof | |
| CN108719331A (en) | A kind of combination microbial inoculum and preparation method thereof of control Ralstonia solanacearum Population, application | |
| CN114957542B (en) | Fluorine-containing macromolecular quaternary ammonium salt with random structure, and preparation method and application thereof | |
| CN109295122B (en) | Preparation method and application of endophytic fungus Chaetomium sp secondary metabolite of Eucalyptus globulus Labill | |
| CN114773504B (en) | Fluorine-containing macromolecular quaternary ammonium salt with two-block structure, and preparation method and application thereof | |
| CN108513982B (en) | Application of AHL molecule as chemical pesticide sterilization synergist in disease control caused by ralstonia solanacearum | |
| CN110810442B (en) | Rapeseed seed meal composition for inhibiting pathogenicity of ralstonia solanacearum and application thereof | |
| CN108715817B (en) | Streptomyces albidoflavus strain and application thereof | |
| CN108752544B (en) | Fluorescence labeling macromolecular quaternary ammonium salt and preparation method and application thereof | |
| CN114380782B (en) | Compound, preparation method and application of bactericide in preventing and treating rubber anthracnose | |
| CN113817625B (en) | Flavobacterium acidophilus and application thereof in improvement of saline-alkali soil | |
| CN101790995A (en) | Biological preparation for prevention and treatment of peanut root-knot nematode, and preparation method and applications thereof | |
| CN116284562A (en) | Poly (acrylamide-methacrylamide primary amine salt) with random structure, and preparation method and application thereof | |
| CN106434415B (en) | A method of utilizing Triadimenol in novel microorganism bacterial strain degradation soil | |
| CN114835852A (en) | Polyacrylamide quaternary ammonium salt with random structure and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |