CN114931139B - Plant disease control composition containing fluopicolide and metalaxyl-M and application thereof - Google Patents
Plant disease control composition containing fluopicolide and metalaxyl-M and application thereof Download PDFInfo
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- CN114931139B CN114931139B CN202210887924.2A CN202210887924A CN114931139B CN 114931139 B CN114931139 B CN 114931139B CN 202210887924 A CN202210887924 A CN 202210887924A CN 114931139 B CN114931139 B CN 114931139B
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
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- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- 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
- A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/46—N-acyl derivatives
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
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- 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
Abstract
The invention discloses a plant disease control composition containing fluopicolide and metalaxyl-M and application thereof, wherein the plant disease control composition comprises the following components: fluopicolide, metalaxyl-M, a dispersing agent, an auxiliary agent, an antifreeze agent, a wetting agent, xanthan gum, a defoaming agent and water. The auxiliary agent is prepared by reacting acrylic acid-2-hydroxyethyl ester, cyclohexyl methacrylate, D-glucosamine sodium sulfate with styrene and linoleic acid to generate a high-molecular surfactant mixture, and then performing aftertreatment by adopting methanol, ammonium persulfate and sodium bisulfate. Compared with the prior art, the plant disease control composition containing fluopicolide and metalaxyl-M prepared by the invention can generate synergistic effect, reduce the solvent volatilization rate, keep good wetting dispersibility and suspension property, and obviously improve the control effect on low-grade fungal diseases.
Description
Technical Field
The invention relates to the technical field of pesticide compositions, in particular to a plant disease control composition containing fluopicolide and metalaxyl-M and application thereof.
Background
Pesticide suspending agents generally refer to aqueous suspending agents, which are viscous suspension preparations formed by using water as a dispersion medium. Compared with other formulations, the preparation has certain advantages in drug effect, safety and economy, can reduce the harm of organic solvents, and has the advantages of convenient use, simple process, good dispersibility, good and lasting drug effect. The appearance of the suspending agent improves the processing technology of the pesticide preparation to a new level, and the suspending agent is an environment-friendly 'epoch-making' new formulation which is consistently recognized by the pesticide industry at home and abroad and is rapidly developed in recent decades.
However, the suspending agent belongs to a multi-component heterogeneous coarse dispersion system, has dynamic and thermodynamic instability, and is particularly characterized in that the phenomena of particle agglomeration, sedimentation and water separation, agglomeration and thickening can occur in the process of development, storage and use. An effective method of improving the stability of the suspension against coalescence is to add suitable polymeric auxiliaries. The auxiliary agent mainly plays a role by adsorbing on the surface of a dispersion particle, the adsorption between the original drug particles and the auxiliary agent can be divided into two types of chemical adsorption and physical adsorption, the adsorption formed by chemical bonds between the molecules of the auxiliary agent and the interfaces of the original drug particles is chemical adsorption, and the adsorption formed by van der waals force, hydrogen bonds and the like is physical adsorption. Usually, the chemical adsorption is relatively stable and is not easy to desorb, while the physical adsorption is greatly influenced by factors such as temperature, external force and the like and is easy to desorb, and the chemical adsorption belongs to unstable adsorption. The suitable polymer auxiliary agent can improve the stability of a suspension system mainly because the interfacial energy of the particles can be reduced, thereby reducing the spontaneous agglomeration of the particles; forming an electric double layer to generate electrostatic repulsion between particles to prevent the particles from coalescing; the polymer auxiliary agent can also form a protective layer after being adsorbed on the surface of the original drug particles, and the particles are kept in a dispersed state through the steric hindrance effect. However, these methods have limitations. When the density difference between the dispersed particles and water is very large, the density difference of the system is difficult to change by adding the high molecular auxiliary agent; the particle settling rate can be slowed to some extent by increasing the viscosity of the system, but too high a viscosity of the system affects the pourability of the system.
The invention patent CN105409976B discloses a bactericidal composition containing efficient metalaxyl-M and flumorph, and the effective components of the bactericidal composition are binary complex of the efficient metalaxyl-M and the flumorph. The bactericidal composition comprises the following components in parts by mass, wherein the mass ratio of the efficient metalaxyl-M to the flumorph is 1-50-1, the mass parts of effective components of the efficient metalaxyl-M and the flumorph in the preparation are 1-80%, and the balance is auxiliary components allowed to be used and accepted in pesticides. Is mainly used for preventing and treating plant gray mold, peronospora and phytophthora. However, the bactericidal composition prepared by the invention has the defects of easy volatilization of solvent, poor compatibility with plants, easy precipitation of functional medicament to form crystal and poor effect on low-grade fungi.
Disclosure of Invention
In view of the defects of poor compatibility, easy precipitation of functional medicaments and low pesticide effect of the suspension pesticide in the prior art, the invention aims to provide the plant disease control composition which has good wetting dispersibility and suspension property and can obviously improve the control effect on low fungal diseases.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a plant disease control composition containing fluopicolide and metalaxyl-M comprises the following components: fluopicolide, metalaxyl-M, a dispersing agent, an auxiliary agent, an antifreeze agent, a wetting agent, xanthan gum, a defoaming agent and water.
Preferably, the plant disease control composition containing fluopicolide and metalaxyl-M comprises the following components in percentage by weight: 3~8% fluopicolide, 8 to 12% metalaxyl, 10 to 25% dispersing agent, 10 to 30% auxiliary agent, 3~8% antifreeze agent, 3~6% wetting agent, 0.1 to 0.8% xanthan gum, 0.1 to 0.5% defoaming agent and the balance of water.
Further preferably, the plant disease control composition containing fluopicolide and metalaxyl-M comprises the following components in percentage by weight: 5% of fluopicolide, 10% of metalaxyl-M, 10% of dispersant, 10% of auxiliary agent, 5% of antifreeze agent, 4% of wetting agent, 0.2% of xanthan gum, 0.3% of defoaming agent and the balance of water.
The plant disease control composition containing fluopicolide and metalaxyl-M is prepared by the following method: weighing fluopicolide, metalaxyl-M, an auxiliary agent, a dispersing agent and water, mixing, stirring for 10 to 30min at 50 to 80r/min, adding an antifreeze agent, a wetting agent, xanthan gum and a defoaming agent, uniformly mixing by high-speed shearing, sanding for 2 to 3h, and uniformly stirring to obtain the plant disease control composition containing fluopicolide and metalaxyl-M.
The preparation method of the assistant comprises the following steps of:
step 1, adding 3~8 parts of styrene, 8 to 15 parts of linoleic acid, 0.5 to 2 parts of 2-hydroxyethyl acrylate, 2~6 parts of cyclohexyl methacrylate and 0.5 to 2 parts of D-glucosamine sodium sulfate into 120 to 180 parts of water to prepare a mixed solution, then adding 0.1 to 0.5 part of azodiisobutyronitrile, adjusting the pH to 9 to 10 by adopting a 20 to 32wt% sodium hydroxide aqueous solution, and reacting for 1 to 3h at 50 to 70 ℃ to obtain a high-molecular surfactant;
and 2, adding 15-30 parts of methanol, 4~8 parts of ammonium persulfate and 4~8 parts of sodium bisulfate into 200-300 parts of water, then adding the high molecular surfactant prepared in the step 1, carrying out oil bath reaction for 3-8h at the reaction temperature of 60-90 ℃, cooling to room temperature, neutralizing with 20-32wt% of sodium hydroxide aqueous solution until the pH value is 7~8, then drying to obtain a crude product, dissolving the crude product in deionized water, dialyzing, collecting a high molecular compound, and freeze-drying to obtain the auxiliary agent.
Preferably, the dialysis is performed by adopting a dialysis membrane with the molecular mass of 1000Da, the deionized water is replaced every 2 to 4 hours until the conductivity of the dialysate is equal to that of the deionized water, and the high molecular compound is collected.
Preferably, the dispersing agent is fatty alcohol-polyoxyethylene ether-9.
Preferably, the antifreeze is at least one of ethylene glycol, propylene glycol and glycerol.
Preferably, the defoaming agent is at least one of silicone and polydimethylsiloxane.
Preferably, the wetting agent is at least one of sodium alkyl benzene sulfonate, sodium alkyl naphthalene sulfonate, polyoxyethylene lauryl ether and sodium lauryl sulfate.
The invention also provides the application of the plant disease control composition containing fluopicolide and metalaxyl-M in controlling plant diseases; the plant diseases are diseases caused by lower fungi.
Fluopyram is a novel benzamide bactericide developed by Germany Bayer crop science company, has high biological activity on oomycetes, and can enable ghost-like proteins on the cell membranes of the oomycetes to generate the delocalization from the cell membranes to cytoplasm, thereby destroying the cell structures and expressing bactericidal activity.
metalaxyl-M is an amide bactericide which is developed by Switzerland in 1977 and takes a benzene ring as a matrix, and is characterized by having protection, treatment and systemic activity, namely a bactericide with higher systemic activity, the action mechanism of the bactericide is similar to that of other bactericides of the same type, and a protein compound II (succinate dehydrogenase) capable of influencing the respiratory electron transfer chain of pathogenic bacteria can be used for achieving the bacteriostatic action, is commonly used for stem and leaf treatment, seed treatment and soil treatment, and is commonly used for preventing and treating downy mildew, epidemic disease, potato late blight and the like of melons, fruits, vegetables and the like.
The mixed pesticide of fluopicolide and metalaxyl-M has poor compatibility on the surface of plants, the prepared suspending agent has a less ideal effect than missible oil, and the solvent is easy to volatilize, so that functional substances form crystals and are not easy to absorb. Therefore, the invention takes styrene and linoleic acid as raw materials, takes acrylic acid-2-hydroxyethyl ester, cyclohexyl methacrylate and sodium vinylsulfonate as monomers, and prepares the auxiliary agent. The volatilization of the solvent is reduced, a good contact absorption effect can be formed between the solvent and crops, and the curative effect on plant diseases caused by low-grade fungi is enhanced.
The adsorption of pesticide molecules on the plant interface is a diffusion control process in a short time, the desorption effect is very small, and the adsorbed macromolecules have no interaction. In addition, the highly hydrophilic and charged substituents of the adjuvant can enhance the adsorption performance between plants and pesticides by increasing the molecular area and reducing the surface adhesion. Benzene rings in the styrene can reduce the polarity of the auxiliary agent and are more stable in the using process. And the density difference between the prepared auxiliary agent and water is small, so that the agglomeration degree of the pesticide composition in the water can be reduced. Therefore, the pesticide composition prepared after the addition of the auxiliary agent has small density difference with water and shows good stability and hydrophilicity.
According to the invention, acrylic acid-2-hydroxyethyl ester, cyclohexyl methacrylate, D-glucosamine sodium sulfate, styrene and linoleic acid react to generate a high molecular surfactant mixture, then methanol, ammonium persulfate and sodium bisulfate are adopted for post-treatment to prepare the assistant, the assistant is added into the pesticide composition to reduce the surface energy among functional particles, and as sulfate ions in the assistant provide electrostatic repulsion, the density of the surfactant molecules at the interface is lower, and the stacking density of the molecules at the gas-liquid interface is lower, so that the surfactant has better surface activity, and dispersed particles can generate electrostatic repulsion due to the charge. And a compact adsorption layer with a complex spatial structure can be formed on the particles, and the particles are adsorbed on the surface of the medicament to form a polymer protective film, so that the further approach and agglomeration of the medicament are prevented, the volatilization of a solvent is reduced, and the stability of the system is increased, thereby generating a steric hindrance effect to prevent the particles from being agglomerated and becoming large, and achieving the purpose of improving the medicament effect.
Compared with the prior art, the invention has the beneficial effects that:
1) The mixing of fluopicolide and metalaxyl-M can obviously improve the control effect on plant diseases caused by low-grade fungi;
2) The high-molecular surfactant mixture is generated by the reaction of acrylic acid-2-hydroxyethyl ester, cyclohexyl methacrylate, D-glucosamine sodium sulfate, styrene and linoleic acid, and then the auxiliary agent is prepared by post-treatment of methanol, ammonium persulfate and sodium bisulfate, so that the electrostatic repulsion and the formed high-molecular protective film can generate a synergistic effect, further agglomeration of the medicament is prevented, volatilization of a solvent is reduced, precipitation of a functional medicament is reduced, and the medicament effect is improved.
3) The activity and the bactericidal effect of the pesticide composition are not simple superposition of the activities of all components, and compared with the existing single preparation, the pesticide composition has obvious synergistic effect, good safety to crops and accordance with the safety requirement of pesticide preparations.
Detailed Description
The invention uses part of raw materials with the following sources:
fatty alcohol polyoxyethylene ether-9, cas No.: 68439-50-9, shanghai kaimem industries, ltd.
Example 1
A method for preparing a plant disease control composition containing fluopicolide and metalaxyl-M, comprising the steps of: weighing 5kg of fluopicolide, 10kg of metalaxyl-M, 10kg of auxiliary agent, 10kg of fatty alcohol-polyoxyethylene ether-9 and 55.5kg of water, mixing for 20min at a stirring speed of 70r/min, adding 5kg of glycol, 4kg of sodium dodecyl benzene sulfonate, 0.2kg of xanthan gum and 0.3kg of tridecafluorooctyltrimethoxysilane, uniformly shearing and mixing at a high speed, sanding for 2.5h, and uniformly stirring to obtain the plant disease control composition containing fluopicolide and metalaxyl-M.
The preparation method of the auxiliary agent comprises the following steps:
step 1, adding 5kg of styrene, 10kg of linoleic acid, 1kg of acrylic acid-2-hydroxyethyl ester, 4kg of cyclohexyl methacrylate and 1kg of D-glucosamine sodium sulfate into 150kg of water to prepare a mixed solution, then adding 0.3kg of azobisisobutyronitrile, adjusting the pH to 9.5 by adopting 30wt% of sodium hydroxide aqueous solution, and reacting for 1.5h at 60 ℃ to obtain a high-molecular surfactant;
and 2, adding 20kg of methanol, 6kg of ammonium persulfate and 6kg of sodium bisulfate into 250kg of water, then adding the high molecular surfactant prepared in the step 1, carrying out oil bath reaction for 5 hours at the reaction temperature of 80 ℃, cooling to room temperature, neutralizing with 30wt% of sodium hydroxide aqueous solution until the pH value is 7.5, then drying with a spray dryer to obtain a crude product, dissolving the crude product in 80kg of deionized water, dialyzing with a dialysis membrane with the molecular weight of 1000Da, replacing the deionized water every 3 hours until the conductivity of the dialysate is equal to that of the deionized water, collecting a high molecular compound, and freeze-drying to obtain the assistant.
Example 2
A plant disease control composition containing fluopicolide and metalaxyl-M was prepared in substantially the same manner as in example 1, with the only difference that: the preparation methods of the auxiliaries are not consistent.
The preparation method of the auxiliary agent comprises the following steps:
step 1, adding 5kg of styrene, 10kg of linoleic acid, 4kg of cyclohexyl methacrylate and 1 kgD-glucosamine sodium sulfate into 150kg of water to prepare a mixed solution, then adding 0.3kg of azobisisobutyronitrile, adjusting the pH to 9.5 by adopting 30wt% of sodium hydroxide aqueous solution, and reacting for 1.5 hours at 60 ℃ to obtain a high-molecular surfactant;
and 2, adding 20kg of methanol, 6kg of ammonium persulfate and 6kg of sodium bisulfate into 250kg of water, then adding the high molecular surfactant prepared in the step 1, carrying out oil bath reaction for 5 hours at the reaction temperature of 80 ℃, cooling to room temperature, neutralizing with 30wt% of sodium hydroxide aqueous solution until the pH value is 7.5, then drying with a spray dryer to obtain a crude product, dissolving the crude product in 80kg of deionized water, dialyzing with a dialysis membrane with the molecular weight of 1000Da, replacing the deionized water every 3 hours until the conductivity of the dialysate is equal to that of the deionized water, collecting a high molecular compound, and freeze-drying to obtain the assistant.
Example 3
A plant disease control composition containing fluopicolide and metalaxyl-M was prepared in substantially the same manner as in example 1, with the only difference that: the preparation methods of the auxiliaries are not consistent.
The preparation method of the auxiliary agent comprises the following steps:
step 1, adding 5kg of styrene, 10kg of linoleic acid, 1kg of acrylic acid-2-hydroxyethyl ester and 1 kgD-glucosamine sodium sulfate into 150kg of water to prepare a mixed solution, then adding 0.3kg of azobisisobutyronitrile, adjusting the pH to 9.5 by adopting 30wt% of sodium hydroxide aqueous solution, and reacting at 60 ℃ for 1.5h to obtain a high-molecular surfactant;
and 2, adding 20kg of methanol, 6kg of ammonium persulfate and 6kg of sodium bisulfate into 250kg of water, then adding the high molecular surfactant prepared in the step 1, carrying out oil bath reaction for 5 hours at the reaction temperature of 80 ℃, cooling to room temperature, neutralizing with 30wt% of sodium hydroxide aqueous solution until the pH value is 7.5, then drying with a spray dryer to obtain a crude product, dissolving the crude product in 80kg of deionized water, dialyzing with a dialysis membrane with the molecular weight of 1000Da, replacing the deionized water every 3 hours until the conductivity of the dialysate is equal to that of the deionized water, collecting a high molecular compound, and freeze-drying to obtain the assistant.
Example 4
A plant disease control composition containing fluopicolide and metalaxyl-M was prepared in substantially the same manner as in example 1 except that: the preparation methods of the auxiliaries are not consistent.
The preparation method of the auxiliary agent comprises the following steps:
step 1, adding 5kg of styrene, 10kg of linoleic acid, 1kg of acrylic acid-2-hydroxyethyl ester and 4kg of cyclohexyl methacrylate into 150kg of water to prepare a mixed solution, then adding 0.3kg of azobisisobutyronitrile, adjusting the pH to 9.5 by adopting 30wt% of sodium hydroxide aqueous solution, and reacting for 1.5h at 60 ℃ to obtain a high-molecular surfactant;
and 2, adding 20kg of methanol, 6kg of ammonium persulfate and 6kg of sodium bisulfate into 250kg of water, then adding the high molecular surfactant prepared in the step 1, carrying out oil bath reaction for 5 hours at the reaction temperature of 80 ℃, cooling to room temperature, neutralizing with 30wt% of sodium hydroxide aqueous solution until the pH value is 7.5, then drying with a spray dryer to obtain a crude product, dissolving the crude product in 80kg of deionized water, dialyzing with a dialysis membrane with the molecular weight of 1000Da, replacing the deionized water every 3 hours until the conductivity of the dialysate is equal to that of the deionized water, collecting a high molecular compound, and freeze-drying to obtain the assistant.
Comparative example 1
A plant disease control composition containing fluopicolide and metalaxyl-M was prepared in substantially the same manner as in example 1, with the only difference that: the preparation methods of the auxiliaries are not consistent.
The preparation method of the auxiliary agent comprises the following steps:
step 1, adding 5kg of styrene and 10kg of linoleic acid into 150kg of water to prepare a mixed solution, then adding 0.3kg of azobisisobutyronitrile, adjusting the pH to 9.5 by adopting a 30wt% sodium hydroxide aqueous solution, and reacting for 1.5h at 60 ℃ to obtain the high-molecular surfactant.
And 2, adding 20kg of methanol, 6kg of ammonium persulfate and 6kg of sodium bisulfate into 250kg of water, then adding the high molecular surfactant prepared in the step 1, carrying out oil bath reaction for 5 hours at the reaction temperature of 80 ℃, cooling to room temperature, neutralizing with 30wt% of sodium hydroxide aqueous solution until the pH value is 7.5, then drying with a spray dryer to obtain a crude product, dissolving the crude product in 80kg of deionized water, dialyzing with a dialysis membrane with the molecular weight of 1000Da, replacing the deionized water every 3 hours until the conductivity of the dialysate is equal to that of the deionized water, collecting a high molecular compound, and carrying out freeze drying to obtain the assistant.
Comparative example 2
A plant disease control composition containing fluopicolide and metalaxyl-M was prepared in substantially the same manner as in example 1, with the only difference that: no auxiliary agent is added.
Test example 1
Hydrophilic Lipophilic Balance (HLB) determination
The hydrophilic-lipophilic balance (HLB) of the copolymer wetting dispersant is determined by a water number method. The water numbers of the different systems were determined using oleic acid (HLB = 1) and sodium oleate (HLB = 18) as standards. Accurately weighing oleic acid and sodium oleate, placing the oleic acid and sodium oleate into a 50mL conical flask, adding 20g of methanol for ultrasonic dissolution, adding 2g of toluene for uniform mixing to obtain a clear solution, titrating with distilled water at 25 ℃, taking the titration end point when the solution becomes turbid obviously, and recording the water volume (mL), namely the water number. A standard curve was established by plotting the water number against the HLB value. Accurately weighing 0.5g of the plant disease control composition containing fluopicolide and metalaxyl-M prepared in the example or the comparative example, titrating (the method is the same as the above) to obtain the water number of a sample to be tested, substituting the water number into a standard curve equation to obtain the HLB value of the pesticide composition, testing each sample for three times, and taking the average value of the HLB value, wherein the average value is shown in Table 1
Table 1: hydrophilic Lipophilic Balance (HLB) test results
(the higher the HLB value, the stronger the wettability and dispersibility of the strain)
As can be seen from the test results of Table 1, the plant disease control composition containing fluopicolide and metalaxyl-M prepared in example 1 has the highest HLB, indicating that the wetting and dispersing properties of the composition are the best, probably because styrene and linoleic acid are used as raw materials, 2-hydroxyethyl acrylate, cyclohexyl methacrylate and sodium vinylsulfonate are used as monomers, a surfactant is synthesized, and then an adjuvant is prepared by post-treatment with methanol, ammonium persulfate and sodium hydrogensulfate. The surface energy between fluopicolide and metalaxyl-M can be reduced and the intermiscibility of fluopicolide and metalaxyl-M can be enhanced when the composition is added into a pesticide composition. And because sulfate ions in the auxiliary agent provide electrostatic repulsion, the molecular density of the surfactant at the interface is lower, and the molecular packing density at the gas-liquid interface is lower, so that the surfactant has better surface activity, and the functional components and the additive can be charged to generate electrostatic repulsion. The 2-hydroxyethyl acrylate, the cyclohexyl methacrylate and the sodium vinyl sulfonate are mutually cooperated to form a compact adsorption layer with a complex spatial structure on functional components by structurally complementing, the adsorption layer is a polymer protective film, further approach and agglomeration of a medicament can be prevented, volatilization of a solvent is reduced, stability of a system is increased, wettability and dispersibility are improved, and therefore a steric hindrance effect is generated to prevent particles from being agglomerated and enlarged, and the purpose of improving the medicament effect is achieved.
Test example 2
The suspension rate is determined according to the method for determining the suspension rate of the pesticide in GB/T14825-2006 national standard. Accurately weighing 2.5g of sample preparation in a 250mL triangular flask, pouring prepared 250mL of hard water (30 +/-1 ℃), shaking the suspension for 240 times within 120s, and then placing in a water tank at the constant temperature of 30 ℃ for standing for 15min; after standing, the mixture is transferred to a 250mL standard measuring cylinder, and hard water at 30 ℃ is added for constant volume. Then upside down with frequency of 2s once shaking 30 after covering the bottle stopperPlacing in 30 deg.C water bath, and keeping the temperature for 30min; then, the suspension liquid of 9/10 (225 ml) at the upper layer of the suspension liquid is quickly sucked by a vacuum pump, and the content of the original drug of the residual suspension liquid at the bottom accounting for 1g of the taken sample is measured according to the methodX2. The suspension ratio is calculated as follows:
X1-total content of active ingredients,%, of the prepared samples;
X2-1/10 active ingredient content,%, of the cylinder bottom;
the test results are shown in table 2. Table 2: test results of suspension Rate
The suspension rate of the pesticide is an important quality index of the pesticide preparation in a suspension system and is also an important parameter for measuring the suspension property of the pesticide preparation. The greater the suspension rate, the better the suspension performance of the pesticide formulation. As can be seen from the test data of table 2, the suspension rate of the plant disease control composition containing fluopicolide and metalaxyl-M obtained in example 1 is the greatest, probably due to the poor compatibility of the mixed pesticide of fluopicolide and metalaxyl-M on the surface of the plant, the effect of the prepared suspension agent is not as good as that of the emulsifiable concentrate, and the solvent is easy to volatilize, causing the functional substance to form crystals and not easy to be absorbed. But the benzene ring in the styrene reacts and combines with the acrylic acid-2-hydroxyethyl ester, the cyclohexyl methacrylate and the sodium vinyl sulfonate, so that the polarity of the auxiliary agent can be reduced, and the styrene is more stable in the using process. And the density difference between the prepared auxiliary agent and water is small, so that the agglomeration degree of the pesticide composition in the water can be reduced. Therefore, the pesticide composition prepared by adding the auxiliary agent has smaller density difference with water, shows better hydrophilicity and stability, and has larger suspension rate.
Test example 3
Measurement of viscosity
The viscosities of examples and comparative examples were measured using an NDJ-1 rotational viscometer (Shanghai balance Instrument plant). The temperature was set at 25 ℃ and each of the examples and comparative samples was tested three times and averaged. The test results are shown in Table 3.
Table 3: results of viscosity measurement
Viscosity is an important index of the stability of a pesticide preparation in a suspension system, according to the Stockes law, the sedimentation rate of dispersed phase particles in the suspension system is inversely proportional to the viscosity of the system, and the larger the viscosity is, the smaller the sedimentation rate of the particles is, and the better the storage stability is; on the contrary, the storage stability is poor. However, the excessive viscosity of the system easily causes poor fluidity of the preparation, and a series of problems are brought to split charging, application and the like. As can be seen from the test results in Table 3, the viscosity of example 1 is the highest, the storage stability is better, the film forming property is better, and the viscosity can be kept within the range of viscosity for good processing and use, which may be caused by the fact that the invention generates polymeric surfactant by the reaction of 2-hydroxyethyl acrylate, cyclohexyl methacrylate, D-glucosamine sodium sulfate, styrene and linoleic acid, and the further prepared auxiliary agent can form a dense adsorption layer with complex spatial structure on the functional agent, and is adsorbed on the surface of the functional agent to form a polymeric protective film, thereby preventing the agent from further approaching and agglomerating, reducing the volatilization of the solvent, reducing the precipitation of the functional agent, properly increasing the viscosity of the system, forming good contact absorption effect with crops, maintaining the wetting effect, and enhancing the curative effect on plant diseases caused by low-grade fungi.
Claims (8)
1. A plant disease control composition containing fluopicolide and metalaxyl-M is characterized by comprising the following components in percentage by weight: 3~8% fluopicolide, 8 to 12% metalaxyl, 10 to 25% dispersing agent, 10 to 30% auxiliary agent, 3~8% antifreeze agent, 3~6% wetting agent, 0.1 to 0.8% xanthan gum, 0.1 to 0.5% defoaming agent and the balance of water;
the preparation method of the auxiliary agent comprises the following steps of:
step 1, adding 3~8 parts of styrene, 8 to 15 parts of linoleic acid, 0.5 to 2 parts of 2-hydroxyethyl acrylate, 2~6 parts of cyclohexyl methacrylate and 0.5 to 2 parts of D-glucosamine sodium sulfate into 120 to 180 parts of water to prepare a mixed solution, then adding 0.1 to 0.5 part of azodiisobutyronitrile, adjusting the pH to 9 and 10 by adopting 20 to 32wt% of a sodium hydroxide aqueous solution, and reacting for 1 to 3h at 50 to 70 ℃ to obtain a high-molecular surface active agent;
and 2, adding 15-30 parts of methanol, 4~8 parts of ammonium persulfate and 4~8 parts of sodium bisulfate into 200-300 parts of water, then adding the high molecular surfactant prepared in the step 1, carrying out oil bath reaction for 3-8h at the reaction temperature of 60-90 ℃, cooling to room temperature, adjusting the pH to 7~8 by using 20-32wt% of sodium hydroxide aqueous solution, then drying to obtain a crude product, dissolving the crude product in water, dialyzing, collecting a high molecular compound, and carrying out freeze drying to obtain the auxiliary agent.
2. A plant disease control composition containing fluopicolide and metalaxyl-M according to claim 1, which comprises the following components in percentage by weight: 5% of fluopicolide, 10% of metalaxyl-M, 10% of dispersant, 10% of auxiliary agent, 5% of antifreeze agent, 4% of wetting agent, 0.2% of xanthan gum, 0.3% of defoaming agent and the balance of water.
3. A plant disease control composition containing fluopicolide and metalaxyl-M according to claim 1, characterized in that: and the dialysis is carried out by adopting a dialysis membrane with the molecular weight of 1000Da, water is replaced every 2 to 4 hours until the conductivity of the dialysate is equal to that of the water, and the high molecular compound is collected.
4. A plant disease control composition containing fluopicolide and metalaxyl-M according to claim 1, wherein: the antifreeze is at least one of ethylene glycol, propylene glycol and glycerol.
5. A plant disease control composition containing fluopicolide and metalaxyl-M according to claim 1, wherein: the defoaming agent is at least one of organic silicon and polydimethylsiloxane.
6. A plant disease control composition containing fluopicolide and metalaxyl-M according to claim 1, wherein: the wetting agent is at least one of sodium alkyl benzene sulfonate, sodium alkyl naphthalene sulfonate, polyoxyethylene lauryl ether and sodium lauryl sulfate.
7. A plant disease control composition containing fluopicolide and metalaxyl-M according to any one of claims 1~6, prepared by the process of: weighing fluopicolide, metalaxyl-M, an auxiliary agent, a dispersing agent and water, mixing, stirring for 10 to 30min at 50 to 80r/min, adding an antifreeze agent, a wetting agent, xanthan gum and a defoaming agent, uniformly mixing by high-speed shearing, sanding for 2 to 3h, and uniformly stirring to obtain the plant disease control composition containing fluopicolide and metalaxyl-M.
8. Use of a plant disease control composition containing fluopicolide and metalaxyl-M according to any one of claims 1~6 for controlling plant disease, wherein: the plant diseases are diseases caused by lower fungi.
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| WO2005044242A1 (en) * | 2003-10-27 | 2005-05-19 | Dow Corning Corporation | Preparations for topical application and methods of delivering an active agent to a substrate |
| CN101389215A (en) * | 2006-01-10 | 2009-03-18 | 英诺瓦佛姆技术有限公司 | Pesticide delivery system |
| CN103843769A (en) * | 2012-12-06 | 2014-06-11 | 仇清华 | Bactericidal composition containing fluopicolide and metalaxyl-m |
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