CN118139530A

CN118139530A - Nanometer suspension for preventing and treating powdery mildew of cucumber

Info

Publication number: CN118139530A
Application number: CN202380012351.1A
Authority: CN
Inventors: 张子勇; 梁冰
Original assignee: Individual
Current assignee: Individual
Priority date: 2022-12-18
Filing date: 2023-11-02
Publication date: 2024-06-04

Abstract

The invention belongs to the field of nano pesticides, and relates to a mancozeb compound nano suspension with a particle size smaller than 100 nanometers and a preparation method thereof. The invention adopts two or three components to be diluted and mixed with water to form the mancozeb compound nano suspension below 100 nanometers. The preparation method comprises the following steps: adding the first component diluent to the second component diluent or adding the second component diluent to the first component diluent under the condition that the stirring speed is not less than the effective stirring speed; forming mancozeb compound nano suspension.

Description

Nanometer suspension for preventing and treating powdery mildew of cucumber

[ Field of technology ]

The invention belongs to the field of nano pesticides, and particularly relates to preparation of binary or ternary compound nano suspension with particle size smaller than 100 nanometers.

[ Background Art ]

Nano pesticides refer to pesticide formulations in which the pesticide particle size is in the order of nanometers. From the viewpoint of application effect and stability, the particle size of the nano-pesticide is preferably 100nm or less, and the smaller the particle size is, the better. Currently, the particle size of mainstream pesticide formulations is on the order of microns, i.e. above a few microns. If the particle size is reduced to the corresponding nanometer level, namely the size is reduced by 1000 times, the effective components with the same mass can theoretically increase the particle number by 10 hundred million times and the surface area by 1000 times on the premise of keeping the particle shape unchanged. The rapid increase of the number and the surface area of the pesticide particles can lead the pesticide to be more uniformly dispersed, the pesticide can be more widely contacted with a control target, and the pesticide effect can be fully exerted and improved. This is the root cause of the development of nano pesticides.

Mancozeb has been used internationally for over fifty years. The usage of the organic sulfur bactericide is always a large-tonnage product, and the organic sulfur bactericide is a protective organic sulfur bactericide with good effect. It features low toxicity, long lasting period, killing multiple groups of bacteria, less resistance and better preventing and treating effect.

Mancozeb belongs to broad-spectrum and non-systemic bactericides with protective effect. Is used for various crops such as fruit trees, ornamental plants of vegetables, tobacco and the like. And can also prevent and treat various important leaf fungus diseases. Is used for preventing and treating early blight and late blight of potato and tomato; downy mildew and black rot of grape; net blotch, stripe blotch, and large blotch of wheat and corn; the plant blight, seedling spot, vegetable downy mildew, anthracnose, epidemic disease and the like of cotton and peanut have good control effects.

The mancozeb can be compounded with various pesticides to form various compound preparations. However, the main dosage forms of the composition are traditional powder, wettable powder, water dispersible granules and suspending agents, which are not only used singly but also used in a compounding way, and are influenced by the physical properties of the composition, namely the composition is insoluble in water and organic solvents. According to the existing pesticide preparation processing technology level, the minimum size of pesticide particles in the preparation is usually more than a few microns, and the size is tens of microns or even tens of microns. The mancozeb pesticide has large particle size, is not beneficial to the exertion of pesticide effect, and has certain drug resistance generated by using a large amount for many years, and the current use amount per unit area is large, and is usually 750 g-2250 g/hm ² of active ingredient. How does this increase its efficacy and decrease its usage per unit area? Is an important content for researching the type of the pesticide.

It is clear that the existing preparation of several mancozeb dosage forms is to synthesize the raw materials first and then process various dosage forms. The method comprises the following specific steps: (1) synthesizing the raw medicine. The method comprises the following two steps: the first step is to synthesize ambam or mancozeb, and the second step is to synthesize mancozeb. The synthesized mancozeb or maneb sodium is water-soluble, can be dissolved in water, and then respectively carries out salt formation and complexation reaction with manganese salt and zinc salt to obtain massive precipitated mancozeb. The precipitated mancozeb is not dissolved in water or organic solvent, and needs to be separated, washed and dried to obtain the mancozeb original drug. (2) processing the preparation. The solid mancozeb raw material is used as a raw material to process the preparation. The mancozeb preparation can be obtained by crushing, grinding, mixing and the like. The preparation process from the ambam or the ambam needs to add corresponding production equipment and workshops such as a filter, a dryer, a pulverizer, a grinder and a mixer, and also needs corresponding production process and processing technology. It can be found that the process is long and energy is consumed from the synthesis of water-soluble mancozeb or maneb sodium to the processing of mancozeb into different solid dosage forms.

The process flow of the traditional mancozeb raw material preparation and the processing into the most common powder and wettable powder is shown in figure 1.

The prior art comprises the following steps: the technical proposal of preparing nano mancozeb by taking mancozeb as a raw material.

Chinese patent No. 201711490378.4 discloses a nanometer Mancozeb zinc powder preparation.

According to the technical scheme disclosed by the invention, nanometer mancozeb in a strict sense, especially mancozeb with the particle size below 100nm, cannot be obtained. It should be noted that, a water-soluble polymer is added as a dispersant in the system, and the aqueous solution should be in a transparent state. The water dispersion of the filter cake is in a suspension state, which shows that the technical scheme can not obtain the true nano suspension, in particular to the mancozeb nano preparation with the particle size smaller than 100 nm.

The comparative technique (CN 201711490378.4) claims that in the reaction for synthesizing mancozeb, nano-sized mancozeb is produced by adding a dispersant and a buffer. However, according to the analysis of the common sense of science, the selection of the dispersant is wrong, and the use of an acidic buffer solution in addition results in the loss of the dispersant. Experiments show that the nano-size of the mancozeb particles can be generated only under the condition that the concentration of the mancozeb is extremely low. Therefore, the comparative technology is considered to be incapable of realizing industrial production of nano mancozeb.

In view of the fact that the particles of mancozeb products in various dosage forms registered in China by pesticide companies at home and abroad are micron-sized, and the defects existing in the technical scheme of the nano mancozeb, the method also reflects that the innovation of the nano mancozeb, particularly the nano mancozeb products with the size smaller than 100nm, has great technical difficulty. This also suggests that to obtain mancozeb nano-suspension, one must innovate thought and develop a new way.

[ Invention ]

The prior application: PCT/CN2022/139831; PCT/CN2022/139832; PCT/CN2022/139833

One of the purposes of the invention is to overcome the defects of the prior art, provide a new thought and method which are different from the prior art for preparing mancozeb zinc powder dosage forms, realize the reaction of mancozeb (or manb, potassium maneb) and manganese salt and zinc salt through the water dilution process, and generate mancozeb, thereby providing the mancozeb nano suspension with water-soluble appearance and transparent appearance, and directly use for spraying.

Said invention also provides a method for preparing said mancozeb nano suspension liquid, and the pesticide spraying equipment can be used for spraying operation.

The innovative idea of the invention is as follows:

The ambam is a water-soluble ammonium salt, which is a single molecule dispersed in water as a component. The manganese salt and zinc salt reacted with the catalyst are also single molecules and metal ions dispersed in water as another component. When the two meet, the reaction between ions can easily form the mancozeb and zinc salt structures. Since both the manganese ion and the zinc ion are polyvalent metal ions, a complex structure may be formed in addition to the salt formation. No matter salifying or complexing, when mixing, the nano crystal grain of mancozeb can be generated by controlling the addition amount of a certain component.

An aqueous solution of one component (e.g., manganese salt, zinc salt) is added to an aqueous solution of another component (e.g., zineb) with a controlled rate of agitation. The dripping speed and the stirring speed are controlled, so that nano crystal grains of the mancozeb and suspension thereof can be generated.

The resulting mancozeb nanocrystalline particles, when the particle size is small in a small amount, are temporarily stably dispersible in an aqueous system. Due to the continuous generation of nanocrystalline grains, collisions, growth and aggregation between the grains occur. When the size of the mancozeb nano crystal grain is close to the wavelength of visible light, opalescence starts to appear in the system, and when the mancozeb nano crystal grain is over, the system is gradually opaque. Under the action of gravity, large-size crystal grains are precipitated. In order to prevent this, a polymeric auxiliary agent must be added to the system. The polymeric auxiliary is a water-soluble polymer, usually an amorphous polymer, and exists in a random coil morphology after being dissolved in water. The random coil is a loose spherical structure formed by spontaneous curling of a water-soluble polymer chain, wherein the inside of the random coil is gathered into a lipophilic and hydrophobic molecular main chain, and the outside of the random coil is a hydrophilic polar group. At this time, when the size of the mancozeb nano-crystal grains generated by the system is smaller than 100 nanometers, under the action of mechanical stirring shearing force, the water-insoluble nano-crystal grains can be diffused into random coils and loaded, and the effective collision, growth, precipitation and precipitation of the crystal grains are isolated and prevented. Therefore, the random coil formed by the water-soluble polymer auxiliary agent has the functions of dispersing, suspending, stabilizing and protecting the mancozeb nano-crystalline grains. The random coil is uniformly dispersed in the water phase, and the nano crystal grains diffused into the random coil are also uniformly dispersed in the water phase. When the grain size is below 100 nanometers, the system is clear and transparent, and the apparent water is soluble, so that the phenomenon of Tdall can occur.

It should be noted that the rate of addition of the components and the rate of agitation into the system during the formation of the nanocrystalline particles, which are important factors affecting the size of the nanocrystalline particles formed, are related to the amount of addition per unit time and the degree of uniformity of dispersion. For the rate of addition, if the size of the produced nanocrystalline particles is targeted to be less than 100 nm, whether the system is clear or transparent is the criterion. The theoretical basis is that when the particle size is less than a quarter of the lower limit of the wavelength of visible light (400-760 nm), no severe refraction and reflection are formed, and the system is therefore transparent. Conversely, if the system is opalescent or opaque, it indicates that the grain size is greater than 100 nanometers.

To achieve this, attention must be paid to the following:

① The mixing speed of the two-component solution (i.e. the addition speed of one of the components) cannot be too fast. Too fast addition, uneven dispersion of the two components and too high local concentration, the speed of the generated crystal grains is also fast, the number of the generated crystal grains is also large, and aggregation among the nano crystal grains is likely to occur, so that the crystal grain size is enlarged. If the system appears opalescent, it is indicated that the grain size is already a few hundred nanometers. Therefore, the addition rate of one of the components is such that the system is always transparent.

② The stirring speed of the system is properly accelerated. The stirring speed of the system relates to the generation speed and the dispersion speed of the nano crystal grains in the water phase. Stirring is sufficient, diffusion is fast, rapid formation and dispersion of nano grains are facilitated, small-size grains are maintained, and aggregation among the grains is avoided. The stirring speed is matched with the adding speed of the components, and the transparent of the system is kept all the time.

Interpretation of the terms

The tyndall phenomenon: the tyndall phenomenon is a phenomenon that when a beam of light passes through a colloid, a bright "path" in the colloid is observed from the direction of normal incidence, and the phenomenon is also called the tyndall effect (TYNDALL EFFECT). The essence of the tyndall effect is a scattering phenomenon when light propagates in a colloid. This occurs mainly because the particle size of the colloidal particles is 1-100 nm, visible light is more significantly scattered when passing through the colloid, and the scattering effect of the true solution on light is very weak. Colloids have a distinct tyndall phenomenon, whereas true solutions with molecules dispersed are scarcely available, and are therefore often used to distinguish between colloidal solutions and true solutions. If the particles are smaller than the wavelength of the incident light, scattering of the light occurs, and the light waves are emitted around the particles, which is called scattered light or opalescence. The tyndall effect is essentially a scattering phenomenon of light or opalescence phenomenon. The scattering effect of the true solution on light is weak. The intensity of the scattered light also increases with increasing concentration of particles in the dispersion. Thus, when the observed solution is clear and transparent, indicating that the particle size in the solution is less than 100nm, the tyndall phenomenon may occur. If the particles are larger than the wavelength of the incident light (400 nm to 740 nm), reflection of the light occurs significantly. As solutions show increasingly heavy opalescence and even opalescence, the particle size has increased to near microns or above. The system comprises: the system refers to a suspension system formed by mixing two components under the premise of controlling the adding speed mode and stirring when the mancozeb nano suspension is prepared. The system is a target product-suspension formed by mixing water, a precursor, a manganese salt zinc salt, a water-soluble polymer auxiliary agent and the like.

The components are as follows: by component is meant a composition comprising one or more ingredients. In principle, any one of the components used in the present invention may be formed as a single component, but the combination of the components should be simplified in view of convenience in packaging, transportation and use. The principle is as follows: ① No reaction occurs between the components; ② The amount of the component formed by the ingredients should not be excessive.

The components are as follows: the components are raw material substances used in the present invention, and include water-soluble mancozeb, manganese salt, zinc salt, water-soluble polymer auxiliary agent and water.

Precursor: the precursor refers to a parent substance used in the reaction of producing the target product mancozeb, namely, water-soluble maneb salts, including maneb, maneb sodium and maneb potassium.

Water-soluble polymer auxiliary agent: the polymer is a polymer substance in which hydrophilic polar groups are contained and which is soluble, and is also called a polymer surfactant or an active agent. The water-soluble polymer auxiliary agent can play roles in dispersion, suspension, emulsification and stabilization. Depending on the nature of the groups, anionic, cationic, zwitterionic and nonionic polymeric auxiliaries can be distinguished.

Particle diameter of microparticles: also known as particle size; the precursor in the system is dispersed with water soluble polymer assistant to form mancozeb crystal grain size, which is also the grain size of other pesticide and is not specific to the microstructure of crystal grain.

The 100 nm scale is as follows: is a statistically significant classification of the size of pesticide particles in a system. All pesticide particle sizes in the suspension exhibit a statistical distribution. The nano suspension below 100 nanometers refers to a peak value on a particle size distribution curve of mass fraction of each fraction of particle classification and corresponding size of the particle is less than 100 nanometers. The detection can be carried out by using a British Markov laser nanometer particle size analyzer, and the processing is carried out by using a Number statistical method.

Stabilization period: refers to the stable time that the nanosuspension can maintain the transparent state after the preparation is completed. To ensure the completion of the spraying operation, the stabilization period should be not less than 1 hour. The invention provides an hour-level stabilization period, which means that the stabilization time is between 1 and 5 hours.

Effective stirring speed: the effective stirring speed refers to that when one component is added into the other component in a certain adding mode, nano crystal grains generated in the system can be timely dispersed through stirring at the stirring speed not smaller than the effective stirring speed, the growth and aggregation of the crystal grains do not occur, and the crystal grain size is not increased to hundreds of nanometers. The transparent state of the system liquid is an effective stirring sign.

And (3) effectively stirring: the mode and speed of adding components and stirring have important influence on the system generating liquid. The stirring mode comprises mechanical stirring, multipoint mechanical stirring, manual stirring and multipoint manual stirring. The stirring speed is high, and good effect is achieved. If the system-produced liquid is in a transparent state, efficient stirring is considered. Otherwise, the stirring is regarded as ineffective.

The adding mode is as follows: the addition mode includes adding the component A to the component B, adding the component B to the component A, or adding the component A and the component B to the system simultaneously, and also includes continuous addition, intermittent addition, trickle addition, dripping addition, spraying addition, fixed-position or mobile-position addition and the like. The two components are mixed and dispersed as soon as possible.

The addition rate is as follows: after the addition mode is determined, the addition amount of the components is controlled with the aim of realizing effective stirring.

Nanoemulsion: also known as nanoemulsions. The method is that a solution formed by the effective components of the pesticide forms a dispersion system of nano-sized emulsion particles under the action of an auxiliary agent dispersed in water. The nanoemulsion is clear and transparent in appearance, and has thermodynamic stability, wherein the particle size is generally below 100 nm.

Myclobutanil/amino-oligosaccharin nanoemulsion: comprises the following two emulsion forms

1) Myclobutanil nano emulsion

2) Myclobutanil and amino oligosaccharin nanoemulsion: sometimes also described as a nanoemulsion of myclobutanil and amino-oligosaccharin, where the amino-oligosaccharin is dissolved in the aqueous phase.

Multielement compounding of mancozeb, myclobutanil and amino oligosaccharin

The mancozeb is a broad-spectrum multi-site protective bactericide, and has the main functions of preventing fungal diseases, and the mancozeb is required to be used in advance when in use, and is preferably mixed with other medicaments, particularly systemic bactericides. Therefore, in order to improve the control effect on crop diseases, mancozeb is often compounded with other bactericides. In order to improve the disease control effect of mancozeb and obtain the multi-target control effect by one-time plant protection, the invention provides a binary, ternary or multi-element compound nano suspension of mancozeb and different bactericides based on the technology of obtaining the mancozeb nano suspension. The method and the scheme provided by the invention can lead the mancozeb compound nanometer suspension to be widely applied.

The myclobutanil (myclobutanil) is 2- (4-chlorophenyl) -2- (1H, 1,2, 4-triazole-1-methyl) capronitrile, is a systemic triazole broad-spectrum low-toxicity bactericide with protective and therapeutic activity, and mainly has an inhibitory effect on the biosynthesis of ergosterol of pathogenic bacteria. The myclobutanil has the functions of preventing and treating, has long lasting period, is safe to crops, and has certain growth stimulation. The plant growth promoting agent can promote the rapid growth of crops, has dark green leaves, strong plants and high yield.

The amino-oligosaccharin (oligosaccharins), also called as oligomer of chitosan, refers to oligosaccharide of D-glucosamine linked by beta-1, 4 glycosidic bond, and is produced by degrading chitosan through biological technology. As a new biological pesticide, it not only can regulate plant growth, but also can induce and activate the immune system of plant, and can raise the disease resistance of plant. It has no toxic side effect to human and animal, easy absorption by crop, no residue and no environmental pollution. The amino oligosaccharin can prevent invasion and expansion of pathogenic bacteria by enhancing the cell structure resistance of induced plants (such as strengthening cell walls, accumulating lignin, forming halos and mastoid, generating knee-loss substances, colloid substances, filling bodies and the like), so as to improve the disease resistance of plants. Can also inhibit the growth of some germs, influence the germination of fungus spores, induce the variation of hypha morphogenesis, change the spore growth and the like. Can excite genes in plants to generate disease-resistant chitinase, glucanase, plant protection element, PR protein and the like, has cell activation effect, is favorable for recovering victimized plants, promotes root and seedling strengthening, enhances stress resistance of crops and promotes plant growth and development.

The mancozeb and the myclobutanil are compounded according to a certain proportion to form a broad-spectrum low-toxicity composite bactericide, and the broad-spectrum low-toxicity composite bactericide has dual functions of protection and treatment. The two sterilization mechanisms make the pathogenic bacteria not suitable to generate drug resistance, and the use is convenient and safe, and the lasting period is longer.

The mancozeb/myclobutanil compound preparation is suitable for various crops, has good control effect on a plurality of higher fungal diseases, and has outstanding effects on cladosporium cucumerinum, powdery mildew and rust disease. Crops and diseases which have been used for control at present are: scab, powdery mildew, rust of pear trees; scab, rust and powdery mildew of apples; scab of peach tree, powdery mildew of persimmon tree; powdery mildew of walnut tree; scab and scab of citrus; scab and leaf spot of bananas; powdery mildew of melons such as cucumber, melon, wax gourd and the like; powdery mildew, rust disease, etc. of cowpea. The existing compound preparation of the mancozeb/myclobutanil comprises the following two effective components in proportion: 20-60/5-2. In the 33 pesticide registration certificates, all the dosage forms are wettable powder, no other liquid dosage forms exist, and no nanometer suspending agent dosage forms exist.

The mancozeb and myclobutanil compound preparation has good curative effect only on fungal diseases, and when bacterial diseases are frequent, other bactericides are required to be added. The amino oligosaccharin has strong preventing and eliminating effects on fungi, bacteria and viruses, and has the effects of nutrition, regulation and detoxification. If amino oligosaccharin is added on the basis of binary bactericide compounding, cheng Daisen manganese zinc/myclobutanil/amino oligosaccharin ternary compound preparation is prepared. Can be widely used for preventing and treating powdery mildew, mosaic disease, lobular disease, alternaria leaf spot, anthracnose, downy mildew, epidemic disease, gummy stem blight, yellow dwarf, rice blast, bacterial wilt, soft rot and other diseases caused by viruses, bacteria and fungi of fruit trees, vegetables, underground rhizomes, tobacco, traditional Chinese medicinal materials and grain cotton crops.

The mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension refers to a nanometer suspension below 100 nanometers; the below 100 nm mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension is formed by diluting and mixing at least two components with water:

Mancozeb/myclobutanil/amino-oligosaccharin nano suspension

The mechanism of formation of the mancozeb nanosuspension has been described in the prior application (PCT/CN 2022/139831). On the basis, myclobutanil/amino-oligosaccharin (optional) is added to further form a nano suspension of the binary or ternary pesticide. The myclobutanil/amino-oligosaccharin is added into the component A in the form of nano emulsion and solution, and when the two components are mixed according to certain conditions, the particle existence form of the myclobutanil/amino-oligosaccharin depends on the dilution water amount and the amount of high polymer auxiliary agent in the system. When the water amount is small, the diluted polymer auxiliary agent can continuously maintain the existence of the nano micelle, at the moment, the mancozeb nano crystal particle and the myclobutanil nano crystal particle coexist, and the optional amino-oligosaccharin is dispersed in water in a single molecule. If the water addition amount is not enough to maintain the concentration of the minimum high molecular auxiliary agent required by the nano colloidal particles, the micelle disappears, the myclobutanil can be separated out in the water in the form of nano crystal grains to become a nano crystal grain mixture of two pesticide active ingredients or a nano crystal grain mixture formed by mixing the two pesticide active ingredients, and the nano crystal grains coexist in the nano suspension, and the amino-oligosaccharin is dissolved in the water.

The two components are as follows:

Component A: a water-soluble mancozeb salt or a water-soluble maneb salt aqueous solution, a water-soluble polymer auxiliary agent and water; the water-soluble mancozeb is one of maneb, maneb sodium and maneb potassium or a mixture of at least two of the mancozeb, the maneb sodium and the maneb potassium; the water-soluble polymer auxiliary agent is a composite auxiliary agent formed by at least one nonionic surfactant or an aqueous solution thereof;

meanwhile, the component A is added with the nano emulsion compounded by myclobutanil/amino-oligosaccharin;

Component B: is a mixture of manganese salt and zinc salt according to a certain proportion; the manganese salt zinc salt is a composition substance of at least one salt respectively;

The component B can be a solid mixture of manganese salt and zinc salt, can be an aqueous solution formed by adding water, and can be further added with a water-soluble polymer auxiliary agent.

The water-soluble polymer auxiliary agent is at least one nonionic surfactant.

The manganese salt is selected from at least one of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate; the zinc salt is at least one selected from zinc sulfate, zinc acetate, zinc chloride and zinc nitrate.

The dosage of the water-soluble polymer auxiliary agent comprises the sum of the dosage of the polymer auxiliary agents in the component A and the component B, and the ratio of the dosage of the polymer auxiliary agent to the water consumption for dilution is not more than 1:1500. The dilution water contains all of the water in the system.

Nonionic surfactant selected from water-soluble starch and its derivatives, water-soluble guar gum and its derivatives, polyoxypropylene-polyoxyethylene block copolymer, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ether, fatty amine polyoxyethylene ether, alkylaryl polyoxypropylene polyoxyethylene ether, aryl phenol polyoxyethylene ether, castor oil polyoxyethylene ether, alkyl polyglycoside, tween, polyvinyl alcohol, polyvinylpyrrolidone, etc. Among them, the degradation products of nonylphenol polyoxyethylene ether have feminization toxicity and should be refused to use. Preferably, the polyoxypropylene-polyoxyethylene block copolymer, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ether, fatty amine polyoxyethylene ether, alkylaryl polyoxypropylene polyoxyethylene ether, castor oil polyoxyethylene ether, alkyl polyglycoside, tween and the like.

Further, the mancozeb nano-suspension below 100 nanometers has an hour-level stabilization period.

When the mancozeb, the manganese salt and the zinc salt are respectively the maneb, the manganese sulfate and the zinc sulfate, the mass ratio ranges are as follows:

ambam, manganese sulfate, zinc sulfate=90:35-55:6-17

Preferably, the ratio of the ambam to the manganese sulfate to the zinc sulfate=90:41 to 45:7 to 9

Further, ambam, manganese sulfate, zinc sulfate=90:41:7

When the mass ratio of the three is equal to that of mancozeb (100 mancozeb) to that of manganese sulfate to zinc sulfate=90:41:7, the mass of the water-soluble polymer auxiliary agent added to the component B in which the zinc salt of manganese salt is dissolved with as little water as possible is preferably not higher than 5% in general so that a cloudy state does not occur.

Stabilization period

The mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension prepared by the invention is a solution with transparent appearance and apparent water solubility, but is not a solution with thermodynamic stability. Thus, the time that the nanosuspension remains in the apparent transparent state is not infinitely long, but there is a stationary phase. In view of the characteristics of the spraying operation, the required operation time should be at least more than 1 hour after the nano-suspension is prepared, so that the length of the stabilization period can be described in terms of hours. Thus, the present invention proposes the concept that a nanosuspension below 100nm exists with a "stationary phase". Namely, the nano-suspension with the wavelength of less than 100nm prepared by the method can finish spraying operation within the period that the solution keeps transparent, and the stable period is at least 1 hour.

From an application point of view, the stationary phase can be further divided into 4 time periods: within 1 hour, 1 to 2 hours, 2 to 5 hours and more than 5 hours.

During the stationary phase, the nanoscale suspension remains transparent, i.e. it is ensured that the particle size is still less than 100nm.

Hour-level stationary phase

From the point of view of the spraying operation, analysis:

The stabilizing time is about 1 hour, and the operation time for spraying operation is not enough; multiple-formulated nanosuspensions with stability periods exceeding 5 hours are difficult to achieve.

The stabilizing time is between 2 and 5 hours, and the spraying operation of most pesticide appliances can be completed in the time.

The hour-level stabilization period refers to a stabilization time of 1-5 hours.

For the hour-level stabilization period, a refinement stage may also be performed.

1-2 Hours is the basic period of the spraying operation; in most cases the spraying device is capable of performing the task.

2-5 Hours is the full period of the spraying operation; can be suitable for delayed spraying operation in special situations.

Components and auxiliary agents of mancozeb/myclobutanil/amino-oligosaccharin nano suspension

The traditional mancozeb/myclobutanil pesticide preparation, such as wettable powder, is usually only one component, and can be sprayed after being diluted by water, but the pesticide particle size is above micron. In order to obtain the nano-scale suspension, at least two component modes are adopted, and water is added for dilution according to a certain method, so that the nano-scale mancozeb/myclobutanil/amino-oligosaccharin suspension below 100 nanometers can be obtained.

Two component scheme

The mancozeb suspension below 100 nanometers has an hour-level stability period and is a system formed by mixing and reacting two components. They are respectively:

Component A: the transparent aqueous solution is formed by combining ambam (or ambam sodium and ambam potassium), myclobutanil/amino-oligosaccharin nanoemulsion and water. Wherein, the precursor of the mancozeb is generated, and the water-soluble polymer surfactant and water which have the functions of dispersion, suspension and stabilization are the basic components of the component A. On the basis, the nano emulsion of the active ingredients can be added.

In the component A, the myclobutanil and amino-oligosaccharin nanoemulsion contains a certain amount of water-soluble polymer auxiliary agent. If necessary, a water-soluble polymer auxiliary agent may be further added.

The component B is a system of a mixture of inorganic manganese salt and zinc salt according to a certain proportion, and the system has three forms: solid inorganic manganese salt and zinc salt (component B ₁), aqueous solution of inorganic manganese salt and zinc salt (component B ₂), aqueous solution of inorganic manganese salt and zinc salt and water-soluble polymer auxiliary agent (component B ₃).

Since the solubility of inorganic manganese salts and zinc salts in water is limited, it is necessary to limit the amount of water used in order to reduce the capacity of component B as much as possible. In addition, the solubility of the inorganic salt is also influenced by the dosage of the auxiliary agent, so that the addition amount of the water-soluble polymer auxiliary agent in the component B is limited.

B ₃ belongs to the improvement scheme, and consists in distributing the water-soluble polymer auxiliary agent into the component A and the component B. In view of the several limitations of component B, there is an upper limit on the proportion of water-soluble polymeric adjuvants in component B, unless the limitation of component B on certain capacity is not taken into account.

Component proportion of mancozeb/myclobutanil/amino-oligosaccharin nano suspension

The two-component scheme comprises three active ingredients: mancozeb, myclobutanil and amino-oligosaccharin.

Component A: the azoxystrobin/amino oligosaccharin nano emulsion is used as the aqueous solution of the ambam (or the sodium, potassium), or the mixture of at least two of the azoxystrobin and the potassium, and then the auxiliary agent can be continuously added.

Component B: dissolving manganese sulfate (or manganese acetate, manganese chloride and manganese nitrate) and zinc sulfate (or zinc acetate, zinc chloride and zinc nitrate) in water according to a certain proportion; adjuvants may also be added.

In the component A and the component B, the amount of the active ingredient is the basis for determining the constitution of the two components. The mancozeb (or maneb sodium and maneb potassium) in the component A is a precursor for generating nano mancozeb and is a basis for determining the composition of the component B.

The invention is exemplified by the application of 1/15 hectare field if 100 g mancozeb, 4 g myclobutanil, 6 g amino oligosaccharin are required. Two-component design was performed based on the formation of (100+4+6) g of a sub-100 nm mancozeb/myclobutanil/amino oligosaccharin nanosuspension.

Component a, requiring, as precursors, ambam or sodium, potassium, preferably ambam, about 90 grams; 100g of myclobutanil/amino-oligosaccharin nanoemulsion (containing 4 g of myclobutanil and 6g of amino-oligosaccharin, and a certain amount of auxiliary agent) is distributed in the component A according to the distribution principle of the auxiliary agent in the component A and the component B, and most of the auxiliary agent is distributed in the component A. If the component A and the component B are calculated according to the mass packaging specification of 500 g, the water consumption is the quantity obtained by subtracting the ambam, the myclobutanil/amino-oligosaccharin nanoemulsion and the high molecular auxiliary agent.

Component B, the amount of inorganic manganese and zinc salts required for reaction with ambam is determined. Manganese sulfate and zinc sulfate are preferred in the present invention. It is generally believed that manganese ions react with mancozeb to form salts in place of ammonium ions, resulting in a mancozeb cyclic or linear polymer structure, while zinc ions complex with sulfur atoms on mancozeb molecules to form complex structures.

Mass ratio of ambam to manganese sulfate to zinc sulfate

The ambam and the manganese ions and the zinc ions are not strictly mixed, and the industrial production ensures the reaction to be complete, and the ratio of the three used is large, which is the upper limit. The invention adopts the proportion lower than that, the reason is that: ① The manganese and zinc ions have large dosage and high concentration, which is not beneficial to the formation and stability of small-size grains; ② The low-dosage manganese salt and zinc salt are used, and even if the reaction is insufficient, all the components of the low-dosage manganese salt and zinc salt are bactericides which can be independently used; ③ The preparation process of the nanometer suspension liquid does not need to wash, separate and dry mancozeb in industrial production, and does not lose components. The molecular ratio and mass of the three are as follows:

Mancozeb (100 mancozeb produced) to manganese sulfate to zinc sulfate=1:0.8:0.15 (molecular ratio); 90:55:17 (mass ratio) (theoretical upper limit)

Preferably, the ratio of mancozeb (100 mancozeb formation) to manganese sulfate to zinc sulfate=1:0.64:0.08 (molecular ratio); 90:43:9 (mass ratio) (industrial production ratio)

More preferably, ambam (100 mancozeb) to manganese sulfate to zinc sulfate=1:0.6:0.06 (molecular ratio); 90:41:7 (mass ratio) (practical application)

Dispensing of auxiliary agent of component A and component B

The auxiliary is mainly in the component A.

The component A mainly contains metiram (or metiram sodium and metiram potassium) and myclobutanil/amino-oligosaccharin nano emulsion.

The reason that the component A and the component B must be dispensed is that the two react when mixed together. If a two-component approach is used, the myclobutanil/amino-oligosaccharin nanoemulsion in component A contains an adjuvant, and an additional adjuvant is needed unless a third component is added as a separate adjuvant. This complicates the components and dilution process. The condition of adding the auxiliary agent in the component A is as follows: both the ambam and the auxiliary agent are dissolved in water and can be mixed, and unstable phenomena such as precipitation and the like can not occur. However, due to the fact that the content of the ambam and the auxiliary agent is high, the viscosity of the ambam and the auxiliary agent is high, the operation is difficult, and therefore a certain amount of water is added to dissolve and dilute the ambam and the auxiliary agent, the viscosity is reduced, and the operation is convenient. The amount of water added, after achieving the above-mentioned objects, should minimize the total mass of component a, reducing the costs of production, packaging and transportation.

The component B is mainly a mixture of manganese salt and zinc salt, or an aqueous solution thereof, or an aqueous solution of a high molecular auxiliary agent thereof.

Component B may be a solid mixture of manganese and zinc salts. It is necessary to dissolve in water before mixing with component A, and for convenience, their aqueous solutions may be used. Their solubility is not high and the amount of water needed is large. Optionally adding or not adding auxiliary agent according to the dissolution condition of the mixed salt. The reasons are two: firstly, a large amount of auxiliary agent is added into the component B, and the surface of a mixed solution of manganese salt, zinc salt, auxiliary agent and water can be coagulated to form a film, so that the next operation is influenced; secondly, if the amount of the auxiliary agent in the component A can suspend and disperse the generated mancozeb/myclobutanil nano-crystal grains, the auxiliary agent can be not added in the component B. However, considering that the pesticide is mainly used for pest control of orchards, the spraying water quantity is large, and is usually up to 300 kg/mu. If the amount of auxiliary agent in component A is not sufficient to support the dispersion and suspension of the nanocrystalline particles, an appropriate auxiliary agent should be added to component B. The premise is that the addition of the auxiliary agent is carried out in the mixed aqueous solution of manganese salt and zinc salt, so that the component B still keeps transparent, and the condition of coagulation and film formation on the surface of the mixed solution does not occur.

When the mass ratio of the mancozeb (100 mancozeb) to the manganese sulfate to the zinc sulfate=90:41:7 is adopted, the mass concentration of the added auxiliary agent is generally not higher than 5% in the component B of the mixed solution of the dissolved manganese salt and the zinc salt.

Although both component a and component B can solve the above-mentioned difficulties by expanding the capacity, the increase in the specifications of the amounts of both components undoubtedly increases the production, packaging and transportation costs. By comprehensively considering the factors, on the premise of generating the nano particles of the mancozeb compound pesticide with unit mass, the relationship between the consumption of each component and the specification of the product is balanced, and the auxiliary agent and the water are used as little as possible, which is an important factor to consider.

Water-soluble polymer auxiliary agent

⑴ The water-soluble polymer auxiliary agent with dispersion and suspension functions relates to the size of the mancozeb/myclobutanil nano-grain size generated during the dilution and mixing of two components or three components and important component substances capable of being stably dispersed and suspended.

⑵ The water-soluble polymer auxiliary agent belongs to a polymer surfactant, has the performances of dispersing, suspending, improving viscosity and the like, and is derived from a hydrophobic chain structure and a hydrophilic functional group. These groups distributed on the terminal and pendant groups are hydroxyl, carboxyl, carboxymethyl, sulfonic, sulfuric, phosphoric, amino, quaternary ammonium groups, etc. According to the nature of the hydrophilic group, natural and synthetic polymers are classified as anionic, cationic, nonionic and zwitterionic polymers.

⑶ The principle of the invention for selecting the water-soluble polymer auxiliary agent is that ① can stably disperse and suspend the generated pesticide nano-crystal grains; ② Is not affected by the reaction of polyvalent metal ions and water-soluble mancozeb; ③ Is as environment-friendly as possible. Therefore, the invention selects the nonionic polymer auxiliary agent of the natural substance derivative. Such as polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymers, various polyoxyethylene ethers having fatty alcohols, fatty acids, fatty amines, alkylphenols, aryl phenols, oleyl groups, etc. as hydrophobic groups, such as peregal (Peregal) series, OP series, tween (Tween) series, polyol series, ricinoleic acid series, alkyl polyglycosides, etc. However, nonylphenol polyoxyethylene ethers having a female toxicity should be avoided.

⑷ The mancozeb/myclobutanil/amino-oligosaccharin nano suspension is produced by the reaction of water-soluble mancozeb (or sodium) with manganese salt and zinc salt in the process of diluting and mixing by adding water, and emulsion particles or nano crystal grains are produced by myclobutanil nano emulsion. The content of the effective components is about 1.00/0.04/0.06 g/liter of water (for example, when the dosage of mancozeb/myclobutanil/amino oligosaccharin is 100/4/6 g/mu respectively, the spraying machine is 100 liters/mu.mu is 1/15 hectare, and the following is the same). The polymer auxiliary agent dosage is controlled, and the mancozeb/myclobutanil nanometer suspension with stable dispersion and the amino oligosaccharin water solution can be obtained.

The consumption of the polymer auxiliary agent is related to the consumption of mancozeb/myclobutanil/amino-oligosaccharin and the dilution water consumption generated by the system. For example, the concentration of the active ingredients is 0.100%/0.004%/0.006%,0.05%/0.002%/0.003% if the dilution water amounts are 100kg and 200kg, respectively, for mancozeb/myclobutanil/amino oligosaccharin are 100/4/6 g/mu, respectively. The concentration of the polymer auxiliary agent is at least in the range of 0.1% -0.2%.

The detection shows that the particle size of the mancozeb/myclobutanil nano suspension is about 30-70 nm. The nanometer suspension can be in a stable state within 2-5 h, does not precipitate or precipitate, and is directly applied to the spraying operation of various pesticide spraying devices.

⑸ The mancozeb/myclobutanil/amino-oligosaccharin nano suspension is mainly mancozeb nano particles, and is formed by reaction in the diluting and mixing process. Not only the synthesis and purification process of the mancozeb technical prepared from the maneb or the maneb sodium in the pesticide technical factory is omitted, but also the multi-step physical processing process of the mancozeb and other technical processed into wettable powder in the pesticide preparation factory is omitted. The solution provided by the invention can be directly applied to plant protection links of agricultural production, the process is obviously energy-saving and environment-friendly, the production cost can be obviously reduced, and the nano suspension dispersion liquid with the mancozeb particle size smaller than 100nm is obtained. The small-size nano particles can fully exert the drug effect, obviously reduce the pesticide dosage and play a role in reducing and enhancing the efficiency in agricultural production.

The flow chart of the preparation of the mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension by dilution with water is shown in figure 2.

The key technology of the invention is as follows:

1. Process for the production of nanosuspensions

The innovation provides a novel mode and a novel method for preparing a nano suspending agent by using a pesticide variety mancozeb which is insoluble in water and organic solvents and contains polyvalent metal ions, and a novel method for preparing the nano suspending agent by compounding the nano suspending agent with other pesticide bactericides and pesticides. The precursor of the target product is mixed with corresponding metal salt by utilizing the process that the pesticide needs to be diluted by adding water, and the mixing and stirring speed of reactants is controlled by utilizing the quick property of ion reaction, so that the directly used nano suspension with the particle size smaller than 100 nanometers is obtained. The method omits the chemical synthesis and purification process of the mancozeb raw medicine prepared from the water-soluble maneb salt in the pesticide raw medicine factory and also omits the multi-step physical processing process of mixing the mancozeb raw medicine and other raw medicines into wettable powder with larger particle size in the pesticide preparation factory. This innovative research idea, mode of preparation and method are the most important key technologies of the present invention. The key technology is also suitable for the process of preparing the nano suspending agent by compounding mancozeb and other pesticides.

2. Dilution water consumption

When the dosages of the component A and the component B are fixed, the dilution water consumption is one of key technologies for controlling the dilution concentration of the two components so as to obtain the mancozeb/myclobutanil/amino-oligosaccharin nano suspension. The amount of dilution water determines the concentration of component a and component B in the diluent. If the water consumption is too small, for example, 20kg, the concentration of the component A and the component B in the diluent is large, the concentration of the produced nanoparticles is high, and the stabilizing time for forming the particle size of 100nm or less is short. If the water amount exceeds 300kg, a transparent diluent can be obtained, but the concentration of the auxiliary contained in the component is significantly reduced, and the stability of the nanosuspension is deteriorated unless the amount of the auxiliary is increased. Thus, when the amounts of component A and component B are fixed, e.g., 500g per component, a suitable dilution water usage, e.g., a water usage range of greater than 20kg and less than 300kg, is one of the key techniques to control the concentrations of the two components and to produce a stable mancozeb/myclobutanil nanosuspension.

3. Types and amounts of adjuvants

The selection and use of the proper types and amounts of auxiliary agents is a key technology for obtaining the mancozeb and the nano suspension of the compound active ingredients. However, when the water-soluble mancozeb salt and the manganese salt zinc salt generate mancozeb nano particles in water, the size of the generated mancozeb nano particles cannot be stabilized only by the dispersion action of a large amount of water and stirring. This is because the particles are not stationary, move continuously, collide with each other, and as a result of the effective collision, the particles merge and grow up, eventually precipitating. An effective method of preventing the size of the formed particles from becoming larger is to select a suitable type of auxiliary agent (also called a dispersant) and determine the appropriate amount thereof so that the formed nanoparticles are uniformly dispersed in the aqueous solution formed by the dispersant. The dispersant is water soluble polymer and may be dissolved in water. The microscopic state of the water-soluble polymer in water is usually present as random coils. The size of the random coil is far larger than that of the newly generated mancozeb particles and myclobutanil particles, and is usually hundreds of nanometers depending on the molecular weight and the concentration. If the nanometer particles of the mancozeb and the composite active ingredient thereof generated at the moment are smaller than 100nm, the particles can enter the random coil, so that the mutual collision among the particles is prevented and slowed down, and the stability of the generated nanometer particles is improved. This is the dispersion, suspension and stabilization that the addition of adjuvants plays.

The invention tests a plurality of different water-soluble polymer types. Among the numerous anionic, cationic and nonionic surfactants, only nonionic polymeric adjuvants have been shown to have the desired effect, such as alkyl alcohols, polyoxyethylene ethers of esters, polyoxypropylene polyoxyethylene ethers of alkylaryl groups, tween-80, alkylpolyglycosides, castor oil polyoxyethylene ethers, fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene ethers, and the like. The anionic surfactant can react with the manganese zinc ions to form water-insoluble precipitate, and the dispersion effect is lost. The invention does not exclude the special case that the optimal combination of the individual cationic surfactants with the appropriate anionic or nonionic surfactants is achieved without precipitation occurring when dissolved in water.

The type and the amount of the water-soluble polymer auxiliary agent used in the invention can be determined by experiments. The judgment conditions are as follows: firstly, the produced mancozeb/myclobutanil/amino-oligosaccharin nano suspension liquid is required to be transparent in appearance and water-soluble in appearance, so that the particle size is ensured to be below 100 nm; secondly, the stabilization time of the transparent nanosuspension is in the range of 2 to 5 hours.

For two-component systems, the auxiliary amounts can be distributed to component A and component B. In principle, the proportions of auxiliary in component A and component B can be arbitrarily allocated if the two components are not capacity-limiting. If there is a limitation on the packaging capacity of the two components, for example, for application to a field of 1/15 hectare (100 g mancozeb is produced), the amount of auxiliary added to component B is greatly limited, considering that the amount of water used to dissolve the manganese salt, zinc salt in component B is large and that the solubility of this inorganic salt solution to the auxiliary is poor. Thus, the amount of the two-component adjuvant dispensed can be determined by the formula:

Auxiliary amount _{( Component (A) B)} = total auxiliary amount-auxiliary amount _{( Component (A) A)} -auxiliary amount _{( Nanoemulsion )}

The amount of auxiliary agent of the present invention is affected by the amount of dilution water. The dilution water consumption is large, and the addition agent consumption is properly increased. The ratio of the amount of auxiliary agent to the amount of dilution water is at least within 1:1500, preferably within 1:1200, more preferably within 1:1000.

4. Addition mode and stirring mode

The feeding mode is also one of important factors influencing the performance of the mancozeb/myclobutanil/amino-oligosaccharin nano suspension. How does the dilution water usage and the ratio of the components a and B distributed after they are determined, during mixing? The size and stability of the resulting particles are affected. For example, the manner of joining may involve the following problems:

whether diluent of component a is added to diluent of component B or diluent of component B is added to diluent of component a?

How does it add? Is pouring into the container for addition, adding in thin stream, or dripping? Is spray addition? Is single point addition, or multiple point addition? Is continuous or intermittent? Etc.

In practice, after the addition mode is determined, stirring mode problems are also involved. Likewise, there are different ways to stir, be it manual stirring, or mechanical stirring? Is single point stirring, or multi point stirring? Is continuous stirring or intermittent stirring? Etc. The stirring mode is closely related to the stirring speed.

The method of feeding, the stirring method and the stirring speed are all related to the concentration of the reactant in the reaction area formed by mixing the two-component diluent instantly and the problem of rapid dispersion of the product. The most direct method for judging the two modes and the standard of stirring speed is to observe whether the product in the system is in a transparent state or not. If the resulting nanosuspension is clear and transparent and has a long settling time, it is indicated that the addition mode is appropriate and that the stirring mode and stirring speed are effective.

Preparation method of mancozeb/myclobutanil/amino-oligosaccharin nano suspension

For the two-component scheme, the invention adopts the following technical scheme:

adding the component A diluent to the component B diluent or adding the component B diluent to the component A diluent under the condition that the stirring speed is not less than the effective stirring speed; the nanometer suspension of mancozeb/myclobutanil is produced.

The component A diluent and the component B diluent are respectively aqueous solutions formed by diluting the component A and the component B with water;

component A: consists of water-soluble mancozeb or water-soluble maneb aqueous solution and water-soluble polymer auxiliary agent; the water-soluble mancozeb is one of maneb, maneb sodium and maneb potassium or a mixture of at least two of the mancozeb, the maneb sodium and the maneb potassium;

meanwhile, the component A is added with the myclobutanil/amino-oligosaccharin nanoemulsion;

Component B: is a mixture of manganese salt and zinc salt or an aqueous solution thereof, which are formed by a certain proportion.

The adding mode, adding speed and stirring speed are controlled, so that 100 nanometer mancozeb/myclobutanil nano-crystal grains are generated in the suspension, and the final suspension is the 100 nanometer mancozeb/myclobutanil/amino-oligosaccharin nano-suspension.

Stirring mode

And (3) manually stirring: this comparison is consistent with most application scenarios; in this case, the stirring speed must meet the physiological requirements of manual stirring and cannot be too fast.

Mechanical stirring: in the field, it is difficult to provide a large container with a stirring device. If such conditions are met, the rotational speed of the large stirring device is typically no more than 100 revolutions per minute. Stirring at a rotational speed close to this is sufficient.

For the manual stirring mode, the stirring speed is required to be in accordance with the operation speed of the physiological function of the human body. In order to obtain a stable target product, the material adding speed can be properly reduced, and the material adding speed is determined by observing that the product presents a transparent state in the system.

Mode and rate of addition

In order to make the added materials more uniform and fine, the materials are rapidly dispersed after entering the system, and one component can be added into the other component in a continuous mode, or can be added in intermittent components or dropwise. For the dripping mode, a manual sprayer commonly used in rural areas can be used for spraying and adding, and the adding mode has the best effect. The adding speed is still determined by observing the transparent state of the product in the system.

For the existing pesticide preparation, water is used as a dispersion medium for spraying, the pesticide preparation is usually required to be diluted by adding water before spraying, or the commonly used pesticide preparations are required to be mixed together, and the process is commonly called "barrel mixing". The invention utilizes the process of 'barrel mixing', and the component A and the component B are mixed according to a certain concentration, a certain adding mode and adding speed under the action of a specific auxiliary agent-dispersing agent, thereby directly obtaining 'barrel mixing' transparent mancozeb/myclobutanil/amino-oligosaccharin nano suspension which can be sprayed on site.

Dilution water consumption

Current experimental data shows that: the starting range is reasonable up and down to 50 kg. This dilution water usage has a strong correlation with our target stationary phase. This is a problem of multiple variables, and the content of adjuvants in the composition, the composition of adjuvants, are also influencing factors.

The purpose of the invention is to obtain a mancozeb/myclobutanil/amino-oligosaccharin suspension at a transparent stabilization period below 100nm for 2-5 hours. When the mass of the precursor per unit mass (for example, 90 g of ambam) and the metal salt (manganese sulfate, zinc sulfate) reacted therewith are fixed, and the mass of myclobutanil and amino-oligosaccharin are also fixed, factors that can affect the nano-size and stability properties of the microparticles also include: dilution water consumption, auxiliary agent consumption and preparation method.

The dilution water consumption can influence the size of the generated nanometer mancozeb crystal grain and the stability period. The reason is that the water is used as a dispersion medium, the concentration of the ambam solution, the manganese sulfate solution and the zinc sulfate solution at the moment of contact reaction and the uniformity of dispersion are affected, and the size of the generated crystal grains, the dispersion effect of the crystal grains and the opportunity of aggregation and growth of the crystal grains are also affected. The amount of auxiliary agent used affects the concentration of the aqueous solution in different water consumption, the size of the dispersion, suspension and stabilization effect and the length of the stabilization time of the generated nano crystal grains. The water consumption is too small, so that a limit is generated, for example, when the water consumption is diluted to 20 kg, the stable time for generating the transparent mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension is about 1 hour, and the spraying operation time cannot be fully ensured. Therefore, the dilution water amount needs to be increased.

The invention selects the dilution water consumption between 30-300 kg, preferably between 50-200 kg for generating 100 g of target product, namely mancozeb suspension with 2-5 hours of transparent stabilization period below 100 nm.

Three-component basic scheme

The basic scheme of the mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension below 100 nanometers is a system formed by three components. They are respectively:

Component A': consists of mancozeb, maneb sodium or maneb potassium solid or aqueous solution thereof, which is a precursor for generating mancozeb nano-crystalline grains.

Component A' may be amitraz or amitraz sodium, amitraz potassium, or a mixture thereof. The single component or the mixture of the two or the three components can be solid, so that the packaging is simple and convenient, the volume is small, the water-soluble compound can be dissolved in water before use and can be dissolved rapidly, but the water-soluble compound can also be used as an aqueous solution, and the water-soluble compound can be directly diluted to a certain volume before use. The component A' can be added with or without adding water-soluble polymer auxiliary agent with certain mass.

Component B': consists of manganese salt and zinc salt solids or aqueous solution thereof in a certain proportion, which are polyvalent metal ions required for generating mancozeb nano-crystalline grains.

The component B' is a mixture of inorganic manganese salt and zinc salt according to a certain proportion. The manganese salt is selected from at least one of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate; the zinc salt is at least one selected from zinc sulfate, zinc acetate, zinc chloride and zinc nitrate. The component B' may be a solid, so that the package is small in volume, or an aqueous solution thereof may be used. Because of the limitation of the solubility, the formed solution has larger capacity, and is not beneficial to storage and transportation, but is convenient to use. The component B' can be added with or without adding water-soluble polymer auxiliary agent with certain mass.

Component C: myclobutanil/amino-oligosaccharin nanoemulsion

The myclobutanil/amino-oligosaccharin nanoemulsion is used as a component C. The myclobutanil/amino-oligosaccharin nano emulsion contains a certain mass of water-soluble high molecular auxiliary agent. If desired, water-soluble polymeric auxiliaries may also be added or not to component C.

The total mass of the water-soluble polymer auxiliary agent required by the three-component scheme is distributed in the component A ', the component B' and the component C and also contained in the myclobutanil/amino-oligosaccharin nanoemulsion in the component C.

Four component basic scheme

The basic scheme of the mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension below 100 nanometers is a system formed by four components. They are respectively:

Component B _i: consists of manganese salt solid or aqueous solution thereof according to a certain proportion, which is manganese metal ion required for generating mancozeb nano-crystalline grains.

The manganese salt is at least one selected from manganese sulfate, manganese acetate, manganese chloride and manganese nitrate.

The component B _i can be solid, and has small package volume; but also an aqueous solution thereof. The solution is limited by the solubility, has larger capacity, is unfavorable for storage and transportation, and is convenient to use.

The component B _i can be further added with a water-soluble polymer auxiliary agent with certain mass.

Component B _ii: consists of zinc salt solid or aqueous solution thereof according to a certain proportion, which is zinc metal ion required for generating mancozeb nano-crystalline grains.

The zinc salt is at least one selected from zinc sulfate, zinc acetate, zinc chloride and zinc nitrate.

The component B _ii can be solid, and has small package volume; the aqueous solution can be limited by the solubility, the solution capacity is large, the storage and the transportation are not facilitated, and the use is convenient.

The component B _ii can be further added with a water-soluble polymer auxiliary agent with certain mass.

Component C: myclobutanil/amino-oligosaccharin nanoemulsion

The total mass of the water-soluble polymeric adjuvants required for the four-component scheme, distributed among component a', component B _i, component B _ii and component C, is also contained in the myclobutanil/amino oligosaccharin nanoemulsion in component C.

The four-component scheme can also be composed of four components of precursor A, manganese salt and zinc salt B, nanoemulsion C and auxiliary agent D.

[ Brief description of the drawings ]

FIG. 1 is a flow chart of a process for preparing a mancozeb original drug and processing the mancozeb original drug into a wettable powder preparation in the prior art;

FIG. 2 schematic flow chart (two components) of preparation of mancozeb/myclobutanil/amino oligosaccharin nanosuspension

FIG. 3 schematic flow chart (three components) for preparing mancozeb/myclobutanil/amino oligosaccharin nano suspension

[ Embodiment ]

The invention relates to a method for preparing a transparent mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension with the size of below 100nm, which comprises the following steps:

in the first step, the component A and the component B are diluted respectively according to different water consumption and different dilution ratios to form a component A diluent and a component B diluent.

Secondly, under the condition of mechanical stirring (preferred) or manual stirring, the stirring speed is not less than the effective stirring speed, and the component A diluent is uniformly added into the component B diluent according to a certain adding mode (continuous or intermittent pouring, dripping, spraying and the like); or in the reverse order.

The three-component scheme comprises the following operation steps:

in the first step, the component A 'and the component B' are diluted respectively according to different water consumption and different dilution ratios to form a component A 'diluent and a component B' diluent.

And secondly, adding the component C into the component A' diluent, and stirring and dispersing uniformly.

Thirdly, under the condition of mechanical stirring (preferred) or manual stirring, the stirring speed is not less than the effective stirring speed, and the component A 'and the component C diluent are uniformly added into the component B' diluent according to a certain adding mode (continuous or intermittent pouring, dripping, spraying and the like); or in the reverse order.

The following are examples:

Example 1

The mancozeb/myclobutanil nano suspension can be used for preventing and treating powdery mildew and downy mildew of cucumber, and the effective components of the mancozeb/myclobutanil nano suspension are respectively about 100/4 g/mu, and the dilution water consumption of spraying cucumber is about 45 kg/mu. The precursor mancozeb required to produce 100 grams of mancozeb was about 90 grams.

The components are as follows: the proportions of the components, the amount of dilution water, the amount of water distribution, the sequence and mode of addition and the test results are shown in the following table:

The operation method comprises the following steps:

The component A and the component B were diluted and dissolved in a ratio of 1/2 of the water consumption of 50 kg, respectively. Under the condition of manual stirring, the component A diluent is added into the component B diluent in a continuous dropwise manner or in an opposite manner, so that the mancozeb/myclobutanil nano-suspension with transparent appearance can be obtained. The stabilization time was 4 hours.

Example 2

The mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension can be used for preventing and treating powdery mildew and downy mildew of cucumber, the dosage of the active ingredients is respectively 60/4/4 g/mu, and the dilution water consumption is about 50 kg/mu. The precursor mancozeb required to produce 60 grams of mancozeb was about 54 grams.

The operation method comprises the following steps:

The components A 'and B' are diluted and dissolved according to the proportion of 3/5 and 2/5 of the water consumption of 50 kg respectively, and then the component C is added into the diluted solution of the component A 'to be uniformly dispersed, so as to form the mixed diluted solution of the component A' and the component C. And adding the component B 'diluent into the mixed diluent of the component A' and the component C in a continuous spraying mode under stirring to obtain the mancozeb/myclobutanil/amino-oligosaccharin nano suspension with transparent appearance, wherein the stability time is 5 hours.

Example 3

The mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension can be used for preventing and treating pear scab, apple tree ring rot and alternaria leaf spot, the dosage of the active ingredients is about 100/4/6 g/mu respectively, and the dilution water consumption is about 250 kg/mu. The precursor mancozeb required to produce 100 grams of mancozeb was about 90 grams.

The operation method comprises the following steps:

The component A and the component B are diluted and dissolved according to the proportion of 2/3 and 1/3 of the water consumption of 250 kg respectively. And adding the component B diluent into the component A diluent in a continuous trickle adding mode under stirring to obtain the mancozeb/myclobutanil/amino-oligosaccharin nanometer suspension with transparent appearance, wherein the stability time is 5 hours.

Claims

1. The nanometer suspension for preventing and treating powdery mildew of cucumber is characterized by being 100 nanometers or less; the nanometer suspension is formed by diluting and mixing two components with water:

component A: a water-soluble mancozeb salt or a water-soluble maneb salt aqueous solution, a water-soluble polymer auxiliary agent and water; the water-soluble mancozeb is one of maneb, maneb sodium and maneb potassium or a mixture of at least two of the mancozeb, the maneb sodium and the maneb potassium;

meanwhile, the component A is added with the myclobutanil nanoemulsion or the myclobutanil and amino-oligosaccharin compound nanoemulsion;

Component B: is a mixture of manganese salt and zinc salt according to a certain proportion; the manganese salt and zinc salt are respectively at least one kind of salt composition substance.

2. The nanosuspension according to claim 1, wherein the nanosuspension of 100 nm or less has an hour-scale stability period.

3. The nanosuspension according to claim 1, wherein component B, is added with a water-soluble polymeric auxiliary agent and water to form an aqueous solution.

4. The nanosuspension according to claim 1, wherein the water-soluble polymeric adjuvant is a nonionic surfactant.

5. The nanosuspension according to claim 1, wherein the ratio of the amount of water-soluble polymeric auxiliary agent to the amount of dilution water is not more than 1:1200.

6. The nanosuspension according to claim 1, wherein when the mancozeb, manganese salt and zinc salt are respectively mancozeb, manganese sulfate and zinc sulfate, the mass ratio ranges are as follows:

ambam, manganese sulfate, zinc sulfate=90:41-55:7-17

Preferably, the ratio of ambam to manganese sulfate to zinc sulfate=90:41 to 43:7 to 9.

7. The nanosuspension according to claim 4, wherein the nonionic surfactant is at least one of the following options: water-soluble starch and its derivatives, water-soluble guar gum and its derivatives, polyoxypropylene-polyoxyethylene block copolymer, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ether, fatty amine polyoxyethylene ether, alkylaryl polyoxypropylene polyoxyethylene ether, aryl phenol polyoxyethylene ether, OP-10, castor oil polyoxyethylene ether, alkyl polyglycoside, tween, polyvinyl alcohol, polyvinylpyrrolidone.

8. The nanosuspension according to any one of claims 1 to 7, wherein the manganese salt is selected from at least one of manganese sulphate, manganese acetate, manganese chloride, manganese nitrate; the zinc salt is at least one selected from zinc sulfate, zinc acetate, zinc chloride and zinc nitrate.

9. A process for the preparation of a nanosuspension for controlling powdery mildew of cucumber according to one of claims 1 to 8; adding the component A diluent into the component B diluent under the condition that the stirring speed is not less than the effective stirring speed; or adding the component B diluent into the component A diluent to form ternary compound nano suspension.

10. The method of claim 9, wherein one component is added to the other component in one of four ways: continuously adding, intermittently adding, dripping, and spraying.