CN107593694B - Aqueous emulsion - Google Patents
Aqueous emulsion Download PDFInfo
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- CN107593694B CN107593694B CN201710778210.7A CN201710778210A CN107593694B CN 107593694 B CN107593694 B CN 107593694B CN 201710778210 A CN201710778210 A CN 201710778210A CN 107593694 B CN107593694 B CN 107593694B
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Abstract
The invention provides an aqueous emulsion which comprises the following raw materials in percentage by mass: 10% of a mixture of difenoconazole and flusilazole, 10% of a solvent DMF 10%, 602# 15% of an emulsifier, deionized water and the balance. According to the aqueous emulsion provided by the invention, the protective flusilazole and the systemic difenoconazole are compounded together, so that the resistance of plant pathogenic bacteria to the difenoconazole and the flusilazole can be delayed, the difenoconazole can be absorbed by plants to play a bactericidal effect, and the flusilazole with a protective effect can be left on the surfaces of the plants to prevent and treat pathogen invasion and infection. The emulsion in water provided by the invention has excellent physicochemical properties such as transparency, precipitation amount, emulsion appearance, dispersibility, stability, cold and hot storage stability and the like, and can be used for preventing and treating various fungal diseases.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to an aqueous emulsion.
Background
Currently, the development of new formulations of pesticides aimed at high efficiency, safety, economy and convenience has attracted much attention. The novel preparation has the characteristics that: water-based, granular, slow-release, low-toxicity, multifunctional and labor-saving. The water-based preparation refers to a pesticide preparation prepared by taking water as a matrix, such as a suspending agent, an aqueous emulsion, a microemulsion and the like. The traditional liquid pesticide is mainly emulsifiable concentrate, a large amount of organic solvent is required to be added when the emulsifiable concentrate is produced, the organic solvent is mainly triphenyl which is inflammable and explosive, harmful to human and livestock and pollutes the environment, the traditional liquid pesticide is extremely unsafe in the production, storage, transportation and use processes, and developed countries prohibit or partially prohibit the application of the traditional liquid pesticide on fruit trees and vegetables.
An emulsion in water (EW), also called dense emulsion, is an environment-friendly pesticide preparation formed by dispersing a water-insoluble solution obtained by dissolving a water-insoluble liquid technical material or a solid technical material in an organic solvent in water, and the appearance of the environment-friendly pesticide preparation is opaque white emulsion. Adding an auxiliary agent and enabling the oil phase to be uniformly distributed in the water phase through a special processing technology to form a stable water emulsion system. The oil droplets usually have a particle size of 0.7 to 20 μm, preferably 1.5 to 3.5 μm.
The emulsion in water uses water to replace all or most of organic solvents, the particle size of the dispersed active ingredient drops is less than 2 microns, the appearance is white milk-shaped, the appearance is not different from that of emulsifiable solution poured into water when the active ingredient drops are diluted by water, and the emulsion in water is easily recognized and accepted by brothers of farmers. Compared with missible oil, it has more advantages: because the environment-friendly glass fiber reinforced plastic composite material does not contain or only contains a small amount of toxic and flammable organic solvent, the environment-friendly glass fiber reinforced plastic composite material has no danger of fire explosion, no unpleasant toxic odor and small irritation to eyes, reduces the pollution to the environment and greatly improves the safety of production, storage, transportation and users; the cheap water is used as a substrate, so that the manufacturing cost is reduced in different ranges; the requirement on a packaging container is far less harsh than that of missible oil, so that the packaging cost can be reduced; the toxicity to warm-blooded animals is greatly reduced, the pesticide is safer than missible oil to plants, and the miscibility with other pesticides and fertilizers is good; the atomized fog drops have larger grain diameter than missible oil when being sprayed, can reduce the drift of effective components and the pollution to the environment, and has no phenomena of residue after spraying wettable powder and shedding of fruit powder after spraying the missible oil after application.
Flusilazole (flusilazole) and difenoconazole (difenoconazole) both belong to novel triazole bactericides and have the effects of broad spectrum, systemic absorption, treatment, eradication and the like. The bactericide has a special action mechanism, the mechanism is that the biosynthesis of ergosterol on the cell membrane of pathogenic bacteria is destroyed, so that the cell membrane can not be normally synthesized to kill the pathogenic bacteria, the bactericide is effective on ascomycetes and fungi imperfecti, and the flusilazole and the difenoconazole are widely used for preventing and treating various diseases such as scab, powdery mildew, leaf spot, rust disease, anthracnose, black spot, anthracnose, gummy stem blight, red spot and the like of various crops such as fruit trees, vegetables and the like at present.
The compounding of the pesticide can mix two pesticides with different action modes together according to a certain proportion, so that the two different pesticides play the greatest role, but how to compound the pesticides specifically can ensure that the compounded pesticides have excellent physicochemical properties such as transparency, precipitation amount, emulsion appearance, dispersibility, stability, cold and hot storage stability and the like is the research direction of technicians in the field at present.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provide the compound pesticide emulsion in water with excellent physicochemical properties such as transparency, precipitation amount, emulsion appearance, dispersibility, stability, cold and hot storage stability and the like.
The aqueous emulsion comprises the following raw materials in percentage by mass:
further, the weight ratio of the difenoconazole to the flusilazole in the aqueous emulsion is 1:9.
Has the advantages that:
according to the aqueous emulsion provided by the invention, the protective flusilazole and the systemic difenoconazole are compounded together, so that the resistance of plant pathogenic bacteria to the difenoconazole and the flusilazole can be delayed, the difenoconazole can be absorbed by plants to play a bactericidal effect, and the flusilazole with a protective effect can be left on the surfaces of the plants to prevent and treat pathogen invasion and infection. The emulsion in water provided by the invention has excellent physicochemical properties such as transparency, precipitation amount, emulsion appearance, dispersibility, stability, cold and hot storage stability and the like, and can be used for preventing and treating various fungal diseases.
Drawings
FIG. 1 is a spectrum of a difenoconazole technical material HP L C;
FIG. 2 is a spectrum of HP L C;
FIG. 3 is a spectrum diagram of HP L C of a sample of difenoconazole-fluorosilicone emulsion in water.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Selection of solvents
Since the difenoconazole and flusilazole raw medicines are solid medicines, a solvent is selected to dissolve the raw medicines. Putting a certain amount of original drug in a test tube, respectively adding different solvents, observing the dissolution condition at room temperature, and selecting the solvent which has the minimum solvent dosage and the best dissolution effect and does not precipitate the original drug at 0 ℃ as the solvent in the preparation of the aqueous emulsion. Selection of the solvent requires: 1. the solubility to the original medicine is good; 2. the physical and chemical properties of the solvent are stable; 3. the toxicity to human, livestock and plants is low; 4. together with the surfactant, reduce surface tension and increase fluidity.
Selection of emulsifiers
The dispersibility and the grain size of the aqueous emulsion and the dosage of the emulsifier are closely related to the type of the emulsifier. Emulsifiers are a prerequisite for the preparation of aqueous emulsions.
The principle of emulsifier selection is that according to the requirement of an emulsion stability determination method in the national standard GB/T1603-2001, the type of a single-agent emulsifier is selected by weighing 1g of difenoconazole and flusilazole according to the proportion of 1:9, adding a solvent with good solubility which is sieved out, adding the solvent with the addition of 1.5g, dissolving (dissolving and weighing on a balance), then weighing 1.5-2 g of the emulsifier, adding the emulsifier into the solution, uniformly stirring, sucking 1ml of a sample at the temperature of 30 +/-2 ℃, slowly dropping the sample into 200ml of standard hard water (the hardness of the standard hard water is 0.342 g/L calculated by calcium carbonate) at the position 2cm away from the water surface, and preparing the emulsifier by weighing 0.304g of anhydrous calcium chloride and 0.139g of magnesium chloride with crystal water into a 1000ml volumetric flask, dissolving the anhydrous calcium chloride and the magnesium chloride with the crystal water into a graduated beaker with distilled water, and observing the emulsifier is repeatedly repeated three times, wherein the emulsification standard is shown in Table 1.
TABLE 1 relationship between the dispersed state and emulsified state of oil phase in water and evaluation level
According to the method, the screened emulsifier is subjected to further cold storage and hot storage experiments, and the specific method comprises the following steps: cold storage stability: placing 10ml sample in 20ml test tube with plug, placing in refrigerator at 0 + -2 deg.C, storing for 7 days to maintain uniform emulsion, and obtaining qualified product without floating oil on the upper part and precipitate on the lower part. Heat storage stability: 10ml of sample is put into a 20ml test tube with a plug and stored in an incubator at the temperature of (54 +/-2) DEG C for 14 days, and the emulsion is required to keep uniform and transparent in appearance, and if a small amount of layering occurs, the sample can be recovered after slight shaking, and the sample is also regarded as qualified.
Selection of water
Water is the main component of the aqueous emulsion, and the content of the effective components of the aqueous emulsion is determined by the total proportion of the water. The water quality has great influence on the emulsified state and physical properties of the aqueous emulsion. When the emulsifier in the formula of the aqueous emulsion is determined, the hardness of water in the formula should be relatively stable. The water quality is changed, and the formula is also adjusted correspondingly. Preparing water with different hardness, performing a preparation experiment of the aqueous emulsion, and determining the stability, the decomposition rate of active ingredients and other properties of the aqueous emulsion sample stored at 54 +/-2 ℃ for 14 days and 0 +/-2 ℃ for 7 days.
Determination of 10% difenoconazole-flusilazole aqueous emulsion formula
Setting gradient for selected factors of different levels by an orthogonal design experiment method, preparing samples with different formulas to carry out hot storage and cold storage experiments, searching an optimal formula by a range method by taking the layering rate of cold and hot storage of the emulsion in water as a measurement standard, comprehensively observing the emulsion stability of the samples after cold and hot storage, and determining the optimal formula.
Determination of content of effective component after cold and hot storage
Analyzing the content of the effective components after cold storage for 7 days and hot storage for 14 days, and calculating the decomposition rate of the effective components within 24 hours, wherein the effective component is qualified if the decomposition rate is less than or equal to 5 percent, analyzing the content of the effective components of the sample by adopting an HP L C instrument, and comparing the content with the content of the effective components of the sample before cold storage and hot storage, and calculating the formula:
HP L C assay conditions:
a chromatographic column: amethyl C18The mobile phase is determined by searching documents and experiments, wherein the mobile phase comprises methanol and water (volume ratio is 85:15), the detection wavelengths comprise difenoconazole 235nm and flusilazole 220nm, the column temperature is 30 ℃, the flow rate is 1.0ml/min, the sample injection amount is 20 mu l, and the retention time comprises about 7.2min of difenoconazole and about 5.3min of flusilazole (figures 1 and 2).
Processing technology of difenoconazole and flusilazole aqueous emulsion
Usually, according to the requirements of the formula, the raw pesticide, the solvent, the emulsifier and the like are added into the oil phase and uniformly mixed, deionized water is used as a water phase, and the water phase is added into the oil phase under high-speed stirring to form emulsion with good stability, namely the aqueous emulsion. On the basis of a single-factor experiment, 4 factors which have large influence on the properties of the aqueous emulsion are screened out to serve as investigation objects, namely 4 factors including solvent content (A), emulsifier content (B), water quality type (C) and solvent type (D), each factor selects 3 levels to perform orthogonal test analysis, and the layering rate of the aqueous emulsion is used as an evaluation index to screen out the optimal processing technology.
Method for measuring pH value of 10% difenoconazole-flusilazole aqueous emulsion
Experiments were performed according to GB/T1601-1993. Taking 1g sample, adding 100ml distilled water into 250ml beaker, stirring for 1min, standing for 1min, and measuring pH value by corrected pH meter.
Screening result of 10% difenoconazole-flusilazole aqueous emulsion solvent
According to the physicochemical properties of difenoconazole and flusilazole, solvents such as mixed xylene, ethanol, cyclohexanone, acetone, toluene, ethyl acetate, N-N Dimethylformamide (DMF), N-propanol and the like are selected from organic solvents for screening, the result shows that the DMF has the best dissolving effect on the two raw medicines after mixing, and the screening result is shown in Table 2.
Table 2 results of solvent screening
As shown in table 2, when the amount of the solvent used was 15%, the crude drug was still not dissolved, and the toluene and xylene were discarded in consideration of the addition of other additives. Acetone as a solvent has a good dissolving effect at normal temperature, but is not used because the flash point is too low. The solvent selected from N-propanol, N-dimethylformamide, dimethyl sulfoxide and cyclohexanone.
The cold-hot storage experiment was performed using the above-selected solvents, and the appearance was observed as shown in Table 3. From the results shown in tables 2 and 3, it is understood that N, N-dimethylformamide is used because dimethyl sulfoxide and cyclohexanone, which are solvents, are required in a large amount to dissolve the original drug and N-propanol is precipitated during the subsequent cold and hot storage.
TABLE 3 Cold and Heat storage status after solvent screening
Screening result of 10% difenoconazole-flusilazole emulsion in water emulsifier
Selection of a single emulsifier is carried out first according to the requirements of GB/T1603-2001. According to the method in GB/T1603-2001, 1.8750g of difenoconazole technical material and 0.2g of flusilazole technical material are weighed, 2g of n-propanol is added for dissolving, 4g of emulsifier is weighed and added into the solution, and the mixture is stirred uniformly. At room temperature, 1ml of the sample was dropped into 200ml of standard hard water at a height of 2cm from the water surface to observe the dispersion. The results are shown in Table 4.
TABLE 4 emulsifier test results
Note: +, -standard number of stages of dispersion, ↓isprecipitated, → is not precipitated,
× respectively representing pass and fail
As shown in Table 4, the emulsifying effect of NP-10, TX-10 and 602# is good, no precipitate exists after 24h, and the experimental process observation shows that the emulsifying effect of 602# is superior to that of NP-10 and TX-10, so 602# is selected as the emulsifier.
Results and analysis of orthogonal experiments
On the basis of the early single-factor experiment, the processing technology of 10% difenoconazole-flusilazole aqueous emulsion is perfected by the orthogonal experiment. Four factors which have great influence on the preparation of the aqueous emulsion are selected, and three levels are set for each factor and are shown in table 5. The results of the hot storage orthogonal experiment are shown in Table 6, and the results of the cold storage orthogonal experiment are shown in Table 7.
TABLE 5 orthogonal design factor horizon
TABLE 6 orthogonal test results of heat storage
TABLE 7 Cold storage Quadrature test results
As can be seen from Table 6, when the layering rate of the difenoconazole-flusilazole aqueous emulsion during hot storage is taken as an evaluation index, the main and secondary sequences of factors discharged from extreme differences are B & gtC & gtA & gtD, and the optimal proportion is A1B2C3D1Namely, the solvent is N, N-dimethylformamide with the dosage of 10 percent, the emulsifier with the dosage of 15 percent and deionized water for water phase.
As can be seen from Table 7, benzene is usedWhen the layering rate of the aqueous emulsion of the difenoconazole and the flusilazole during cold storage is taken as an evaluation index, the main and secondary sequences of factors discharged by range difference are B & gtC & gtA & gtD, and the optimal ratio is A1B2C3D1Namely, the solvent is N, N-dimethylformamide with the dosage of 10 percent, the emulsifier with the dosage of 15 percent and deionized water for water phase.
The best formula obtained by cold and hot storage is A1B2C3D1Therefore, the final formula is determined by using 10% of N, N-dimethylformamide, 15% of emulsifier and deionized water for water phase as the solvent.
Measurement result of cold and hot storage decomposition rate of 10% difenoconazole and flusilazole aqueous emulsion
The prepared 10% aqueous emulsion of difenoconazole and flusilazole is stored for 7 days at 0 +/-2 ℃ and for 14 days at 54 +/-2 ℃, and an HP L C instrument is adopted to detect the content of the aqueous emulsion sample, so that the degradation rates of the difenoconazole and the flusilazole are less than 5 percent, and the international requirements are met.
Processing method of 10% difenoconazole-flusilazole aqueous emulsion
Dissolving difenoconazole and flusilazole in DMF, adding 602#, stirring uniformly, adding deionized water, stirring for 9.9min by using a high-speed internal cutting disperser 5000r/min to obtain uniform liquid, namely the difenoconazole-flusilazole aqueous emulsion.
Measurement result of pH value of 10% difenoconazole-flusilazole aqueous emulsion
The pH value of the 10% difenoconazole-flusilazole aqueous emulsion is 6.02 by measuring a sample through a pH meter.
Table 810% results of pH value measurement of Difenoconazole Flusilazole aqueous emulsion
With the increasing awareness of people on food safety, the preparation of the emulsion in water is receiving more attention from people and is now a hot spot of current research. Common formulations on the markets of difenoconazole and flusilazole are mainly missible oil and wettable powder, and the emulsion in water is less. The research examines the factors one by one, optimizes the formula of the aqueous emulsion, prepares the aqueous emulsion according to the optimal formula and represents the performance of the aqueous emulsion.
The preparation of the aqueous emulsion is influenced by a plurality of factors, four factors which have great influence on the preparation of the aqueous emulsion are selected on the basis of gradually selecting a solvent, an emulsifier, water quality and the like in the research, three levels are set, the four factors are optimized by adopting an orthogonal design method, and the obtained optimal ratio is as follows: the solvent is N, N-dimethylformamide accounting for 10 percent, the emulsifier is 602# accounting for 15 percent of the total ratio, and the water phase is deionized water accounting for 65 percent.
The preparation of the 10% difenoconazole-flusilazole aqueous emulsion has the advantages that since the difenoconazole and the flusilazole are solid raw medicines, the organic solvent has good solubility to the raw medicines, the physical and chemical properties are stable, crystals cannot be separated out in cold and hot storage, the aqueous emulsion prepared by adopting the N, N-dimethylformamide as the organic solvent has stable physical and chemical properties, and the dissolved medicines have good pourability.
When the aqueous emulsion is prepared, the emulsifier has the function of better dispersing the oil phase in the water phase and dispersing the oil phase into tiny particles which are uniformly distributed in the water phase to form a stable aqueous emulsion system. 602# as an emulsifier has good dispersibility to the aqueous emulsion, and has no floating oil on the upper part and no precipitate on the lower part under the condition of cold and hot storage.
When the aqueous emulsion is prepared, the requirement on water quality is high, and the water quality has an important effect on the stability of the emulsion. Therefore, when the surfactant in the formula of the aqueous emulsion is determined, the hardness of water in the formula also enables the aqueous emulsion system to be relatively stable. And finally, deionized water is used as a water phase, so that the cold and hot storage properties of the aqueous emulsion are stable.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (1)
1. The aqueous emulsion is characterized by comprising the following raw materials in percentage by mass:
the mass ratio of the difenoconazole to the flusilazole is 1:9.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101084752A (en) * | 2007-07-19 | 2007-12-12 | 安徽华星化工股份有限公司 | Germicide composition |
| CN102349506A (en) * | 2011-09-13 | 2012-02-15 | 广西田园生化股份有限公司 | Ultralow-volume solvent containing Flusilazole |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101084752A (en) * | 2007-07-19 | 2007-12-12 | 安徽华星化工股份有限公司 | Germicide composition |
| CN102349506A (en) * | 2011-09-13 | 2012-02-15 | 广西田园生化股份有限公司 | Ultralow-volume solvent containing Flusilazole |
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