CN107593694A - A kind of aqueous emulsion - Google Patents
A kind of aqueous emulsion Download PDFInfo
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- CN107593694A CN107593694A CN201710778210.7A CN201710778210A CN107593694A CN 107593694 A CN107593694 A CN 107593694A CN 201710778210 A CN201710778210 A CN 201710778210A CN 107593694 A CN107593694 A CN 107593694A
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- aqueous emulsion
- flusilazole
- difenoconazole
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Abstract
The present invention provides a kind of aqueous emulsion, its raw material according to mass percent meter, including：The mixture 10% of Difenoconazole and Flusilazole, solvent DMF 10%, emulsifying agent 602#15%, deionized water, surplus.Aqueous emulsion provided by the invention; together with the Difenoconazole compounding of the Flusilazole of protectiveness and absorbability; the resistance of phytopathogen p-phenylene methyl cyclic-azole and Flusilazole can be delayed; Difenoconazole can be absorbed by plant; play the effect of sterilization; and the Flusilazole for having protective effect can stay in plant surface, anti-pathogen invasion infection.The physicochemical properties such as aqueous emulsion provided by the invention its transparency, amount of precipitation, emulsion appearance, dispersiveness, stability, cold thermodynamic stability are excellent, the preventing and treating available for a variety of fungal diseases.
Description
Technical field
The present invention relates to chemical technology field, more particularly to a kind of aqueous emulsion.
Background technology
Currently, with efficient, safety, economy, conveniently developed for the pesticides new formulation of target, extensive pass has been caused
Note.The characteristics of novel form is：Water-borne modification, spheroidizing, sustained releaseization, low toxicityization, multifunction and Labor-saving.Liquid formulation Water-borne modification
Refer to the formulations of pesticide prepared using water as matrix, such as suspending agent, aqueous emulsion and microemulsion.Traditional liquor agricultural chemicals using missible oil as
It is main, substantial amounts of organic solvent is must be added to when producing missible oil, these organic solvents are again with inflammable and explosive, harmful to people and animals, pollution
Based on the triphen of environment, it is absolutely unsafe during production, storing and use, developed country has forbidden or part is forbidden in fruit
Used on tree, vegetables.
Aqueous emulsion (EW) is also known as emulsifiable concentrate, is that liquid active compound or solid-state active compound not soluble in water are dissolved in obtained by organic solvent
Solution not soluble in water, be dispersed in water, a kind of environmentally friendly type pesticidal preparations of formation, its outward appearance is opaque white
Color emulsion.Add auxiliary agent and by special processing technology, be distributed in aqueous phase with making oil phase, form stable water and milk
Agent system.Oil bead diameter is usually 0.7~20 μm, it is usually desirable to 1.5~3.5 μm.
Aqueous emulsion replaces wholly or largely organic solvent with water, and particle diameter is less than 2 microns after active component droplet distribution, outside
White milk shape is seen, being poured into water outward appearance with missible oil when being diluted with water has no difference, easily by peasant brother's recognition and acceptance.
Compared with missible oil, it has the advantages of more：Due to being free of or containing only a small amount of poisonous, inflammable organic solvent, no Fire explosion danger
Danger, it is small to eye irritation without unpleasant toxic odor, reduce the pollution to environment, substantially increase to producing, store and transport and
The security of user；Using cheap water as matrix, manufacturing cost has the reduction of different amplitudes；Requirement to packing container is also remote
Not as missible oil harshness, packing cost can be reduced；Warm-blooded animal toxicity is substantially reduced, to plant than missible oil safety, with other
Agricultural chemicals and fertilizer miscibilty are good；The mist droplet particle size being atomized during sprinkling is bigger than missible oil, can reduce the drift of active ingredient and to environment
Pollution, do not have after wettable powder spray after vestiges and missible oil spray after phenomena such as making fruit powder come off.
Flusilazole (flusilazole) belongs to Novel triazole sterilization with Difenoconazole (difenoconazole)
Agent, there is wide spectrum, interior inhale, treat, rooting out and other effects.The mechanism of action is more special, and its mechanism is on destruction pathogen cell membrane
The biosynthesis of ergosterol, so that cell membrane can not normally synthesize and kill germ, the bactericide is to Ascomycetes and half
Perfect fungus fungi is effective, and Flusilazole, Difenoconazole have been widely used for preventing and treating the black star of the crops such as more planting fruit-trees, vegetables at present
The multiple diseases such as disease, powdery mildew, leaf spot, rust, anthracnose, black spot, anthrachose of grape, blight dis-ease, spot blight, rust.
The compounding of agricultural chemicals can mix the agricultural chemicals of two kinds of different modes of action by a certain percentage, make two kinds of differences
Agricultural chemicals plays maximum effect, but specifically how to compound, and just can guarantee that the agricultural chemicals after compounding in transparency, amount of precipitation, emulsion
It is the direction of current those skilled in the art's research that the physicochemical properties such as outward appearance, dispersiveness, stability, cold thermodynamic stability are excellent.
The content of the invention
It is an object of the invention to solve the defects of above-mentioned prior art is present, there is provided a kind of transparency, amount of precipitation, emulsion
The excellent Recompounded pesticide aqueous emulsion of the physicochemical properties such as outward appearance, dispersiveness, stability, cold thermodynamic stability.
A kind of aqueous emulsion, its raw material according to mass percent meter, including：
Further, aqueous emulsion as described above, the mass ratio of the Difenoconazole and Flusilazole is 1:9..
Beneficial effect：
Aqueous emulsion provided by the invention, can together with the Difenoconazole compounding of the Flusilazole of protectiveness and absorbability
To delay the resistance of phytopathogen p-phenylene methyl cyclic-azole and Flusilazole, Difenoconazole can be absorbed by plant, play and kill
The effect of bacterium, and the Flusilazole for having protective effect can stay in plant surface, anti-pathogen invasion infection.It is provided by the invention
The physicochemical properties such as aqueous emulsion its transparency, amount of precipitation, emulsion appearance, dispersiveness, stability, cold thermodynamic stability are excellent, can use
In the preventing and treating of a variety of fungal diseases.
Brief description of the drawings
Fig. 1 difenoconazole technical material HPLC spectrograms；
Fig. 2 flusilazole HPLC spectrograms；
The HPLC spectrograms of Fig. 3 Difenoconazole Flusilazole aqueous emulsion samples.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below technical scheme in the present invention carry out it is clear
Chu, it is fully described by, it is clear that described embodiment is part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
The selection of solvent
Because Difenoconazole and flusilazole are solid chemicals, therefore solvent need to be selected and dissolve active compound.Take a certain amount of
Active compound is placed in test tube, is separately added into different kinds of liquid solvents, observes its dissolving situation at room temperature, selects solvent load most
Small, solute effect is best, and does not separate out the solvent of active compound as the solvent in aqueous emulsion preparation at 0 DEG C.Solvent is selected to need：
1. the solubility of pair active compound is good；2. the stable in physicochemical property of solvent；3. couple people and animals, the toxicity of plant are low；4. and surfactant
Surface tension is reduced together, increases mobility.
The selection of emulsifying agent
The dispersiveness of aqueous emulsion, the size of particle diameter and the number of emulsifier are closely related with the species of emulsifying agent.Breast
Agent is to prepare the prerequisite of aqueous emulsion.
The principle of emulsifying agent selection：Required according to stability of emulsion assay method in national standard GB/T1603-2001, to single dose
Emulsifier select as follows：Weigh Difenoconazole and Flusilazole according to 1:9 ratios have 1g altogether, add sift out it is molten
Solvent good Xie Du, addition 1.5g are dissolved and (dissolve and weigh on balance).The addition of 1.5~2g emulsifying agents is weighed again
Uniform stirring in solution, under the conditions of 30 ± 2 DEG C, draw 1ml samples and be slowly added drop-wise to equipped with 200ml at water surface 2cm
(standard hard water in standard hard water:For hardness using calcium carbonate as 0.342g/L, compound method is as follows:Weigh anhydrous calcium chloride
0.304g and magnesium chloride 0.139g with the crystallization water are in 1000ml volumetric flask, with the beaker of distilled water dissolved dilution to scale
Middle observation.) every kind of emulsifying agent in triplicate, emulsification standard is shown in Table 1.
The relation of the oil phase of table 1 dispersity, emulsified state and assessment grade in water
Make further cold storage and heat storage to the emulsifying agent filtered out first accordingly to test, specific practice：Cold storage stability：
10ml samples are taken in 20ml tool plug test tubes, are positioned over temperature in the refrigerator of (0 ± 2) DEG C, to preserve 7d, homogeneous emulsus can be kept
Liquid, on without oil slick, lower no precipitation person is qualified.Heat storage stability：Sample 10ml is taken to be positioned over (54 in 20ml tool plug test tubes
± 2) 14d is stored in insulating box DEG C, it is desirable to which emulsion outward appearance keeps transparent and homogeneous, if there is a small amount of layering, after slight shaking
Resilient person is also considered as qualified.
The selection of water
Water is the main component of aqueous emulsion, water account for always than how much decision aqueous emulsions active constituent content.Water quality is to water
The emulsified state and physical property of emulsion have tremendous influence.After the emulsifying agent in water emulsion formula determines, the hard of reclaimed water is formulated
Degree should also be stablized relatively.Water quality changes, and formula also needs accordingly to adjust.The water of different hardness is prepared, the preparation for carrying out aqueous emulsion is real
Test, measure aqueous emulsion sample stores the performances such as 7d stability, active ingredient resolution ratio in 54 ± 2 DEG C of 14d and 0 ± 2 DEG C of storages.
The determination of 10% Difenoconazole Flusilazole water emulsion formula
Gradient is set to the factor of selected varying level with orthonormal design of experiments method, different formulations are made into sample carries out heat
Storage and cold storage are tested, and using the layering ratio of the cold and hot storage of aqueous emulsion as criterion, find optimization formula with range method, comprehensive observing is cold
Sample emulsion stability after heat storage, determines optimum formula.
The measure of active constituent content after cold and hot storage
The active constituent content after cold storage 7d, heat storage 14d is analyzed, and active ingredient resolution ratio, resolution ratio are calculated in 24h
≤ 5% be qualified.Sample carries out the sample active constituent content before active constituent content analysis, with cold and hot storage using HPLC instrument
Contrast.Calculation formula：
HPLC condition determinations：
Chromatographic column：Amethyst C18- H (4.6 ㎜ × 250 ㎜, 5 μm)；Detector：UV-detector.By searching document
Mobile phase is determined with preliminary experiment：Methanol-water (volume ratio 85:15)；Detection wavelength：Difenoconazole 235nm, Flusilazole 220nm；
30 DEG C of column temperature；Flow velocity：1.0ml/min；The μ l of sample size 20；Retention time：Difenoconazole is about 7.2min, and Flusilazole is about
5.3min (Fig. 1,2).
The processing technology of Difenoconazole Flusilazole aqueous emulsion
Typically according to the requirement of formula, active compound, solvent, emulsifying agent etc. are added among oil phase and are well mixed, deionization
Water is aqueous phase, under high velocity agitation, aqueous phase is added in oil phase, it is aqueous emulsion to form the emulsion having good stability.In list
On the basis of Factor Experiment, 4 factors being had a great influence to aqueous emulsion property are filtered out as investigation object, i.e. solvent
(A), 4 emulsifier content (B), water quality type (C), solvent species (D) factors, it is orthogonal that each factor chooses 3 horizontal progress
Analysis of experiments, using the layering ratio of aqueous emulsion as evaluation index, screen best processing technology.
The assay method of 10% Difenoconazole Flusilazole aqueous emulsion pH value
Tested according to GB/T 1601-1993.1g samples are taken in 250ml beakers, add 100ml distilled water, stirring
1min, stands 1min, and the pH meter of calibrated mistake determines its pH value.
10% Difenoconazole Flusilazole aqueous emulsion solvent screening result
According to the physicochemical property of Difenoconazole and Flusilazole, mixed xylenes, ethanol, ring are have selected from organic solvent
Hexanone, acetone, toluene, ethyl acetate, N-N dimethylformamides (DMF), normal propyl alcohol equal solvent are screened, the results showed that DMF
Best to two kinds of mixed solute effects of active compound, the selection result is shown in Table 2.
The result of the solvent screening of table 2
As seen in Table 2, toluene could not still dissolve active compound with dimethylbenzene when solvent load reaches 15%, it is contemplated that it
The addition of other auxiliary agents afterwards, therefore toluene and dimethylbenzene are cast out.For acetone as solvent, dissolved solution effect is preferable, but considers
It is too low to its flash-point, therefore do not use.Therefore the solvent filtered out has normal propyl alcohol, DMF, dimethyl sulfoxide (DMSO), ring
Hexanone.
Cold and hot storage experiment is carried out using the above-mentioned solvent filtered out, and outward appearance is observed such as table 3.Consolidated statement 2, table 3
As a result, it is known that solvent dimethyl sulfoxide (DMSO) and cyclohexanone dissolving active compound requirement are more, and normal propyl alcohol can analyse in cold and hot storage afterwards
Go out active compound, therefore select DMF.
Cold and hot storage situation after the solvent screening of table 3
The selection result of 10% Difenoconazole Flusilazole aqueous emulsion emulsifying agent
According to GB/T1603-2001 requirement, single emulsifier is first selected.With reference in GB/T1603-2001
Method, difenoconazole technical material 1.8750g is weighed, flusilazole 0.2g, adds normal propyl alcohol 2g to be dissolved, then weigh 4g emulsifications
Agent adds solution, is stirred uniformly.At ambient temperature, 1ml samples are taken to be added drop-wise at the height apart from water surface 2cm
Scattered situation is observed in 200ml standard hard waters.As a result such as table 4.
The emulsifying agent experimental result of table 4
Note：+ ,-it is the standard series of dispersiveness, ↓ to precipitate, → not precipitate,× represent qualified, unqualified respectively
NP-10, TX-10,602# emulsifying effectiveness as shown in table 4 is preferable, and is found after 24h without precipitation, experimentation observation
602# emulsifying effectiveness is better than NP-10, TX-10, therefore from 602# as emulsifying agent.
Orthogonal experiment results and analysis
On the basis of early stage experiment of single factor, design this orthogonal experiment and improve 10% Difenoconazole Flusilazole water and milk
The processing technology of agent.Four factors being had a great influence to making aqueous emulsion are selected, each factor sets three levels to be shown in Table 5.Heat
Storage Orthogonal experiment results are shown in Table 6, and cold storage Orthogonal experiment results are shown in Table 7.
The orthogonal design factor level table of table 5
The heat storage orthogonal experiments table of table 6
The cold storage orthogonal experiments of table 7
When as can be seen from Table 6, using the layering ratio during heat storage of Difenoconazole Flusilazole aqueous emulsion as evaluation index, by
The factor primary and secondary order of extreme difference discharge is B ＞ C ＞ A ＞ D, optimum proportioning A1B2C3D1, i.e. solvent is DMF
Dosage 10%, emulsifier 15%, aqueous phase deionized water.
As can be seen from Table 7, when layering ratio during storage cold using Difenoconazole Flusilazole aqueous emulsion is evaluation index, by
The factor primary and secondary order of extreme difference discharge is B ＞ C ＞ A ＞ D, optimum proportioning A1B2C3D1, i.e. solvent is DMF
Dosage 10%, emulsifier 15%, aqueous phase deionized water.
Because cold and hot storage show that optimum formula is A1B2C3D1, therefore it is final determine that formula is that solvent is N, N- dimethyl formyls
Amine dosage 10%, emulsifier 15%, aqueous phase deionized water.
The measurement result of the cold and hot storage resolution ratio of 10% Difenoconazole Flusilazole aqueous emulsion
The 10% Difenoconazole Flusilazole aqueous emulsion that will be prepared, 7d, 54 ± 2 DEG C of bars are stored under the conditions of being placed in 0 ± 2 DEG C
14d is stored under part, aqueous emulsion sample size is detected using HPLC instrument.The equal ＜ 5% of the degradation rate of Difenoconazole and Flusilazole, symbol
Close international requirement.
10% Difenoconazole Flusilazole aqueous emulsion processing method
Difenoconazole is dissolved in DMF with Flusilazole, and the rear 602# that adds stirs, and deionized water is added, with high speed
Cut disperser 5000r/min, the homogeneous liquid stirred after 9.9min is Difenoconazole Flusilazole aqueous emulsion.
The measurement result of 10% Difenoconazole Flusilazole aqueous emulsion pH value
Sample is measured by pH meter, the pH value for obtaining 10% Difenoconazole Flusilazole aqueous emulsion is 6.02.
The pH value measurement result of the Difenoconazole Flusilazole aqueous emulsion of table 8 10%
With the gradual enhancing of the food-safe consciousness of people, the preparation of aqueous emulsion is more paid close attention to by people, now
Turn into the focus studied at present.Difenoconazole and Flusilazole in the market common dosage forms are based on missible oil, wettable powder, water
Emulsion is less.Factor prepared by influence aqueous emulsion is more, and this research is investigated one by one to these factors, and aqueous emulsion is matched somebody with somebody
Side optimizes, and prepares aqueous emulsion by optimum formula, the performance of aqueous emulsion is characterized.
Prepare aqueous emulsion is influenceed by factors, and this is studied on the basis of solvent, emulsifying agent, water quality etc. is progressively selected,
Have a great influence four factors to preparing aqueous emulsion are selected, three levels are set, it is optimized using orthogonal design, obtained
Optimum proportioning be：Solvent is N,N-dimethylformamide accounting 10%, emulsifying agent be 602# account for always than 15%, aqueous phase is goes
Ionized water accounting 65%.
The preparation of 10% Difenoconazole Flusilazole aqueous emulsion, because Difenoconazole and Flusilazole are solid active compound,
Organic solvent should have good dissolubility to active compound, stable in physicochemical property, crystal will not be separated out in cold and hot storage, using N,
The aqueous emulsion stable in physicochemical property that dinethylformamide is prepared as organic solvent, and the medicine after dissolving inclines with good
Property.
When preparing aqueous emulsion, the effect of emulsifying agent is oil phase to be made preferably to be dispersed in aqueous phase, and oil phase is disperseed into poling
Small particulate is evenly distributed among aqueous phase, forms stable aqueous emulsion system.602# divides aqueous emulsion as emulsifying agent
Dissipate property it is good, under the conditions of cold and hot storage, on without oil slick, lower no precipitation.
When preparing aqueous emulsion, the requirement to water quality is higher, and water quality has the function that important to the stability of emulsion.Cause
This, after the surfactant in water emulsion formula determines, being formulated the hardness of reclaimed water should also make aqueous emulsion system relatively stable.
It is finally stable by the use of deionized water as aqueous phase, the cold and hot storage property of aqueous emulsion.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (2)
- A kind of 1. aqueous emulsion, it is characterised in that its raw material according to mass percent meter, including：
- 2. aqueous emulsion according to claim 1, it is characterised in that the mass ratio of the Difenoconazole and Flusilazole is 1: 9。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710778210.7A CN107593694B (en) | 2017-09-01 | 2017-09-01 | Aqueous emulsion |
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| CN201710778210.7A CN107593694B (en) | 2017-09-01 | 2017-09-01 | Aqueous emulsion |
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| CN107593694A true CN107593694A (en) | 2018-01-19 |
| CN107593694B CN107593694B (en) | 2020-07-24 |
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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 |
-
2017
- 2017-09-01 CN CN201710778210.7A patent/CN107593694B/en not_active Expired - Fee Related
Patent 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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