CN101946794B - Cypermethrin water emulsion and preparation method thereof - Google Patents
Cypermethrin water emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention provides cypermethrin water emulsion, which comprises the following components in percentage by mass: 2 to 15 percent of cypermethrin, 3 to 10 percent of soybean oil, 1 to 10 percent of lauric acid diethanolamide, 1 to 3 percent of mixture of crylic acid and acrylic ester, 4 to 8 percent of white oil, 1 to 5 percent of diatomite, 2 to 10 percent of low HLB value surfactant, 0.5 to 2.5 percent of n-butyl alcohol, 1 to 5 percent of ethanediol and 0.2 to 3.0 percent of organosilicon defoamer. In the invention, according to a theory of reversed phase suspension emulsion polymerization, plant oil is taken as a medium of a continuous phase, and high polymer is taken as a macromolecular emulsifier at the same time; the cypermethrin water emulsion obtained by a certain preparation method has the advantages of high dispersibility, good effectiveness, high flowability before and after cold and hot storage, no agglomeration, and high chemical stability; and the cypermethrin water emulsion is stored under the hot condition at the temperature of 54+/-2 DEG C for two weeks, and resolution ratio is blew 10 percent.
Description
Technical field
The present invention relates to pesticide field, be specifically related to a kind of cypermethrin pesticide emulsion in water and preparation method thereof.
Background technology
Agricultural chemicals is the important means of production of modern agriculture, for guaranteeing that crops high-quality, high yield have indispensable effect.China is large agricultural country, and agricultural is the basis of national economy, but the per capita cultivated land is well below world average level, and the growth of the raising of level of agricultural production, the protection of agroecological environment and farmers' income is more closely related with the development of pesticide industry.Producer is too much indiscriminate excessively, and aggregate level is not high, the research and development strength weakness, and quality is uneven, and the industry of product structure is more and more, and agricultural chemicals also more and more is much accounted of the influence of crops and environment.The old formulation of agricultural chemicals such as missible oil, pulvis is self-evident to the harm that environment causes.
According to incompletely statistics, annual about 300,000 tons of the bulk drugs that consume of China, the finished medicines of making various preparations is about 1,500,000 tons.Wherein, formulation is that the finished medicines of missible oil accounts for half, promptly about 750,000 tons.1,500,000 tons of agricultural chemicals finished medicines, the overwhelming majority is used for the plant protection in farmland.
Along with the continuous reinforcement of people's environmental consciousness, more and more stricter about the rules of agricultural chemicals, not only require the pesticidal properties brilliance, but also good environment facies dissolubility will be arranged.At present in the formulations of pesticide, missible oil is very important and the sizable a kind of formulation of the market share, but missible oil is because of with an organic solvent making agricultural chemicals become inflammable and explosive dangerous material in a large number, increased many unsafe factors for the keeping, use etc. of production, packing, storage, transportation and the agricultural chemicals of agricultural chemicals, and it also show especially day by day to environment, accumulation harm that ecology and food security caused.
According to incompletely statistics, annual about 300,000 tons of the bulk drugs that consume of China, the finished medicines of making various preparations is about 1,500,000 tons.Wherein, formulation is that the finished medicines of missible oil accounts for half, promptly about 750,000 tons.For this reason, annual about 400,000 tons of the organic solvents such as supporting toluene, dimethylbenzene that need are used to prepare missible oil.Domestic annual 1500000 tons of agricultural chemicals finished medicines that consume, the overwhelming majority is used for the plant protection in farmland.Only in a kind of agricultural chemicals of weed killer herbicide, the annual organic solvent that sprays in available arable land is 350,000 tons.Because agricultural chemicals is that equilibrium sprays, organic solvent wherein is emulsified, so its extent of injury is considerably beyond the discharging of industrial wastes of equivalent amount, at coastal and dense waterway net region, flowed into rivers,lakes and seas, drinking water and aquatile are polluted and endanger.China ploughs has 2.5 hundred million mu to be subjected to pesticide pollution, accounts for about 15% of national arable area, and in fact situation may be even more serious.It is contaminated that 82% river is arranged in 532 rivers of China, causes and 44% surface water pollution is an agricultural.
Therefore, aqua type preparations such as aqueous emulsion and microemulsion because of its with water to replace organic solvent, thereby become the research focus gradually as clear water emulsion, microemulsion, soluble concentrate etc., owing to market competition look agricultural chemicals comes into one's own.Aggravation and the reinforcement of people's environmental consciousness, aqueous emulsion is as the alternative kind of inflammable, explosive, poisonous oil-based formulation missible oil, just becoming a new direction of pesticidal preparations development.
In general, the pesticide original medicine that is used for process water emulsion requires: 1. fusing point is less than 60.0 ℃; 2. tool is fat-soluble, and solvability should be less than below 0.1% (1000mg/L) in the water, a small amount of solvent of interpolation not water-soluble [1]; 3. can be steady in a long-term in water; When 4. mixing, there is not chemical change between former medicine with other agricultural chemicals.Water-soluble high agricultural chemicals is very big to the emulsion stability influence, can not be processed into aqueous emulsion.The active ingredient of aqueous emulsion is generally below 30%, and concentration is too high, is the water-in-oil type suspended substance from the oil-in-water type phase inversion easily.The aqueous emulsion outward appearance is opaque emulsion, and oil bead diameter is generally 0.7～20 μ m, and more satisfactory scope is 1.5～3.5 μ m.
The stability of pesticide emulsion in water and dispersed all has material impact for the application effect of agricultural chemicals.And its stability and dispersed directly is subjected to the influence of emulsifier characteristics and compound method.Because most of former medicines are water insoluble, so particularly important to the preparation of aqueous formulation with research, the screening of the supporting emulsifier of aqua type preparation.Efficient emulsifier can directly carry out emulsification to former medicine and be mixed with water base chemical preparation, has complied with the requirement of the world today to ecological environmental protection, and therefore great development space and market are arranged.According to the estimation of existing output: produce 1000000 tons of agricultural chemicals per year, wherein pulvis and missible oil occupy 70%, are exactly 700,000 tons, are 5% to calculate according to the consumption of emulsifier, and annual emulsifier requirement is 3.5 ten thousand tons, is that market is huge.Use this macromolecule emulsifier can with former medicine directly preparation become stable water base chemical preparation, thereby significantly reduced the use of the organic solvent toluene that needs will water-fast former medicine to prepare in the time of becoming missible oil, dimethylbenzene etc.And the different in kind of agricultural chemicals itself is also different to the character of the requirement of emulsifier and final formed emulsifier.Therefore, at different agricultural chemicals, should adopt suitable emulsifier and preparation process.
Aqueous emulsion development abroad in recent years is very fast, existing several 10 kind commercializations, for example kinds such as Tebuconazole, penconazole, cadusafos, triaguron, aclonifen, smart azoles diclofop-methyl.Only account for Britain agricultural chemicals market less than 1% as aqueous emulsion agent in 1993, and just rapidly increase to 5% after 5 years.China from 90 years 20th century for this reason, annual about 400,000 tons of the organic solvents such as supporting toluene, dimethylbenzene that need are used to prepare missible oil.Domestic annual the consumption for just beginning to develop aqueous emulsion agent progressively developed as 4.5% beta-cypermethrin, 5.7% cyfloxylate, 10% cypermethrin, 10% sumicidin, 40% diazinon, 25% propiconazole, 20% dimethachlon, 30% chlopyrifos and aqueous emulsion agent kinds such as health medication 10% powerful gram and 5% Ji Shu.But China's aqueous emulsion is in the development phase at present, all is inappreciable on kind, quantity and the ratio that accounts in agricultural chemicals market, and its effect also is to have certain deficiency, and wherein, stability of formulation is the difficult point of research always.At present, it is slower that the formulation of agricultural chemicals is improved development, though domestic have research to this formulation, reports very fewly, and industrialized product still less.In today more and more higher to the demand of pesticide emulsion in water; the pesticide emulsion in water formulation of exploitation high-quality; help agricultural chemicals to the development of aspects such as low toxicity, nontoxic, efficient, environmental protection, this has significant meaning and far-reaching influence for the sustainable development of China and the protection of ecotope.
Summary of the invention
The objective of the invention is to demand and the deficiencies in the prior art, the aqueous emulsion of cypermethrin that a kind of stability is high, emulsifying power is high is provided at present pesticide emulsion in water.
Another object of the present invention is to provide the preparation method of this aqueous emulsion of cypermethrin.
This experimental basis anti-phase suspension emulsion polymerisation theory, and the cypermethrin agricultural chemicals melted in soybean oil, directly former medicine is suspended or emulsification, be more conducive to environmental protection; Domestic showing all adopts simple small-molecular emulsifier to produce, and the method that the present invention adopts macromolecule and small-molecular emulsifier to cooperatively interact, emulsifying power is higher.
The invention provides a kind of aqueous emulsion of cypermethrin specifically, the material that contains following mass fraction: cypermethrin 2～15%, the mixture 1～3% of soybean oil 3～10%, lauric acid diethyl amide 1～10%, acrylic acid and acrylate, diatomite 1～5%, low HLB value surfactant (macromolecule polyoxy vinethene or fatty alcohol-polyoxyethylene ether) 2～10%.The mass ratio of acrylic acid and acrylate is 1～5: 1 in acrylic acid wherein and the acrylate, and their molecular weight is 500,000 to 20,000,000.
Remove this, also contain the white oil of mass fraction 4～8%; 0.5～2.5% n-butanol; 1～5% ethylene glycol and mass fraction 0.2～3.0% silicone defoaming agent.
The present invention provides the preparation method of this cypermethrin pesticide emulsion in water simultaneously, and the state the when release sequence of material is with mutual the mixing in the preparation process all can have significant effects to the character characteristics of aqueous emulsion final molding, also is vital therefore.
The preparation method of invention may further comprise the steps: (1) is divided into three parts with soybean oil, and HLB value surfactant, diatomite and first's soybean oil are mixed into base-material; (2) cypermethrin mixes formation cypermethrin-base material mixture with base-material, second portion soybean oil; (3) cypermethrin-base material mixture further mixes with mixture, lauric acid diethyl amide and the third part soybean oil of acrylic acid and acrylate, forms the thick product of aqueous emulsion of cypermethrin.Remove this, cypermethrin-base material mixture also mixes with white oil simultaneously in the step (3); The thick product of formed aqueous emulsion of cypermethrin also further is mixed into aqueous emulsion of cypermethrin with n-butanol, ethylene glycol, silicone defoaming agent and water.
The present invention is mainly according to anti-phase suspension emulsion polymerisation theory, and in the medium of vegetable oil as continuous phase, the while, as macromole emulsifying agent, the main chain of high molecular polymer was a hydrophily with high molecular polymer, and long side chain is a lipophile.Polymerisation is carried out on the surface of acrylic acid and acrylate emulsion droplet, in the later stage of reaction, further add crosslinking agent N, N '-methylene-bisacrylamide, make the faint cross-linked structure of intermolecular formation, after this structure can be dissolved in water or swelling scatter, have faint bridge architecture, this bridge architecture is playing main effect aspect the suspension of drop and solid particle.This amphiphilic high molecular polymer has the feature of high HLB value emulsifier, and and system in the little molecule phase inversion agent of high HLB value cooperatively interact, form oil-water emulsifiers efficiently.The efficient emulsifier of this kind not only can make the former medicine of liquid form microemulsion, and can make the former medicine of solid more all even stable under the effect of macromolecule bridge architecture, the easier performance of drug effect.
Various materials and proportioning thereof in the present invention's prescription are the combinations through drawing after repeatedly groping.Below concrete test method and result are further specified.
(1) evaluation index
1. stability test
The performance indications of aqueous emulsion are more, as active constituent content, outward appearance, dispersiveness, dilution stability, pourability, heat storage physical and chemical stability, cold storage stability, pH value, fineness, viscosity etc.
Wherein, the most important with heat (cold) storage physical stability, can only consider heat storage physical stability in the initial screening formula stage.Cold storage stability then mainly by the consumption decision of components such as emulsifier, co-emulsifier, antifreezing agent, can consider to guarantee the antifreezing agent of certain consumption during formula development, in order to avoid preparation freezes at low temperatures, can temporarily not consider the cold storage stability of preparation;
The active constituent content index can not considered; For beta-cypermethrin, the pH value generally is controlled at neutrality, slightly acidic scope gets final product, and need not special regulation and control, does not therefore generally also consider; The pourability test needs more amount of formulation, and this can cause waste in the experiment stage of fumbling, can be replaced by the flowability of observing preparation.
In sum, index be will investigate and outward appearance (flowability), dispersiveness, heat storage stability, cold storage stability will be decided to be.
Because physical parameter also can reflect the character and the stability of system, for example: the former medicine of beta-cypermethrin is the meeting hydrolysis in the strong basicity environment, therefore beta-cypermethrin agricultural chemicals system should be controlled pH under neutral and solutions of weak acidity, thereby the measurement of physical parameter volume is also especially important, can consider that the physical parameter of measuring comprises density, pH, viscosity, surface tension etc.
2. outward appearance
Comprise flowability and uniformity, if not homogeneous liquid or have water, oil to separate out or mobile extreme difference is then defective.
3. dispersed
When referring to that aqueous emulsion adds in the entry (30 ℃, hardness 342mg/L), dispersion and emulsion automatically forms the ability of emulsion, can be divided into following 4 grades: excellent---splash in the water after, be cloud and disperse, form emulsion, do not have visible particle in the dispersion process; Very---disperse automatically, have particle to sink, but to the bottom, can disperse substantially, or after being sink to the bottom, can comparatively fast going up to expand and disperse; Can---part is disperseed automatically, has particle to sink, and could disperse after need rocking or be inverted; Difference---can not disperse automatically, be graininess or cotton-shaped sinking, after shaking strongly, could disperse
4. heat storage stability
Method (Gui Wenjun, Cheng Jingli, Wei Fanglin with reference to Gui Wenjun etc., development [J] Deng .5.7% cyfloxylate aqueous emulsion. the Zhejiang agricultural science, 2004, (4): 218-220), get a certain amount of sample of preparation, seal up for safekeeping in the ampere bottle, take out after in (54 ± 2) ℃ insulating box, storing 14d, observe its appearance change, investigate its bleed, (no oil is separated out to analyse oily situation, and the bleed rate is lower than 10%, then is qualified).
5. low-temperature stability
Method (Gui Wenjun with reference to Gui Wenjun etc., Cheng Jingli, Wei Fanglin waits the development [J] of .5.7% cyfloxylate aqueous emulsion. Zhejiang agricultural science, 2004, (4): 218-220), get a certain amount of sample of preparation, seal up for safekeeping in the ampere bottle, store 7d in (0 ± 2) ℃ refrigerator, observe appearance change, investigate bleed, analyse oily rate.
(2) selection of emulsifier
Invention is 1-5 with the mass ratio: 1 acrylic acid and acrylate for emulsifier, in this mixture, the main chain of high molecular polymer is a hydrophily, long side chain is a lipophile, it has faint cross-linked structure, this structure can be in water dissolving or swelling and scatter, have faint bridge architecture after the dispersion, bridge architecture plays an important role to the suspension of drop and solid particle.
This amphiphilic macromolecule has the feature of high HLB value emulsifier, and and system in the little molecule phase inversion agent of high HLB value cooperatively interact, form oil-in-water emulsifiers efficiently.The efficient emulsifier of this kind not only can make the cypermethrin agricultural chemicals form microemulsion, and can make former medicine more all even stable under the effect of macromolecule bridge architecture, the easier performance of drug effect.
(3) solvent
Thereby this experiment purpose promptly is the use that reduces organic solvent product is developed to eco-friendly direction, for this reason, select the plant soybean oil as solvent, thereby replaced organic solvent dimethylbenzene etc.In the pesticidal emulsifiable process because cypermethrin (its fusing point is less than 60 ℃), can low-temperature heat, former medicine is melted in soybean oil, this course of dissolution is very easy to be finished, even and leave thermal source and cool, the former medicine of dissolving can not separated out yet.
(4) base-material
Diatomite is as suspending agent, the stability of this aqueous emulsion system is played an important role, but therefore diatomite must just produce base-material through relevant treatment such as overactivations.Base-material is macromolecule polyoxy vinethene/fatty alcohol-polyoxyethylene ether, diatomite, soybean oil three's a mixture, and wherein soybean oil is as continuous phase, in order to keep mobile and stable, its content maximum; Diatomite is as the suspending agent of final formulation of pesticide, and its consumption should have strict demand; Macromolecule polyoxy vinethene/fatty alcohol-polyoxyethylene ether then is diatomaceous activator, its activation, and consumption is less.Through test of many times, the present invention has determined their optimization consumption, and this is to effective dispersion of realizing this agricultural chemicals and keep its stability, also is important parameters.Concrete parameter optimisation procedure is as follows:
1. the preliminary prescription of base-material is as shown in table 1
Table 1 base-material is tentatively filled a prescription
2. the determining of diatomite consumption in the base material formulation
Diatomaceous content determines it is crucial in the base material formulation, because diatomite is as suspending agent, its consumption has strict requirement.Amount then may influence product stability very little; Amount is too many, then will certainly cause feeding-up.Therefore experimentize with diatomaceous content standard, the result of comparative trial is as shown in table 2.
The diatomite consumption determines in table 2 base material formulation
The result shows that the prescription shown in the sequence number 2 is qualified, so diatomite content is chosen as sequence number 2 in the base material formulation.
3. the determining of activator A7 consumption in the base material formulation
Its test and result are as shown in table 3.
The A7 consumption is determined in table 3 base material formulation
The result shows that A7 content is chosen as sequence number 4,5 in the base material formulation, from the angle that economizes in raw materials, selects sequence number 4.
4. base material formulation is summed up
Comprehensive previous experiments result, finally determine base-material optimum formula such as following table 4:
Table 4 base-material optimum formula
Illustrate: base-material is the khaki mixed liquor.
(5) auxiliary agent
Required auxiliary agent mainly contains co-emulsifier, antifreezing agent, defoamer, dispersant or the like
N-butanol is not an emulsifier itself, but reduces interfacial tension owing to being adsorbed on oil-water interfaces, therefore can play stabilization, the Chang Zuowei co-emulsifier.
Antifreeze: antifreeze commonly used has ethylene glycol, propane diols, glycerine, hexylene glycol, urea, ammonium sulfate, NaCl, CaCl2 etc.The present invention finds that ethylene glycol can be used as preferred antifreeze.
Defoamer:, need to add defoamer in order to eliminate the foam in the process.The present invention adopts the organosilicon silicon defoaming agent.
(6) water emulsion formula determines
1. preliminary experiment interpretation of result and optimization experiment design
Through preliminary test and analysis, invention has all been made the configuration of optimizing to various amount of substances in the prescription.Concrete test and result are as follows:
(1) fixed amount.
A. former concentration: for the aqueous emulsion system, former concentration is a minor amount, gets fixed value.
B. solvent soybean oil (being designated as A): be fixed as 5%,, make solid-state former medicine dissolving and liquid stateization as former medicine solvent.
C. auxiliary agent: for certain agricultural chemicals system, auxiliary dosage all has normative reference separately, because these auxiliary agents extensively are used, thereby, formed certain term of reference in the industry, so its consumption generally can be used as fixed amount, this concrete consumption of testing each auxiliary agent is respectively: 1. n-butanol (co-emulsifier), 0-5%, 0 expression is not used; 2. ethylene glycol (antifreezing agent), 5%; 3. silicone defoaming agent, consumption is fixed on 0.1%-0.5%.
(2) with single factors (high polymer) variable quantity.
Mineral oil (continuous phase) and high molecular polymer mass ratio 1: 1 are as continuous phase.
(3) independent variation amount.
As the factor of independent variation amount, must be to play an important role, to the component of aqueous emulsion system character and stability generation material impact, also just so, and need be independent them, the design orthogonal experiment is taken all factors into consideration.The component that the aqueous emulsion system is produced material impact is not difficult to analyze, and should be emulsifier, i.e. high molecular polymer and A13, and this tests another needs that independent what consider then is base-material consumption and prescription soybean oil, totally four factors:
1. the high polymer soybean oil of 2. filling a prescription is designated as 3. 4. base-material of A13 of B
2. preliminary experiment conclusion
Through above analysis, draw result as shown in table 5
Each amounts of components summation (total amount 300g) of table 5 water emulsion formula
3. orthogonal experiment is determined the aqueous emulsion optimum formula
By a large amount of experiments, tentatively determined the amount ranges of independent variation amount in the table 5, selection factor level, design orthogonal experiment, as the orthogonal table of table 6 to table 10, each experiment all is that fixed total amount is 300g, and former medicine virtual 10% does not add, soybean oil A5%, ethylene glycol 5%, organosilicon 1g etc. is fixed amount, and white oil becomes 1: 1 ratio with high polymer, and each experimental design course division is as follows
Table 6 orthogonal table 1: the high polymer consumption is determined
The above results shows that the high polymer consumption should be controlled at 1%, otherwise can cause aqueous emulsion feeding-up, and is mobile poor, and even overground difficulty
Determine that the high polymer factor level is 1%, design orthogonal experiment, result such as following table
Table 7 orthogonal table 2
The above results shows that soybean oil B consumption should center on 5% design factor level, and above-mentioned sequence number 6 is to be worth further improved benchmark
Launch experiment on table 2-9 experiment sequence number 6 bases, soybean oil B only changes the A13 consumption around 5% design, and the result is as follows
Table 8 orthogonal table 3
Table 9 orthogonal table 4
Above-mentioned experiment, sequence number 6 are best, 15d bleed still extremely low (in 5%), and No. 8 then above 10%; But in the cycle of 14d, 2 all is qualified, but the two all analyses oil stain and resemble, and promptly oil is up poly-, but does not separate out.
Table 10 orthogonal table 5
4. the aqueous emulsion optimum formula is summed up
Above-mentioned by analysis result of the test is determined shown in the preferred water emulsion formula breast table 11.
Table 11 aqueous emulsion optimum formula
As can be seen from the above table, the aqueous emulsion optimum formula is: high polymer 1%, soybean oil 6%～8%, A13:2%～4%, base-material 1%～3%
(7) formulation of pesticide determines
On the above-mentioned basis of determining water emulsion formula, next select best water emulsion formula, toward wherein adding former medicine, the experiment division is as follows:
1. former medicine is the pressed powder class
(1) the co-emulsifier n-butanol 1%
Each experiment all is that fixed total amount is 300g, and former medicine 10% is dissolved among the 5% soybean oil A, ethylene glycol 5%, and organosilicon 1g etc. is fixed amount, and white oil becomes 1: 1 ratio with high polymer, as shown in table 12.
The former powder class of table 12 formulation of pesticide (containing n-butanol)
(2) the co-emulsifier n-butanol 0%
Former powder class agricultural chemicals does not contain the prescription of n-butanol, and its test and result are shown in table 13-15.
The former powder class of table 13 formulation of pesticide (not containing n-butanol)
The former powder class of table 14 formulation of pesticide (not containing n-butanol)
The former powder class of table 15 formulation of pesticide (not containing n-butanol)
All above-mentioned experiments are not ideal, are mainly reflected on the flowability, after leaving standstill, to such an extent as to product can solidify in retrogradation, illustrate that water emulsion formula is not ideal to former powder class agricultural chemicals in 2.6
2. former medicine is a crude oil class
The crude oil class agricultural chemicals does not contain the prescription of n-butanol, and its test and result are shown in table 16.
Table 16 crude oil class formulation of pesticide (not containing n-butanol)
The aqueous emulsion of this experiment gained is fine to the former drug effect fruit of crude oil class, and products obtained therefrom is qualified; To the former medicine of former powder class, because normal temperature is easy to solidify after leaving standstill, make mobile variation, so when making aqueous agricultural-chemical, should select crude oil, or former powder is made the crude oil use with aqueous emulsion.
(8) product parameters
Use the cypermethrin technical material of different content, its result is shown in table 17.
Table 17 product parameters
And the preparation process of agricultural chemicals of the present invention is also to the significant effects that forms of aqueous emulsion, and its preparation process should be carried out according to following steps:
The first step: according to the amount on the prescription.A7, diatomite, soybean oil are pressed 0.5g respectively; 3g: 9.5g (in fact for have enough amounts mould, amplify several times in this ratio), standby the mixture 1～1.5h. that on colloid mill, mills.
Second step: stir adding No. 26 white oils again in the polymer adding cup, stir evenly back adding A13 and stir evenly, add soybean oil again, homogeneous is standby.
The 3rd step: soybean oil is added in the cup, add former medicine and be dissolved into crude oil, stir evenly; Again base-material is added in the cup, stir evenly.
The 4th step: slowly add inside second step and stir the 3rd step, standby.
The 5th step: add n-butanol, silicone defoaming agent, antifreezing agent at another beaker, water is supplied surplus.
The 6th step: the 4th step was added in the 5th step, and 1h then mills on colloid mill.
Compared with prior art, the present invention has following beneficial effect:
(1) aqueous emulsion of cypermethrin provided by the invention, its favorable dispersibility, drug effect is brought into play easily.
(2) the invention provides the cypermethrin (crude oil class) that aqueous emulsion is made, the good fluidity before and after the hot and cold storage, do not lump, chemical stability is good, and 54 ± 2 ℃ of heat 2 weeks of storage, its resolution ratio is below 10%.
Embodiment
Below just embodiment come specific explanations the present invention, but embodiment does not do any qualification to the present invention.
Embodiment 1
The preparation of aqueous emulsion of cypermethrin:
1. the preparation of base-material: diatomite is dried under 140 ℃ of temperature in advance, with fatty alcohol-polyoxyethylene ether .05g, diatomite 3g, soybean oil 9.5g mixes, and the 1h that mills on colloid mill is standby.
2. mass ratio 1-5: add No. 26 white oils again in 1 acrylic acid and the acrylate mixture 0.5g adding cup and stir, stir evenly the back and add lauric acid diethyl amide 1g, stir evenly, add soybean oil again, homogeneous is standby.
3. soybean oil 5g is added in the cup, add the cypermethrin dissolving of 28.0g mass content 95%, stir evenly; Again base-material is added in the cup, stir evenly.
4. the 3rd step was slowly added the 2nd step the inside and stir, standby.
5. add n-butanol 1.5g, silicone defoaming agent 1.0g, ethylene glycol 3g at another beaker, add entry again and make total amount reach 300g.
6. the 4th step was added in the 5th step, the 1h that mills on colloid mill then finally forms aqueous emulsion of cypermethrin.
Embodiment 2
Embodiment 1 prepared aqueous emulsion of cypermethrin and permethrin milk oil dilution become same multiple, carries out the control of insect test:
1. for studying thing: fragrant taro (Apios americana), kind: the fragrant taro in civilian hilllock
2. controlling object: prodenia litura (Spodoptera litura)
3. test method:
3.1 experimental scheme
Four processing: C (aqueous emulsion of cypermethrin dilution) are established in test: cypermethrin content is respectively 0.092% and 0.074%; D (permethrin milk oil dilution) cypermethrin content is respectively 0.092% and 0.074%.With the clear water is contrast, 3 repetitions, and district's group is arranged at random, sub-district area 44.46m
2
3.2 test method
Tested on October 13rd, 2009 to October 15 and carry out the fragrant taro Tanaka of Baiyun District, Guangzhou City Mt salon.The field of vegetables physical features is smooth, loam, and the content of organic matter is higher, mu surplus the area 50.1 mu of testing ground area.Test is carried out routine by each concentration of treatment and is converted water spray, dispenser once, spraying equipment is a WS-16 type manual sprayer, spraying evenly, and is thoughtful.The every sub-district 4L of spray amount (presses 60L/667m
2Meter).With the clear water is blank, 3 repetitions of every processing.Prodenia litura is based on the 3-6 instar larvae during dispenser.
3.3 investigation method
The test investigate altogether 4 times, carry out the investigation of insect population radix before the dispenser, behind the medicine behind 6h, the medicine behind 30h, the medicine 54h carry out efficacy survey.Adopt the investigation of diagonal five point taking methods, every sub-district 5 points, 10 leaves of every some investigation amount to 50, add up the prodenia litura larva number alive in the different length of times.According to investigation result, calculate the insect population respectively handle five repetitions go down rate and control efficiency by " pesticide field efficacy medicine test criterion ".Computing formula is as follows:
2.4 the weather condition of duration of test
Test weather the moon on the same day, gentle breeze, duration of test weather conditions basically identical, temperature is at 24 ℃-32 ℃.
4. result of the test
The result is shown in table 17.1000 times of processing of test medicine 9.2% aqueous emulsion of cypermethrin, 6h, 30h behind the medicine, 54h are respectively 85.65%, 90.46% and 82.07%, 1250 times to the average preventive effect of prodenia litura and handle 6h, 30h behind the medicine, 54h the average preventive effect of prodenia litura is respectively 70.05%, 73.37% and 69.61%.The processing of 1000 times of reagent agents and 1250 times all can the fragrant taro of better prevention on Spodoptera litura larvae.The reagent agent of two processing all behind medicine 30h the preventive effect of prodenia litura is reached the highest, 54h still keeps preventive effect preferably behind the medicine.
Table 17 medicament is to the field test results of prodenia litura on the fragrant taro
Annotate: different lowercases is illustrated in the significance of difference on 5% level in the table.
1087 times of processing of contrast medicament 10% permethrin milk oil, 6h, 30h, 54h are respectively 90.48%, 92.69% and 89.15% to the average preventive effect of Spodoptera litura larvae behind the medicine, and 1359 times of processing 6h, 30h, 54h behind medicine are respectively 75.33%, 77.31% and 73.41% to the average preventive effect of prodenia litura, this result of the test contrasts two processing of medicament prodenia litura on the fragrant taro has all been played good control efficiency as can be seen.
The test medicine data that investigation obtains with the contrast medicament are carried out significance of difference analysis through SPSS13.0 software, the result shows: on 5% level, between three investigation results, control efficiency to Spodoptera litura larvae between the processing of reagent agent and the identical using dosage of contrast medicament is suitable, the indifference significance, and the preventive effect that two medicament low concentrations are handled significantly is lower than the preventive effect that high concentration is handled.
In sum, when reagent agent is identical with contrast medicament mu effective ingredient consumption, the Spodoptera litura larvae on the fragrant taro of the equal energy of the cypermethrin of two-form better prevention, and preventive effect is suitable.This result of the test shows that for cypermethrin, it is feasible utilizing Water-borne modification formulation-aqueous emulsion to substitute the stronger missible oil of contaminative.
Claims (2)
1. aqueous emulsion of cypermethrin, it is characterized in that containing the material of following mass fraction: cypermethrin 2 ~ 15%, the mixture 1 ~ 3% of soybean oil 3 ~ 10%, lauric acid diethyl amide 1 ~ 10%, acrylic acid and acrylate, diatomite 1 ~ 5% and low HLB value surfactant 2 ~ 10%, white oil 4 ~ 8%, n-butanol 0.5 ~ 2.5%, ethylene glycol 1 ~ 5%, silicone defoaming agent 0.2 ~ 3.0%; Surplus is a water;
The mass ratio of acrylic acid and acrylate is 1 ~ 5:1 in described acrylic acid and the acrylate, and the molecular weight of acrylic acid and acrylate is 50-2000 ten thousand; Described low HLB value surfactant is APEO or fatty alcohol-polyoxyethylene ether.
2. the preparation method of an aqueous emulsion of cypermethrin as claimed in claim 1, it is characterized in that adopting the batch mixed method, may further comprise the steps: (1) is divided into three parts with soybean oil, will hang down HLB value surfactant, diatomite and first's soybean oil and be mixed into base-material; (2) cypermethrin mixes formation cypermethrin-base material mixture with base-material, second portion soybean oil; (3) cypermethrin-base material mixture further mixes with mixture, lauric acid diethyl amide and the third part soybean oil of acrylic acid and acrylate, forms the thick product of aqueous emulsion of cypermethrin; Wherein cypermethrin-base material mixture also mixes with white oil simultaneously in the step (3); The thick product of formed aqueous emulsion of cypermethrin also further is mixed into aqueous emulsion of cypermethrin with n-butanol, ethylene glycol, silicone defoaming agent and water.
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| CN103583550B (en) * | 2013-11-21 | 2015-07-22 | 山东中新科农生物科技有限公司 | Emulsion in water (EW) of theta-cypermethrin and nitenpyram and application of same |
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| CN1871915A (en) * | 2005-06-03 | 2006-12-06 | 南京第一农药有限公司 | Aqueous emulsion of syn type cypermethrin, and preparation method |
| CN101002566A (en) * | 2006-01-17 | 2007-07-25 | 上海农乐生物制品股份有限公司 | High performance aqueous emulsion of cypermethrin, and its preparing method |
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| CN101002566A (en) * | 2006-01-17 | 2007-07-25 | 上海农乐生物制品股份有限公司 | High performance aqueous emulsion of cypermethrin, and its preparing method |
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