Water-based pesticide formulation and preparation method thereof
Technical field
The present invention relates to a kind of pesticidal preparations and preparation method thereof, especially a kind of Biphenthrin water-based pesticide formulation and preparation method thereof.
Background technology
The Traditional Agricultural pharmaceutically dosage form has missible oil, wetting powder and pulvis, but all has certain deficiency: the missible oil product needed is used a large amount of organic solvents, exists inflammable and explosive and the problem such as Environmental security; Wetting powder and pulvis produce a large amount of dust in production and use procedure, affect health and environment.In recent years, along with the day by day enhancing of people's environmental consciousness, the increasingly stringent that requires to environmental protection adds on the global oil price to rise, be restricted exploitation safety and the Water-borne modification of environmental protection and the developing direction that the spheroidizing formulation has become world pesticide with the cream preparation of organic solvent as thinner.Waterborne preparation is take water as thinner or a class environment-friendly pesticides new formulation of matrix, comprises suspending agent, microemulsion, aqueous emulsion and water-dispersible granules etc., and in addition new waterborne preparation still constantly occurs.At present, developed country's water-based pesticide formulation has accounted for more than 50% of agricultural chemicals total amount, and China is because of reasons such as research is started late, insufficient investments, and the conventional dosage forms such as missible oil, wetting powder still account for about 70% of agricultural chemicals gross yield, and this situation is demanded urgently changing.
The chemical name of Biphenthrin (bifenthrin): 2-methyl biphenyl-3-ylmethyl-(Z)-(1RS)-and suitable-3-(2-chloro-3,3,3-three fluoro-1-acrylic)-2,2-dimethyl cyclopropane carboxylic acid ester, molecular formula C
23H
22F
3ClO
2, outward appearance: sterling is solid, former medicine is light brown solid; Molecular weight: 422.86; Vapour pressure: 2.4 * 10
-2Pa (25 ℃); Fusing point: 68~70.6 ℃ of sterlings, 57~64 ℃ of former medicines; Dissolubility: water 0.1mg/L, acetone 1.25kg/L, and dissolve in chloroform, carrene, ether, toluene etc.; Density: relative density (d25) 1.210; Stability: stable to light, also more stable in acid medium, store at normal temperatures 1 year still more stable, but in alkaline medium, can decompose; Toxicity: Biphenthrin is medium to the person poultry toxicity; Very high to fish toxicity; Be 54.5mg/kg to rat acute Oral toxicity LD50; To rabbit acute dermal toxicity LD50 greater than 2000mg/kg; Skin and eyes are had no stimulation, without teratogenesis, carcinogenic, mutagenesis; To the birds low toxicity, LD50 is 1800mg/kg to the quail acute oral toxicity, to wild duck greater than 4450mg/kg; Biphenthrin is very high to fish toxicity, is 0.00015mg/L to rainbow trout LC50 (96 hours), water flea LC50 (48 hours) 0.00016mg/L, but because this medicament has very high affinity interaction in soil, and water-soluble low again, the impact of historical facts or anecdotes border is less; Biphenthrin is medium to honeybee toxicity; To the high poison of silkworm; Very high to Lepidoptera, orthoptera and two spotted spider mite insect insecticidal activity, be mainly and tag and stomach poison function, have repellent and Antifeedant Effects concurrently, without interior suction and fumigation activity, its effect is rapid, and the lasting period is long, and insecticidal spectrum is wide, can act on cotton bollworm, two-spotted spider mite, citrus red mite, cabbage caterpillar, applicable to cotton vegetables, fruit tree, tea tree etc.
In at present domestic registration is produced, Biphenthrin mainly is processed into missible oil, microemulsion, aqueous emulsion use, because the quantity of solvent of using in the missible oil production process is very large, not only can be to environment, waste petroleum resources, and the production accumulating is used all dangerous, relevant policies have been put into effect in countries in the world, the production and application of restriction missible oil.
Microemulsion is waterborne preparation, belongs to the environmental protection formulation, the international code name ME of formulation, the production storing and transporting security of microemulsion is better than missible oil, because the oil bead diameter minimum (≤20 nanometer) that oil phase disperses in the preparation, outward appearance is transparent liquid, is the thermodynamically metastable customization agent in the pesticide processing field.But, the Biphenthrin production and processing is become microemulsion, need to use than the more surfactant of missible oil, be generally 1.5 to 3 times of consumptions of oil phase, and for transparent warm area is expanded to more than 0~50 ℃, reach the storage requirement, need to use the more cosurfactants such as alcohols, cost is relatively high.
Aqueous emulsion also is one of agricultural chemicals waterborne preparation, belong to the environmental protection formulation, the international code name EW of formulation, once claimed emulsifiable concentrate (Concentrate Emulsion), being the former medicine of liquid pesticidal that makes with liquid or with solvent is scattered in preparation in the water with the droplet of 500~5000 nanometers, and outward appearance is milky milk shape liquid.But because its oil bead diameter is 500 nanometers above (seeing also Fig. 1), system is thermodynamic unstable system, need to increase external enwergy during production, carrying out high-speed stirred disperses, and after finishing dispersion, need to increase thickener and antifreezing agent as the stabilizing agent of system, production technology is comparatively complicated, therefore yield poorly, the production time is long, energy consumption is high, and equipment investment is also larger.
In view of this, necessary a kind of easy processing, novel aqueous chemical preparation of thermodynamically stable Biphenthrin and preparation method thereof of providing.
Summary of the invention
The object of the invention is to: a kind of easy processing, thermodynamically stable Biphenthrin waterborne preparation and preparation method thereof are provided.
The applicant finds through large quantity research and experiment, during take predetermined substance as surfactant, only need use a small amount of aromatic hydrocarbon solvent, Biphenthrin can be mixed with stable emulsion.Accordingly, the invention provides a kind of water-based pesticide formulation, it comprises the Biphenthrin of 2.5%~10% mass ratio, the surfactant of 2.5%~10% mass ratio, solvent and the water of 2.5%~10% mass ratio, and 98% above oil bead diameter of wherein said preparation is between 30~300 nanometers.
Be further to reduce the use of solvent, can in water-based pesticide formulation, add the brilliant stabilizing agent of phosphoric acid ester resistive connection of 0~5% mass ratio, such as in triethyl phosphate, triphenyl phosphate, the tributyl phosphate one or more.
Described surfactant is one or more the mixture in styryl phenol polyethenoxy ether, EO/PO block polyether phosphate, lauryl sulfate and the dodecyl benzene sulfonate.
As a kind of improvement of water-based pesticide formulation of the present invention, described surfactant is the mixture of EO/PO block polyether phosphate, lauryl sodium sulfate and calcium dodecyl benzene sulfonate.
As the further improvement of water-based pesticide formulation of the present invention, the preferred proportion of EO/PO block polyether phosphate, lauryl sodium sulfate and calcium dodecyl benzene sulfonate is 10~20: 0.5~5 in the described surfactant: 2~8.
Described solvent is aromatic hydrocarbon solvent, preferred C10 and above aromatic solvent.
Above-mentioned surfactant and Biphenthrin and a small amount of aromatic hydrocarbon solvent are mixed, need not add alcohols solvent, can simple agitation be separated into a kind of translucent milky liquid (MEW) in water, this emulsion particle diameter is in 30~300nm scope, 0~50 ℃ of lower stable performance.This dosage of surfactant is few, only have 30%~80% of oil phase, and the used emulsifier of conventional microemulsion is 1.5 to 3 times of oil phase, the particle size range≤20nm of microemulsion, and outward appearance is fully transparent; The particle size range of conventional aqueous emulsion is at 500~5000nm, and appearance milky white is opaque, needs to add the stability at normal duration of storage of thickener guarantee system.
The preparation process of above-mentioned water-based pesticide formulation comprises:
1) get by mass percentage 2.5%~10% Biphenthrin, 2.5%~10% surfactant, 2.5%~10% solvent, 0~5% the brilliant stabilizing agent of resistive connection, all the other are water;
2) Biphenthrin is dissolved in the brilliant stabilizing agent of solvent and resistive connection, adds again surfactant and mix and obtain oil phase;
3) add the required water yield in the still that is mixed, under 60~180 rev/mins mixing speed, oil phase is added to the water to stir, and obtains translucent Biphenthrin waterborne preparation.
As a kind of improvement of the preparation method of water-based pesticide formulation of the present invention, the described the 2nd) mixing by stirring under 60~180 rev/mins of speed in the step realize.
Compared with prior art, it is simple that water-based pesticide formulation of the present invention has a production equipment, and need not antifreezing agent and thickener can be realized Thermodynamically stable, also reduced the use of a large amount of organic solvents, meets environmental requirement.
Description of drawings
Below in conjunction with accompanying drawing and each embodiment, the present invention and useful technique effect thereof are elaborated, wherein:
Fig. 1 is the Biphenthrin emulsion in water particle diameter distribution map that conventional method is produced.
Fig. 2 is the particle diameter distribution map of Biphenthrin waterborne preparation embodiment 1 of the present invention.
Embodiment
Water-based pesticide formulation of the present invention, by Biphenthrin being dissolved in a small amount of varsol, add again that consumption equates with oil phase or still less, be generally the surfactant of oil phase 30~80%, for further reducing the use of solvent, can add simultaneously the stabilizing agent of a small amount of phosphoric acid ester resistive connection crystalline substance; The oil phase that mixes only need under simple stirring at low speed (60~180 rev/mins), be added to the water the novel aqueous chemical preparation (MEW) that can obtain take Biphenthrin as active ingredient.Its concrete preparation process is as follows:
1) get by mass percentage 2.5%~10% Biphenthrin, 2.5%~10% surfactant, 2.5%~10% solvent, 0~5% stabilizing agent, all the other are water; 2) Biphenthrin is dissolved in the brilliant stabilizing agent of solvent and resistive connection, adds again surfactant and mix and obtain oil phase; 3) add the required water yield in the still that is mixed, under 60~180 rev/mins mixing speed, oil phase is added to the water to stir, and obtains translucent Biphenthrin waterborne preparation (MEW).
Described solvent is varsol, preferably aromatic hydrocarbon solvent, preferably C10 and above aromatic solvent; Surfactant is one or more the mixture in styryl phenol polyethenoxy ether, EO/PO block polyether phosphate, lauryl sulfate, the dodecyl benzene sulfonate, the mixture of preferred EO/PO block polyether phosphate, lauryl sulfate and dodecyl benzene sulfonate; Stabilizing agent is the brilliant stabilizing agent of phosphoric acid ester resistive connection, such as triethyl phosphate, triphenyl phosphate, tributyl phosphate etc.
The particle size range of the Biphenthrin waterborne preparation (MEW) that the present invention makes is thermodynamic stable system in 30~300 nanometers, and long term storage is not stratified, bleed not.
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention describes with following specific embodiment, but the present invention is limited to absolutely not these examples.The following stated only is preferably embodiment of the present invention, only is used for explaining the present invention, can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that all any modifications of making within the spirit and principles in the present invention, be equal to replacement and improvement etc., all should be included within protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with appended claims.
Embodiment 1:
Get Biphenthrin 25kg, after trimethylbenzene 50kg dissolving, add again EO/PO block polyether phosphate 30kg, lauryl sodium sulfate 2kg, calcium dodecyl benzene sulfonate 8kg, after stirring under 60~180 rev/mins, join in the 885kg water, continue the Biphenthrin waterborne preparation (MEW) that under 60~180 rev/mins, stirs and namely obtain 2.5% mass ratio.Gained preparation outward appearance is translucent, particle diameter distribution 50~250 nanometers (seeing also Fig. 2), and storage at normal temperature is appearance stablity after 2 years, and after measured, the relative degradation rate of Biphenthrin content only is 0.86%;-25 ℃ of lower freezing 7 days normal temperature unfreezing again, the preparation performance is normal after 3 times repeatedly.
Embodiment 2:
Get Biphenthrin 50kg, after durene 80kg, triethyl phosphate 5kg dissolving, add again EO/PO block polyether phosphate 45kg, lauryl sodium sulfate 3kg, calcium dodecyl benzene sulfonate 12kg, after stirring under 60~180 rev/mins, join again in the 805kg water, continue the Biphenthrin waterborne preparation (MEW) that under 60~180 rev/mins, stirs and namely obtain 5% mass ratio.Gained preparation outward appearance is translucent, measures particle diameter and is distributed as 35~250 nanometers, and storage at normal temperature is appearance stablity after 2 years, and the relative degradation rate of Biphenthrin content that records only is 0.76%;-25 ℃ of freezing 7 days normal temperature unfreezing again, the preparation performance is normal after 3 times repeatedly.
Embodiment 3:
Get Biphenthrin 100kg, after the above aromatic solvent 80kg of C10, tributyl phosphate 8kg dissolving, add again EO/PO block polyether phosphate 55kg, lauryl sodium sulfate 5kg, calcium dodecyl benzene sulfonate 20kg, after stirring under 60~180 rev/mins, join again in the 732kg water, continue the Biphenthrin waterborne preparation (MEW) that under 60~180 rev/mins, stirs and namely obtain 10% mass ratio.Gained preparation outward appearance is translucent, measures particle diameter and is distributed as 40~266 nanometers, and storage at normal temperature is appearance stablity after 2 years, and the relative degradation rate of Biphenthrin content that records only is 0.52%;-25 ℃ of freezing 7 days normal temperature unfreezing again, the preparation performance is normal after 3 times repeatedly.
Embodiment 4:
Get Biphenthrin 25kg, after durene 50kg dissolving, add again styryl phenol polyethenoxy ether 35kg, lauryl sodium sulfate 1.5kg, DBSA amine 8.5kg, after stirring under 60~180 rev/mins, join in the 880kg water, continue the Biphenthrin waterborne preparation (MEW) that under 60~180 rev/mins, stirs and namely obtain 2.5% mass ratio.Gained preparation outward appearance is translucent, particle diameter distribution 45~250 nanometers, and storage at normal temperature is appearance stablity after 1.5 years, and after measured, the relative degradation rate of Biphenthrin content only is 1.06%;-25 ℃ of lower freezing 7 days normal temperature unfreezing again, the preparation performance is normal after 3 times repeatedly.
Embodiment 5:
Get Biphenthrin 50kg, after C10 aromatic hydrocarbons 80kg, triphenyl phosphate 3.5kg dissolving, add again EO/PO block polyether phosphate 45kg, dodecyl sulphate potassium 2.5kg, calcium dodecyl benzene sulfonate 12kg, after stirring under 60~180 rev/mins, join again in the 807kg water, continue the Biphenthrin waterborne preparation (MEW) that under 60~180 rev/mins, stirs and namely obtain 5% mass ratio.Gained preparation outward appearance is translucent, measures particle diameter and is distributed as 40~250 nanometers, and storage at normal temperature is appearance stablity after 2 years, and the relative degradation rate of Biphenthrin content that records only is 2.14%;-25 ℃ of freezing 7 days normal temperature unfreezing again, the preparation performance is normal after 3 times repeatedly.
Get 2.5% Biphenthrin waterborne preparation (MEW) of the embodiment of the invention 1 and the Biphenthrin missible oil of 2.5% mass ratio, the Biphenthrin emulsion in water of 2.5% mass ratio, the Biphenthrin microemulsion of 2.5% mass ratio, with 1000 times of dilutions eggplant is carried out the Tetranychus cinnabarinus control respectively, the results are shown in following table:
The different preparations of table 1 Biphenthrin are to the control efficiency contrast table of Tetranychus cinnabarinus on the eggplant
The medicament title |
24h lethality % |
48h lethality % |
1000 times of the embodiment of the invention 1 dilutions |
81 |
96 |
1000 times of 2.5% Biphenthrin missible oil dilutions |
78 |
95 |
1000 times of 2.5% Biphenthrin emulsion in water dilutions |
53 |
86 |
1000 times of 2.5% Biphenthrin microemulsion dilutions |
83 |
94 |
Contrast spray clear water |
0 |
6.5 |
As seen, the drug effect of Biphenthrin waterborne preparation of the present invention and be not less than other preparations of Biphenthrin of same concentration.
By above description as can be known, the outward appearance of the Biphenthrin waterborne preparation (MEW) that the present invention makes is translucent, wherein the oil bead diameter more than 98% is in 30~300 nanometers, be thermodynamic stable system, need not add the system stabilizers such as thickener, antifreezing agent, can store for a long time and not stratified, bleed not.Unlike microemulsion, need to add cosurfactant such as alcohols and other polar solvent and a large amount of surfactants in order to realize stable system, just fineness of dispersion is reached≤20 nanometers; Also unlike aqueous emulsion, particle diameter is more than 500 nanometers and belong to thermodynamic unstable system, and layering or bleed phenomenon will appear in storage time one length, so that in order to guarantee the stability of preparation system, need to add in addition thickener and antifreeze stabilizing agent.
Biphenthrin waterborne preparation of the present invention (MEW), can be in subzero 30 ℃ of stability to 50 ℃ of retentions above freezing, in subzero 5 ℃ and following meeting glaciation, but still directly entry is used, use after also can under normal temperature condition, reverting to liquid, therefore can add as required when producing or do not add antifreezing agent, and can not affect the preparation performance.
When producing waterborne preparation of the present invention (MEW), only need 60~180 rev/mins stirring at low speed equipment, and do not need to use the high energy and high speed mixing plant or be called high-shear emulsifying equipment (1000~15000 rev/mins), production equipment is simple, output is changeable, thereby production cost is greatly reduced.
That is to say, compared with prior art, the present invention has following outstanding advantages and positive effect: 1, reduced the use of a large amount of organic solvents, thereby reduced the pollution to environment, saved petroleum resources; 2, water is cooked the medium of agricultural chemicals, and production and application is safer; 3, dosage of surfactant is less than microemulsion, need not cosurfactant, and the preparation particle size range is thermodynamic stable system in 30~300 nanometers, long term storage is not stratified, bleed not; Only need simple agitation (60~180 rev/mins) when 4, producing, need not high energy, high-speed mixing equipment or be called high-shear emulsifying equipment (1000~15000 rev/mins), energy consumption is low, output is large, cycle is short, production cost is greatly reduced, energy savings; 5, need not antifreezing agent and thickener, preparation the problems such as bleed, layering can not occur.