CN101828571B - Pesticide water suspending agent containing high-efficiency lambda-cyhalothrin and preparation method thereof - Google Patents
Pesticide water suspending agent containing high-efficiency lambda-cyhalothrin and preparation method thereof Download PDFInfo
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- CN101828571B CN101828571B CN 201010173040 CN201010173040A CN101828571B CN 101828571 B CN101828571 B CN 101828571B CN 201010173040 CN201010173040 CN 201010173040 CN 201010173040 A CN201010173040 A CN 201010173040A CN 101828571 B CN101828571 B CN 101828571B
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Abstract
The invention discloses a pesticide water suspending agent containing high-efficiency lambda-cyhalothrin and a preparation method thereof. The pesticide water suspending agent containing the high-efficiency lambda-cyhalothrin comprises 10.0% of lambda-cyhalothrin, 6.0% of nonyl phenol polyoxyethylene ether, 0.45% of thickening agent WJZ-04, 3% of defoaming agent 8431, 6.0% of anti-freezing agent (ethylene glycol), and the balance of water. The low-temperature and hot storage stability experiment testifies that the water suspending agent has no obvious delamination in appearance and good dispersity in water; the indexes meet the relative requirements of the suspending agents; and the result of the field efficacy trials shows that the suspending agent has good control effect on cucumber aphids. Water is used as the diffusion medium for the suspending agent so that no inflammable and phytotoxicity problems of the organic solvent occur. The suspending agent has good dispersity and adhesiveness, high suspending rate, strong ability of adhering to the surface of the plant, and good rain washing resistance, thereby the suspending agent has remarkable and lasting pesticide effect in comparison with the wettable powder; meanwhile, the suspending agent is more benefit for protecting the natural environment and lightens the damage to the environment. The invention has the advantages of low production cost, practical process, environment protection, no pollution and good application performance.
Description
Technical field
The invention belongs to the organic agricultural chemicals applied technical field, relate to the formulations of pesticide that contain gamma cyhalothrin, especially a kind of pesticide suspension concentrate that contains gamma cyhalothrin and preparation method thereof and application.
Background technology
21st century, the use of agricultural chemicals is still one of human Main Means of struggling with disease pest and weed in agricultural production.A large amount of uses along with agricultural chemicals, a large amount of organic solvents have caused pollution to environment, continuous enhancing along with people's environmental consciousness and security knowledge, at present, the formulations of pesticide more and more are subject to making a pet of of people and pay attention to towards the formulation of the future development, particularly aqueous suspension agent of water baseization, spheroidizing, slow release, multi-functional, Labor-saving and environment-friendly type.Pesticide suspension concentrate (Suspension Concentrate, SC) be a kind of environment amenable environment-protection pesticide formulation take water as medium, by some auxiliary agent by the solid pesticide that is insoluble to or is slightly soluble in water, adopt soybean dietary fiber to be scattered in more equably in the water, form the very thin higher suspension of a kind of particle diameter, can flow, stable liquid-solid attitude preparation.Because pesticide suspension concentrate has good Environmental compatibility, drug effect is high, cost is low and safety is used in processing, shows one's talent in water base property preparation, has very large development potentiality.
At present external existing hundreds of suspending agent exploitations are put into production, but in China, the conventional dosage forms such as missible oil, wetting powder, pulvis still have comparative advantage, aqueous suspension agent is less, and mostly have stable not problem, the made pesticide suspension concentrate that contains gamma cyhalothrin of the present invention is through low temperature and heat storage stability experiment, and outward appearance is without obvious layering, favorable dispersibility in the water, indices meet the suspending agent relevant criterion.The present invention will play certain impetus to the development of China's formulations of pesticide, and the application of its invention also can bring good economic benefit to enterprise.
The gamma cyhalothrin chemical name is alpha-cyano-3-phenoxy benzyl-3-(2-chloro-3,3,3-three fluoro-1-acrylic-1-acrylic)-2,2-dimethyl cyclopropane carboxylic acid ester.A kind of novel pyrethroid insecticides, have tag, stomach poison function, without systemic action, insecticidal spectrum is wide, insecticidal action is fast, holding effect is long.This product can be widely used in Lepidoptera, coleoptera and the homoptera pest of the crops such as control cotton, fruit tree, soybean, vegetables.
Its structural formula is as follows:
Summary of the invention
An object of the present invention is to provide a kind of pesticide suspension concentrate that contains gamma cyhalothrin.
Another object of the present invention has provided preparation method and the application aspect Lepidoptera, coleoptera and the homoptera pest disease of the crops such as control cotton, fruit tree, soybean, vegetables thereof that contains the high-performance cyhalothrin pesticide aqueous suspension agent.For achieving the above object, technology contents disclosed by the invention is as follows:
A kind of pesticide suspension concentrate that contains gamma cyhalothrin is characterized in that it is comprised of following raw material:
Gamma cyhalothrin 10～20%,
Wetting dispersing agent 1.0～8.0%,
Thickener 0.2～6.0%,
Antifreezing agent 3.0～8.0%,
Defoamer 1～5%,
Water complements to 100%.
Wherein in the pesticide suspension concentrate suspension particle diameter at 2～5 μ m.
The pesticide suspension concentrate that the present invention is more preferably, it is comprised of following raw material: the former medicine of 10.0% gamma cyhalothrin, 6.0% polyoxyethylene nonylphenol ether, 0.45% thickener WJZ-04,3% defoamer, 8431,6.0% antifreeze glycols, water complements to 100%.Wherein in the pesticide suspension concentrate suspension particle diameter at 2～5 μ m.
Pesticide suspension concentrate of the present invention, wetting dispersing agent wherein is: one or more the combination of alkylaryl polychloroprene APEO, calcium dodecyl benzene sulfonate, nonyl phenol formaldehyde resin APEO, calcium lignosulfonate, polyoxyethylene nonylphenol ether or alkylaryl polyoxyethylene ether phosphate.
Pesticide suspension concentrate of the present invention, thickener wherein is: xanthans XG, WJZ-04 or CMC.
Pesticide suspension concentrate of the present invention, antifreezing agent wherein is: glycerine or ethylene glycol; Defoamer is: 8431.
The preparation method of pesticide suspension concentrate of the present invention is characterized in that being undertaken by following step:
(1) by the requirement of above-mentioned photograph prescription, former medicine gamma cyhalothrin, wetting dispersing agent, antifreezing agent, defoamer and water mixing are sized mixing, pre-dispersed with high-shear emulsion machine;
(2) the gained slurry is moved into the sand milling tank, passes into cooling water and carry out sand milling, sand milling to the suspension particle diameter of material after 2～5 μ m reach 98% or more, filtration, for subsequent use;
(3) thickener is mixed with 1～2% the aqueous solution, joins in the slurry after the filtration, detect the qualified finished product that is after the debugging.
The present invention's method for optimizing of filling a prescription is as follows:
1 experiment material and method
1.1 experiment material
The former medicine of gamma cyhalothrin: white or off-white color pressed powder, effective component content 95%.
Wetting dispersing agent: calcium dodecyl benzene sulfonate, nonyl phenol formaldehyde resin APEO, calcium lignosulfonate, sodium metnylene bis-naphthalene sulfonate, polyoxyethylene nonylphenol ether, alkylaryl polyoxyethylene ether phosphate.
Thickener: xanthans XG, WJZ-04, CMC.
Antifreezing agent: glycerine, ethylene glycol.
Defoamer: 8431.
1.2 experimental instrument
Sand mill (0.1L, 0.3L, 1.5L), laboratory high-speed shearing emulsion machine, NDJ-1 viscosimeter, PH meter, laboratory centrifuge, laser granulometry.
1.3 experimental technique
Adopt wet method sand milling ultramicro grinding.According to the prescription requirement, former medicine, auxiliary agent and water mixed sizes mixing, pre-dispersed with high-shear emulsion machine after, slurry is moved into the sand milling tank, pass into cooling water and carry out sand milling, after sand milling is qualified to the particle diameter of material, filter, for subsequent use.Thickener is mixed with the aqueous solution of different proportion, joins in the slurry after the filtration, detect the qualified finished product that is after the debugging.
1.4 the mensuration of aqueous suspension agent physicochemical property
The assay method of the dispersiveness of aqueous suspension agent, centrifugal stability, viscosity, pH value, pourability, suspensibility, cold storage stability, heat storage stability all carries out with reference to suspending agent quality standard and the method for inspection in " formulations of pesticide processing book series " (third edition), and the gamma cyhalothrin content analysis adopts liquid chromatography.
2 prescription screenings
2.1 the selection of wetting dispersing agent
The suspension system of pesticide suspension concentrate comes from a kind of thermodynamic unstable system between colloidal dispersion system and rough segmentation are loose.The particle diameter of aqueous suspension agent generally has several microns sizes, because particle diameter is very little, the surface free energy of particle is very large, easy adsorption-condensation between particle.In order to increase the stability of aqueous suspension agent; usually must add a certain amount of wetting dispersing agent; around dispersed phase particles, form firm diaphragm; or formation electric double layer; make the pesticide granules surface charging; mutually repel between charged particle and dispersion is tended towards stability, make it in storage process, not occur cohesion and knot end phenomenon.Even a small amount of layering is arranged, can become stable suspension system through shaking gently still, and have good in dispersiveness.
According to the physical and chemical performance of gamma cyhalothrin and the research experience of similar products processing thereof, we select different nonionics and anion wetting dispersing agent to carry out screening (table 1)
Table 1 wetting dispersing agent is selected test
| Project | 1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# |
| Gamma cyhalothrin % | 10.5 | 10.5 | 10.5 | 10.5 | 10.5 | 10.5 | 10.5 | 10.5 |
| Sodium metnylene bis-naphthalene sulfonate | 4.0 | 2.0 | 2.0 | 2.5 | ||||
| Calcium lignosulfonate | 3.0 | 2.5 | 3.5 | 2.0 | ||||
| Polyoxyethylene nonylphenol ether | 6.0 | |||||||
| The alkylaryl polyoxyethylene ether phosphate | 3.0 | |||||||
| Calcium dodecyl benzene sulfonate | 0.5 | 1.0 | 0.5 | 1.0 | 0.5 | |||
| The nonyl phenol formaldehyde resin APEO | 1.5 | 1.0 | 3.5 | 2.0 | ||||
| Suspensibility | 90 | 86 | 90 | 85 | 89 | 86 | 93 | 97 |
| Dispersed | Can | Can | Can | Can | Can | Can | Very | Very |
| Centrifugal stability | Bad | Very | Bad | Bad | Bad | Bad | Can | Very |
| Heat storage stability | Poor | Poor | Poor | Poor | Poor | Poor | Can | Can |
2.2 the selection of thickener
The viscosity of suspending agent is a key factor that affects the product bin stability.Viscosity is too little, product easily layering after placement a period of time, easy caking; Viscosity is too large, and it is serious that product is difficult for toppling over wall built-up, brings difficulty for processing and use.In order to improve the pourability of product, improve suspensibility and bin stability, must make product that a suitable viscosity is arranged.For this reason, according to the experience of developing suspending agent in the past, on the basis of 8# prescription, we screen several thickeners and have carried out stability test, find to select WJZ-04 thickener effect better, and it the results are shown in Table 2.
The centrifugal stability of preparation is best during from the selection result as can be known, with XG (0.5%) and WJZ-04.But preparation viscosity is higher when adding 0.4%XG, is difficult for flowing and sticking wall; When adding WJ-04, formulation flows is better, therefore finally determine WJZ-04 as the thickener of 10% gamma cyhalothrin SC, its consumption is 0.45%
Table 2 thickener is selected test
| The thickener kind | Consumption | Viscosity (mpa.s) | Centrifugal stability |
| XG | 0.2 | 300 | Bad |
| XG | 0.5 | 1750 | Very |
| WJZ-04 | 0.4 | 950 | Very |
| WJZ-04 | 0.45 | 1200 | Excellent |
| WJZ-04 | 0.5 | 1450 | Very |
| CMC | 2.5 | 225 | Bad |
| CMC | 6.0 | 750 | Very |
2.3 the selection of antifreezing agent
Pesticide suspension concentrate take water as medium, its prescription not only will be suitable for storing under the southern high-temperature condition and using, and will be suitable for storage and use under northern area cold.The former can add antifreezing agent less, and the latter must add an amount of antifreezing agent, to guarantee normal result of use.
We have done comparative trial to ethylene glycol, glycerine commonly used, and both consumptions are even to be 6.0%.When test finds to make antifreezing agent with glycerine, although the aqueous suspension agent outward appearance is unchanged during cold storage, mobilely obviously descend, and there is not this situation in ethylene glycol.Therefore, this formulation selection ethylene glycol is as antifreezing agent, and its consumption is 6.0%.
2.4 the selection of defoamer
The production technology of agricultural chemicals suspension agent adopts Wet multi-stage sand milling superfine grinding more, and a large amount of air is brought and be dispersed into to the dispersion impeller of High Rotation Speed into atomic little bubble, and the suspending agent volume is expanded rapidly.These micro-bubbles not only can affect viscosity (mobile variation), metering and packing, and will reduce significantly production efficiency.If can not froth breaking, this may make the creeping type become dilatant fluid.So, in pharmaceutical formulation, add a certain amount of defoamer, and require defoamer good intermiscibility to be arranged with each component of preparation.This prescription is characterized in that with 8431 defoaming effect is good, and good with each component intermiscibility of preparation, consumption is few, dosage 3.0%, and price is low.
Determining and checking of 3 optimal formulations
The technical indicator of 3.110% gamma cyhalothrin aqueous suspension agent
Table 3 technical indicator
| Project | Index |
| Outward appearance | White, can flow, thick liquid. |
| Gamma cyhalothrin content, % | 10.0±1.0 |
| Suspensibility, % | ≥90 |
| The pH value | 4.0～7.0 |
| Particle diameter (3～5 μ m) | ≥90％ |
| Pourability | Qualified |
| Heat storage stability | Qualified |
| Cold storage stability | Qualified |
3.2 optimal formulation is by intersection screening and heat storage stability test to former steps, obtained optimal formulation, its prescription is as follows: the former medicine of 10.0% gamma cyhalothrin, 6.0% polyoxyethylene nonylphenol ether, 0.45% thickener WJZ-04,3% defoamer, 8431,6.0% antifreeze glycols, water complements to 100%.
Press the sample of optimal formulation preparation, detect its all technical, its result such as table 4
Table 4 sample detection result
| Sequence number | The pH value | Suspensibility (%) | Particle diameter (μ m) | Pourability | Dispersed | Cold storage stability | Heat storage stability |
| 1 | 5.3 | 98.2 | 3.25 | Very | Very | Qualified | Qualified |
| 2 | 5.2 | 98.4 | 3.22 | Very | Very | Qualified | Qualified |
| 3 | 5.4 | 98.5 | 3.37 | Very | Very | Qualified | Qualified |
| 4 | 5.3 | 98.2 | 3.30 | Very | Very | Qualified | Qualified |
4. result
(1) obtained optimal formulation, its prescription is as follows: the former medicine of 10.0% gamma cyhalothrin, and 6.0% polyoxyethylene nonylphenol ether, 0.45% thickener WJZ-04,3% defoamer, 8431,6.0% antifreeze glycols, water complements to 100%.
(2) preparation is through low temperature and heat storage stability experiment, and outward appearance is without obvious layering, and favorable dispersibility in the water, indices meet the suspending agent relevant criterion.
Pesticide suspension concentrate provided by the invention has following positive achievement as insecticide:
(1) formulation of change gamma cyhalothrin is suspending agent, during use, without dust harzard, to operator and Environmental security.
(2) formulation of change gamma cyhalothrin can make the peasant more convenient when using this product, and is quick.
(3) the inflammable and drug injury problem that is produced by organic solvent can not occur take water as dispersion medium in suspending agent.
(4) dispersiveness of suspending agent and plate-out ability are all relatively good, and suspensibility is high, and the ability that sticks to the plant corpus surface is more intense, resistance of rainwater washing against, thereby drug effect is than wetting powder significantly and also more lasting.
(5) change the gamma cyhalothrin formulation, be conducive to the conservation of nature environment, alleviate the destruction that environment is caused.
Description of drawings
Fig. 1 is pesticide suspension concentrate preparation flow figure.
Embodiment
Embodiment 1
Prescription forms: the former medicine of 10.0% gamma cyhalothrin, and 6.0% polyoxyethylene nonylphenol ether, 0.45% thickener WJZ-04,3% defoamer, 8431,6.0% antifreeze glycols, water complements to 100%.
Embodiment 2
Prescription forms: 10.0% gamma cyhalothrin, and 5% alkylaryl polychloroprene APEO, 2.5% thickener xanthans XG, 3% defoamer, 8431,5.0% antifreeze glycols, water complements to 100%.
Embodiment 3
Prescription forms: 15.% gamma cyhalothrin, and 6.5% nonyl phenol formaldehyde resin APEO, 0.2% thickener WJZ-04,3% defoamer, 8431,5.0% antifreeze glycols, water complements to 100%.
Embodiment 4
Prescription forms: 20.0% gamma cyhalothrin, and 8.0% alkylaryl polychloroprene APEO, 3.0% thickener xanthans XG, 3% defoamer, 8431,6.0% antifreezing agent glycerine, water complements to 100%.
Embodiment 5
Prescription forms: 10.0% gamma cyhalothrin, and 5% polyoxyethylene nonylphenol ether, 6.0% thickener WJZ-04,3% defoamer, 8431,3.5% antifreezing agent glycerine, water complements to 100%.
The preparation method of embodiment 1-5:
(1) by the requirement of above-mentioned photograph prescription, former medicine gamma cyhalothrin, wetting dispersing agent, antifreezing agent, defoamer and water mixing are sized mixing, pre-dispersed with high-shear emulsion machine;
(2) the gained slurry is moved into the sand milling tank, passes into cooling water and carry out sand milling, sand milling to the suspension particle diameter of material after 2～5 μ m reach 98% or more, filtration, for subsequent use;
(3) thickener is mixed with the aqueous solution of 1-2%, joins in the slurry after the filtration, detect the qualified finished product that is after the debugging.
Embodiment 6 (Application Example)
Carry out efficacy testing by the obtained 10% gamma cyhalothrin aqueous suspension agent of the embodiment of the invention 1 prescription respectively at these four areas of Chongqing, Liaoning, Heilungkiang and Tianjin, the result is as follows:
Table 510% gamma cyhalothrin aqueous suspension agent is to the field control effectiveness test result (Chongqing) of cucumber aphid
According to table 5 statistics as can be known: each processes 10% gamma cyhalothrin aqueous suspension agent and contrast medicament, to the field efficacy of cucumber aphid, behind medicine, be respectively in 2 days: 92.58% (12 g/has), 90..86% (9 g/has), 88.41% (6 g/has) and 90.80% (contrast medicament); Behind the medicine 7 days, each preventive effect of processing respectively was: 94.61%, 92.75%, 91.18% and 92.66% (contrast medicament).In 2 investigation, each preventive effect of processing of test medicine increases with the increase of using dosage, compares with other producers registered like products, and using dosage is identical, and preventive effect is suitable.Each preventive effect of processing behind the medicine 7 days is higher than behind the medicine 2 days preventive effect.Each processes test medicine and the contrast medicament, behind medicine 2 days consistent with 7 days preventive effect variation tendency, namely except difference between 9 g/has of processing of 10% gamma cyhalothrin aqueous suspension agent and contrast medicament significantly, all the other respectively between processing preventive effect difference reach significance level.And behind the medicine in each time investigation, do not find the plant phenomenon of being injured.
Table 610% gamma cyhalothrin aqueous suspension agent is to the field control effectiveness test result (Liaoning) of cucumber aphid
As can be seen from Table 6, test medicine 10% gamma cyhalothrin aqueous suspension agent has good control efficiency to the cucumber aphid, and middle dosage and high dose are processed each phase preventive effect and reached more than 90%.Through statistical analysis, the result shows: the control efficiency that the high dose of 1 day, 2 days, 5 days and 10 days is processed behind the medicine is significantly higher than the preventive effect that low dosage is processed; Middle dosage is processed each phase preventive effect and also is higher than low dosage and processes, and 1 day high, medium and low dosage preventive effect three difference was remarkable after variance analysis showed medicine, behind the medicine in 2 days and the 10 days preventive effects dosage and the two difference of low dosage not remarkable; Reach significant difference between 1 day preventive effect of test medicine high dose and contrast chemicals treatment, difference is not remarkable between each phase preventive effect of middle dosage and contrast medicament, 1 day, 5 days and 10 days preventive effects and contrast significant difference between medicament behind the low dosage medicine.
The preventive effect that 1 day high, medium and low three dosage are processed behind the medicine reaches respectively 93.61%, 89.74% and 87.14%, show that 10% gamma cyhalothrin aqueous suspension agent has good quick-acting, behind medicine 10 days dosage process preventive effect still up to 90% with in view of, show that test medicine has preferably lasting effect.
Table 710% gamma cyhalothrin aqueous suspension agent is to the field control effectiveness test result (Heilungkiang) of cucumber aphid
As can be seen from Table 7,6 g/has of processing of reagent agent 10% gamma cyhalothrin aqueous suspension agent, bad to the control efficiency of aphid, but 8～12 g/has of processing are better to the preventive effect of aphid, and preferably preventive and therapeutic effect and control action are arranged.The test medicine 10% gamma cyhalothrin aqueous suspension agent of effective ingredient same dose is suitable with quick-acting (1～3 day) drug effect of contrast medicament 25 grams per liter gamma cyhalothrin aqueous suspension agents, but the drug effect that surpasses 7 days just significantly decreases, and has significant difference with the contrast medicament.
Table 810% gamma cyhalothrin aqueous suspension agent is to the field control effectiveness test result (Tianjin) of cucumber aphid
As can be seen from Table 8, reagent agent 10% gamma cyhalothrin aqueous suspension agent improves along with the increase of dispenser dosage the preventive effect of cucumber aphid, it is suitable that 12 g/has of processing and 9 g/has of contrast medicament 2.5% efficient cyhalothrin emulsifiable concentrates are processed preventive effect, and there is not significant difference between the two in the preventive effect of 1 day, 3 days and 7 days behind the medicine.
To the analysis showed that above drug effect is reported the result, gained gamma cyhalothrin aqueous suspension agent of the present invention has preferably preventive effect to the cucumber aphid, and drug effect all is higher than contrast medicament or suitable with the contrast medicament.
The present invention is after the preferred embodiment that describes in detail, being familiar with this technology personage can be well understood to, can carry out various variations and modification not breaking away under above-mentioned claim and the spirit, all foundations technical spirit of the present invention all belongs to the scope of technical solution of the present invention to any simple modification, equivalent variations and modification that above embodiment does.And the present invention also is not subject to the embodiment that gives an actual example in the specification.
Claims (3)
1. pesticide suspension concentrate that contains gamma cyhalothrin is characterized in that it is comprised of following raw material:
The former medicine of 10.0% gamma cyhalothrin, 6.0% polyoxyethylene nonylphenol ether, 0.45% thickener WJZ-04,3% defoamer, 8431,6.0% antifreeze glycols, water complements to 100%.
2. the preparation method of the described pesticide suspension concentrate of claim 1 is characterized in that being undertaken by following step:
(1) according to the prescription requirement, former medicine gamma cyhalothrin, wetting dispersing agent, antifreezing agent, defoamer and water mixing are sized mixing, pre-dispersed with high-shear emulsion machine;
(2) the gained slurry is moved into the sand milling tank, passes into cooling water and carry out sand milling, sand milling to the suspension particle diameter of material after 2～5 μ m reach 98% or more, filtration, slurry is for subsequent use;
(3) thickener is mixed with 1～2% the aqueous solution, joins in the slurry after the filtration, detect the qualified finished product that is after the debugging.
3. the described pesticide suspension concentrate that contains gamma cyhalothrin of claim 1 is used for the application of the sick aspect of Lepidoptera, coleoptera and homoptera pest of control cotton, fruit tree, soybean, vegetable crop as insecticide.
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| CN102550545A (en) * | 2010-12-17 | 2012-07-11 | 南京红太阳股份有限公司 | Cyhalothrin suspension agent containing vegetable oil and derivatives of vegetable oil and preparation method and application of cyhalothrin suspension agent |
| CN102550546A (en) * | 2010-12-17 | 2012-07-11 | 南京红太阳股份有限公司 | Alpha-cypermethrin suspension preparation containing vegetable oil and derivatives thereof, as well as preparation method and application of alpha-cypermethrin suspension preparation |
| US10881100B2 (en) | 2014-01-29 | 2021-01-05 | Rotam Agrochem International Company Limited Chai Wan | Aqueous suspoemulsion containing lambda-cyhalothrin and methods for making and using the same |
| CN106212518A (en) * | 2016-08-10 | 2016-12-14 | 江苏春江润田农化有限公司 | A kind of production method of the former medicine of gamma cyhalothrin |
| CN115968902A (en) * | 2022-12-28 | 2023-04-18 | 宁夏格瑞精细化工有限公司 | Acetamiprid and efficient cyhalothrin-containing aqueous suspension and preparation method thereof |
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| CN1951194A (en) * | 2006-11-15 | 2007-04-25 | 江苏省农业科学院 | Fipronil and etofenpronx mixed pesticide |
| CN101361487A (en) * | 2008-09-28 | 2009-02-11 | 江苏省农药研究所股份有限公司 | Disinsection acaricidal cream and aqueous emulsion containing alpha-cyano-N-benzyl pyrazole acidamide compound |
| CN101647444A (en) * | 2009-09-17 | 2010-02-17 | 深圳诺普信农化股份有限公司 | Agricultural composition containing tebufenpyra |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1951194A (en) * | 2006-11-15 | 2007-04-25 | 江苏省农业科学院 | Fipronil and etofenpronx mixed pesticide |
| CN101361487A (en) * | 2008-09-28 | 2009-02-11 | 江苏省农药研究所股份有限公司 | Disinsection acaricidal cream and aqueous emulsion containing alpha-cyano-N-benzyl pyrazole acidamide compound |
| CN101647444A (en) * | 2009-09-17 | 2010-02-17 | 深圳诺普信农化股份有限公司 | Agricultural composition containing tebufenpyra |
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