CN103210952B - Methidathion nano-emulsion and preparation method thereof - Google Patents
Methidathion nano-emulsion and preparation method thereof Download PDFInfo
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- CN103210952B CN103210952B CN201210376780.0A CN201210376780A CN103210952B CN 103210952 B CN103210952 B CN 103210952B CN 201210376780 A CN201210376780 A CN 201210376780A CN 103210952 B CN103210952 B CN 103210952B
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Abstract
The invention discloses a methidathion nano-emulsio, wherein raw materials for preparing the methidathion nano-emulsion comprise 1-5% methidathion original drug, 2-10% of organic solvent, 3.5-13% of emulsifier, 5-17.5% of cosolvent, 0.1-0.5% of antifreeze, and the balance water, wherein a total amount of all components is 100%. The raw materials of the methidathion nano-emulsio further comprise 0-0.5% by weight of thickening agent and/or 0-0.25% by weight of antifoaming agent. The invention provides an aqueous preparation of a nano-emulsion, which replaces a poisonous and harmful organic solvent in a traditional methidathion emulsifiable solution preparation, reduces toxicity, implements green and environmental protection characteristics, and raises stability of the aqueous preparation of methidathion.
Description
(1) technical field
The present invention relates to pesticidal preparations field, particularly relate to a kind of methidathion nanoemulsion and preparation method thereof.
(2) background technology
Methidathion, chemical name is: S-2,3-dihydro-5-methoxyl group-2-oxo-1,3,4-thiadiazoles-3-ylmethyl 0,0-Methyl disulfide substituted phosphate, English common name: Methidathion, CAS numbering: 950-37-8, molecular formula: C
6h
11n
2o
4pS
3, molecular weight: 302.32, structural formula is as follows:
Methidathion, it is a kind of organophosphorus insecticide of wide spectrum, activity is higher, drug effect is rapid, resistance of rainwater washing against after spraying, have tag, stomach toxicity and osmosis, can infiltrate in plant tissue, chewing type and sucking pest are all had to killing effect, especially scale insect is had to special efficacy, mite class is had to certain control action.Be applicable to prevent and treat various pests on the crops such as fruit tree, cotton, tea tree, vegetables.Be applicable to the insect of peanut, soybean, cotton, fruit tree, vegetables.Control crop pests is as wheat aphid, midge worm, mythimna separata, corn borer, soybean aphid, soybean pod borer etc.Control vegetable-crop pest-insect is as diamond-back moth, tomato moth, prodenia litura, Oeobia undalis etc.
The main formulation of methidathion is 20%, 40% missible oil, when use, 40% missible oil is watered to 800 ~ 1000 times, and consumption of organic solvent is up to more than 70%.Tradition methidathion cream preparation is owing to containing a large amount of inflammable organic solvents in missible oil, and in long-term use procedure, a large amount of organic solvents evaporate in atmosphere, and environment has been caused to serious pollution.Aqueous emulsion is taking water as medium, both can improve the operating environment of factory, has avoided the murder by poisoning of organic solvent to operator, has avoided again the waste of a large amount of organic solvents and the pollution to the Nature.But, although current domestic some pesticide emulsion in water that occurred, its stability can not be guaranteed, and easily occurs the phenomenon such as layering, flocculation in storage process.
Nanoemulsion is a class new formulation, and particle diameter is 20-500 nm, and its dynamic stability is high, optical clarity good, viscosity is low, is the desirable novel aqueous pesticidal preparations of a class.
(3) summary of the invention
The object of the invention is to prepare the nanoemulsion of methidathion, by adding emulsifier, cosolvent, thickener, antifreeze and defoamer to prepare the nanoemulsion of stable methidathion.
The technical solution used in the present invention is as follows:
A kind of methidathion nanoemulsion, taking methidathion as active ingredient, the raw material of preparing described methidathion nanoemulsion comprises the composition of following percentage by weight:
The method of preparing described methidathion nano-emulsion comprises the following steps: (1) takes each component raw material by above-mentioned percentage by weight, first former methidathion medicine and organic solvent, partial emulsifier A is stirred and is dissolved, and is fully uniformly dispersed, and makes first-phase; (2) by remaining emulsifier B and the water-soluble generation second-phase of other remaining reagent; (3) second-phase, under the stirring of 700-2000 rev/min of rotating speed, is slowly added dropwise to second-phase by first-phase, continues to stir 30-60 minute, makes described methidathion nanoemulsion;
Organic solvent of the present invention is toluene, hexane, toluene, acetone, ethanol, n-octyl alcohol, is preferably toluene.
Cosolvent of the present invention is polyethylene glycol compounds, is preferably PEG-200, PEG-400 or PEG-600.
Emulsifier of the present invention is the summation of emulsifier A and emulsifier B; That is to say, the 3.5-13% that total mass fraction of emulsifier A and emulsifier B is all raw materials, wherein, the quality consumption of described emulsifier A be generally emulsifier gross mass consumption 10 ~ 35%.
Emulsifier of the present invention is Sulfonates emulsifier, polyethers emulsifier or the composite blended emulsifier of their arbitrary proportion.Wherein, described Sulfonates emulsifier is preferably alkyl benzene calcium sulfonate (as agriculture breast 500) or sodium alkyl benzene sulfonate; Described polyethers emulsifier is preferably alkylphenol polyoxyethylene (as agriculture breast 100), poloxalkol, fatty alcohol-polyoxyethylene ether, T-80 (as Tween-60, Tween-80) or sorbitan fatty acid ester (Arlacel-60, Arlacel-80).
Concrete, more preferably described emulsifier is the combination of one or more arbitrary proportions in agriculture breast 500, agriculture breast 100, Tween-60, Tween-80, Arlacel-60 or Arlacel-80.
Antifreeze of the present invention is one or more any combination in ethylene glycol, propane diols or glycerine.
The raw material of the described methidathion nanoemulsion of preparation of the present invention comprises the composition of following percentage by weight, refer to that mentioned component is for reaching the requisite composition of the technology of the present invention object, but also can require the functional additive that adds some nanoemulsion be there is no to negative effect, such as thickener, defoamer etc. for some specific functions.
Concrete, the raw material that the present invention prepares described methidathion nanoemulsion can also comprise the defoamer of quality percentage mark 0-0.5% thickener and/or quality percentage mark 0-0.25%; Described thickener and/or defoamer for step (2) as other remaining reagent parts and remaining emulsifier B and the water-soluble generation second-phase of other remaining reagent;
Thickener of the present invention is cellulose ether and derivative class thickener or polyethylene glycol stearate diester, concrete preferred described thickener is the two stearates of hydroxyethylcellulose, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, methylhydroxypropylcellulose, carboxymethyl cellulose or Macrogol 6000 (being called for short PEG6000DS), more preferably PEG6000DS, ethylhydroxyethylcellulose or carboxymethyl cellulose.
Defoamer of the present invention is preferably silicone defoaming agent, more preferably emulsion-type silicon oil foam killer, and as L-101, L-1000 series that Shanghai Li Qi auxiliary chemicals Co., Ltd produces, the JY-810-1 model that Shanghai Jian Yu Chemical Co., Ltd. produces etc.
Described quality percentage mark 0-0.5% thickener refers to that the percentage by weight of thickener in all raw material components is 0-0.5%, 0 referring to and be infinitely close to 0 and be not 0 wherein, quality percentage mark is the percentage of thickener with respect to all material compositions, that is to say, in the situation that other component percentages are constant, add 0-0.5% thickener, the consumption of corresponding water reduces, and the consumption of water ensures that the summation of all components is 100%.
The defoamer of described quality percentage mark 0-0.25% refers to that the percentage by weight of defoamer in all raw material components is 0-0.25%, 0 referring to and be infinitely close to 0 and be not 0 wherein, quality percentage mark is the percentage of thickener with respect to all material compositions, that is to say, in the situation that other component percentages are constant, add 0-0.5% thickener, the consumption of corresponding water reduces, and the consumption of water ensures that the summation of all components is 100%.
The present invention's water used can be running water or deionized water.
In described step (1), be fully uniformly dispersed and can utilize conventional mixer means, preferably under ultrasonic, shake 5-20 minute.
In described step (3), described first-phase is slowly added dropwise to second-phase, slow dropping is wherein in order to be conducive to form nano-emulsion, and rate of addition is 0.15 ~ 0.25mL/min conventionally.
Further, preferred methidathion nanoemulsion of the present invention is prepared from by the composition of following percentage by weight:
Described preparation method is: (1) takes each component raw material by above-mentioned percentage by weight, first former methidathion medicine and organic solvent, partial emulsifier A is stirred and is dissolved, and under ultrasonic, shakes 5-20 minute, makes first-phase; (2) again by water-soluble to remaining emulsifier B, cosolvent, thickener, antifreeze, defoamer generation second-phase; (3) second-phase, under the stirring of 700-2000 rev/min of rotating speed, is slowly added dropwise to second-phase by first-phase, continues to stir 30-60 minute, makes described methidathion nanoemulsion.
The present invention also provides a kind of preparation method of methidathion nanoemulsion, and described methidathion nanoemulsion is prepared from by the composition of following percentage by weight:
Described preparation method is: (1) takes each component raw material by above-mentioned percentage by weight, first former methidathion medicine and organic solvent, partial emulsifier A is stirred and is dissolved, and under ultrasonic, shakes 5-20 minute, makes first-phase; (2) again by water-soluble to remaining emulsifier B, cosolvent, thickener, antifreeze, defoamer generation second-phase; (3) second-phase, under the stirring of 700-2000 rev/min of rotating speed, is slowly added dropwise to second-phase by first-phase, continues to stir 30-60 minute, makes described methidathion nanoemulsion;
Described organic solvent is toluene, hexane, toluene, acetone, ethanol or n-octyl alcohol;
Described cosolvent is polyethylene glycol compounds;
Described emulsifier is Sulfonates emulsifier or polyethers emulsifier or the composite blended emulsifier of their arbitrary proportion;
Described emulsifier is the summation of emulsifier A and emulsifier B;
Described antifreeze is one or more any combination in ethylene glycol, propane diols or glycerine.
Compared with prior art, its beneficial effect is embodied in the present invention:
1, the present invention utilizes this class aqueous formulation of nano-emulsion to substitute poisonous and hazardous organic solvent in traditional methidathion cream preparation, has reduced toxicity, realizes environmental protection.
2, utilize the high performance of dynamic stability of nanoemulsion to improve the stability of methidathion aqueous formulation.
3, in aqueous emulsion, add water-soluble good compound of polysaccharide or derivative as thickener, because polysaccharide derivates has good biodegradability, therefore make the stability-enhanced while of methidathion nanoemulsion of preparation still keep greenization.
(4) brief description of the drawings
The particle diameter distribution map of the methidathion nanoemulsion that Fig. 1 embodiment 1 makes
(5) embodiment:
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited to this:
The detection method of the particle diameter of nano-emulsion of the present invention is as follows: get 100 times of prepared methidathion nano-emulsion sample deionized water dilutions, with laser particle analyzer (Zetasizer Nano-ZS, Malvern, UK) measure the average grain diameter of nano-emulsion and particle diameter distributes.
Embodiment 1
Preparation process is as follows:
1, take former medicine, emulsifier, cosolvent, thickener, antifreeze, defoamer and the water of above-mentioned formula.
2, methidathion is added in conical flask, after adding toluene stirring and dissolving, then add sorbester p17 to stir, then the lower concussion of ultrasonic (50 W, 40 kHz) 10 minutes, form first-phase.
3, PEG-400, polysorbate60, PEG6000DS, ethylene glycol, defoamer are added in conical flask, add water to 100g, stir to dissolving, form second-phase.
4, second-phase, under the stirring of 1000 revs/min of rotating speeds, is slowly added dropwise to second-phase (rate of addition is 0.2mL/min) by first-phase, continues to stir 30 minutes, forms uniform nano-emulsion, and the particle diameter of nano-emulsion distributes as shown in Figure 1.The detection method of the particle diameter of described nano-emulsion is as follows: get 100 times of prepared methidathion nano-emulsion sample deionized water dilutions, average grain diameter and the particle diameter of measuring nano-emulsion with laser particle analyzer (Zetasizer Nano-ZS, Malvern, UK) distribute.
Methidathion nanoemulsion prepared by said method, through 0～4
oc refrigerates 2 weeks without crystallization, and 54 ± 2
othe storage of C heat still presented pellucidity after 2 weeks, without analysing oily phenomenon; After nanoemulsions dilution, present light blue fluorescence, good emulsion stability.
Embodiment 2
Preparation process is as follows:
1, take former medicine, emulsifier, cosolvent, thickener, antifreeze, defoamer and the water of above-mentioned formula.
2, methidathion is added in conical flask, after adding toluene stirring and dissolving, then add sorbester p17 to stir, then the lower concussion of ultrasonic (50 W, 40 kHz) 5 minutes, form first-phase.
3, PEG-200, polysorbate60, PEG6000DS, glycerine, defoamer are added in conical flask, add water to 100g, stir to dissolving, form second-phase.
4, second-phase is under the stirring of 1200 revs/min of rotating speeds, first-phase is slowly added dropwise to second-phase (rate of addition is 0.25mL/min), continue to stir 50 minutes, form uniform nano-emulsion, the method of pressing embodiment 1 is surveyed the particle diameter of nano-emulsion, record average grain diameter 80 nm, low-temperature stability is qualified, thermodynamic stability (54 ± 2
oc, 2 weeks) resolution ratio≤10%.
Embodiment 3
Preparation process is as follows:
1, take former medicine, emulsifier, cosolvent, thickener, antifreeze, defoamer and the water of above-mentioned formula.
2, methidathion is added in conical flask, after adding toluene stirring and dissolving, then add agriculture breast 500 to stir, then the lower concussion of ultrasonic (50 W, 40 kHz) 10 minutes, form first-phase.
3, PEG-400, polysorbate60, ethylhydroxyethylcellulose, propane diols, defoamer are added in conical flask, add water to 100g, stir to dissolving, form second-phase.
4, second-phase is under the stirring of 700 revs/min of rotating speeds, first-phase is slowly added dropwise to second-phase (rate of addition is 0.2mL/min), continues to stir 50 minutes, form uniform nano-emulsion, the method of pressing embodiment 1 is surveyed the particle diameter of nano-emulsion, records average grain diameter 110 nm.Low-temperature stability is qualified, thermodynamic stability (54 ± 2
oc, 2 weeks) resolution ratio≤10%.
Embodiment 4
Preparation process is as follows:
1, take former medicine, emulsifier, cosolvent, thickener, antifreeze, defoamer and the water of above-mentioned formula.
2, methidathion is added in conical flask, after adding toluene stirring and dissolving, then add agriculture breast 500 to stir, then the lower concussion of ultrasonic (50 W, 40 kHz) 20 minutes, form first-phase.
3, PEG-400, Tween 80, carboxymethyl cellulose, ethylene glycol, defoamer are added in conical flask, add water to 100g, stir to dissolving, form second-phase.
4, second-phase is under the stirring of 700 revs/min of rotating speeds, first-phase is slowly added dropwise to second-phase (rate of addition is 0.2mL/min), continues to stir 60 minutes, form uniform nano-emulsion, the method of pressing embodiment 1 is surveyed the particle diameter of nano-emulsion, records average grain diameter 70 nm.Low-temperature stability is qualified, thermodynamic stability (54 ± 2
oc, 2 weeks) resolution ratio≤10%.
Embodiment 5
Preparation process is as follows:
1, take former medicine, emulsifier, cosolvent, thickener, antifreeze, defoamer and the water of above-mentioned formula.
2, methidathion is added in conical flask, after adding toluene stirring and dissolving, then add sorbester p18 to stir, then shake 15 minutes under ultrasonic, form first-phase.
3, PEG-200, Tween 80, PEG6000DS, glycerine, defoamer are added in conical flask, add water to 100g, stir to be dissolved, form second-phase.
4, second-phase is under the stirring of 1500 revs/min of rotating speeds, first-phase is slowly added dropwise to second-phase (rate of addition is 0.2mL/min), continues to stir 35 minutes, form uniform nano-emulsion, the method of pressing embodiment 1 is surveyed the particle diameter of nano-emulsion, records average grain diameter 150 nm.Low-temperature stability is qualified, thermodynamic stability (54 ± 2
oc, 2 weeks) resolution ratio≤10%.
Embodiment 6
Preparation process is as follows:
1, take former medicine, emulsifier, cosolvent, thickener, antifreeze, defoamer and the water of above-mentioned formula.
2, methidathion is added in conical flask, after adding toluene stirring and dissolving, then add sorbester p17 to stir, then the lower concussion of ultrasonic (50 W, 40 kHz) 10 minutes, form first-phase.
3, PEG-600, polysorbate60, PEG6000DS, ethylene glycol, defoamer are added in conical flask, add water to 100g, stir to dissolving, form second-phase.
4, second-phase is under the stirring of 1200 revs/min of rotating speeds, first-phase is slowly added dropwise to second-phase (rate of addition is 0.2mL/min), continues to stir 50 minutes, form uniform nano-emulsion, the method of pressing embodiment 1 is surveyed the particle diameter of nano-emulsion, records average grain diameter 180 nm.Low-temperature stability is qualified, thermodynamic stability (54 ± 2
oc, 2 weeks) resolution ratio≤10%.
Embodiment 7
Preparation process is as follows:
1, take former medicine, emulsifier, cosolvent, thickener, antifreeze, defoamer and the water of above-mentioned formula.
2, methidathion is added in conical flask, after adding toluene stirring and dissolving, then add agriculture breast 500 to stir, then the lower concussion of ultrasonic (50 W, 40 kHz) 20 minutes, form first-phase.
3, PEG-400, polysorbate60, PEG6000DS, ethylene glycol, defoamer are added in conical flask, add water to 100g, stir to dissolving, form second-phase.
4, second-phase is under the stirring of 1000 revs/min of rotating speeds, first-phase is slowly added dropwise to second-phase (rate of addition is 0.15mL/min), continues to stir 40 minutes, form uniform nano-emulsion, the method of pressing embodiment 1 is surveyed the particle diameter of nano-emulsion, records average grain diameter 160 nm.Low-temperature stability is qualified, thermodynamic stability (54 ± 2
oc, 2 weeks) resolution ratio≤10%.
Embodiment 8
Preparation process is as follows:
1, take former medicine, emulsifier, cosolvent, thickener, antifreeze, the water of above-mentioned formula.
2, methidathion is added in conical flask, after adding toluene stirring and dissolving, then add sorbester p17 to stir, then shake 5 minutes under ultrasonic, form first-phase.
3, PEG-200, polysorbate60, ethylhydroxyethylcellulose, propane diols, defoamer are added in conical flask, add water to 100g, stir to dissolving, form second-phase.
4, second-phase is under the stirring of 1500 revs/min of rotating speeds, first-phase is slowly added dropwise to second-phase (rate of addition is 0.15mL/min), continues to stir 30 minutes, form uniform nano-emulsion, the method of pressing embodiment 1 is surveyed the particle diameter of nano-emulsion, records average grain diameter 90 nm.Low-temperature stability is qualified, thermodynamic stability (54 ± 2
oc, 2 weeks) resolution ratio≤10%.
Embodiment 9
Preparation process is as follows:
1, take former medicine, emulsifier, cosolvent, antifreeze, the water of above-mentioned formula.
2, methidathion is added in conical flask, after adding toluene stirring and dissolving, then add sorbester p17 to stir, then the lower concussion of ultrasonic (50 W, 40 kHz) 5 minutes, form first-phase.
3, PEG-400, polysorbate60, ethylene glycol are added in conical flask, add water to 100g, stir to dissolving, form second-phase.
4, second-phase is under the stirring of 2000 revs/min of rotating speeds, first-phase is slowly added dropwise to second-phase (rate of addition is 0.2mL/min), continues to stir 30 minutes, form uniform nano-emulsion, the method of pressing embodiment 1 is surveyed the particle diameter of nano-emulsion, records average grain diameter 130 nm.Low-temperature stability is qualified, thermodynamic stability (54 ± 2
oc, 2 weeks) resolution ratio≤10%.
Claims (6)
1. a methidathion nanoemulsion, the raw material that it is characterized in that preparing described methidathion nanoemulsion comprises the composition of following percentage by weight:
The total amount of all the components is 100%;
The method of preparing described methidathion nano-emulsion comprises the following steps: (1) takes each component raw material by above-mentioned percentage by weight, first former methidathion medicine and organic solvent, partial emulsifier A are stirred and dissolved, fully be uniformly dispersed, make first-phase; (2) by remaining emulsifier B and the water-soluble generation second-phase of other remaining reagent; (3) second-phase, under the stirring of 700-2000 rev/min of rotating speed, is slowly added dropwise to second-phase by first-phase, continues to stir 30-60 minute, makes described methidathion nanoemulsion;
Described organic solvent is toluene;
Described cosolvent is PEG-200, PEG-400 or PEG-600;
Described emulsifier is the summation of emulsifier A and emulsifier B;
Described emulsifier A is agriculture breast 500, Arlacel-60 or Arlacel-80, and described emulsifier B is Tween-60 or Tween-80;
Described antifreeze is one or more any combination in ethylene glycol, propane diols or glycerine.
2. methidathion nanoemulsion as claimed in claim 1, the raw material that it is characterized in that preparing described methidathion nanoemulsion also comprises the defoamer of quality percentage mark 0-0.5% thickener and/or quality percentage mark 0-0.25%; Described thickener and/or defoamer for step (2) as other remaining reagent parts and remaining emulsifier B and the water-soluble generation second-phase of other remaining reagent;
Described thickener is the two stearates of hydroxyethylcellulose, methyl hydroxyethylcellulose, ethylhydroxyethylcellulose, methylhydroxypropylcellulose, carboxymethyl cellulose or Macrogol 6000; Described defoamer is silicone defoaming agent.
3. methidathion nanoemulsion as claimed in claim 2, is characterized in that described methidathion nanoemulsion is prepared from by the composition of following percentage by weight:
The total amount of all the components is 100%;
Described preparation method is: (1) takes each component raw material by above-mentioned percentage by weight, first former methidathion medicine and organic solvent, partial emulsifier A is stirred and is dissolved, and under ultrasonic, shakes 5-20 minute, makes first-phase; (2) again by water-soluble to remaining emulsifier B, cosolvent, thickener, antifreeze, defoamer generation second-phase; (3) second-phase, under the stirring of 700-2000 rev/min of rotating speed, is slowly added dropwise to second-phase by first-phase, continues to stir 30-60 minute, makes described methidathion nanoemulsion.
4. methidathion nanoemulsion as claimed in claim 2 or claim 3, is characterized in that described defoamer is emulsion-type silicon oil foam killer.
5. the methidathion nanoemulsion as described in one of claim 1～3,10～35% of the gross mass consumption that the quality consumption that it is characterized in that described emulsifier A is emulsifier.
6. a preparation method for methidathion nanoemulsion, is characterized in that described methidathion nanoemulsion is prepared from by the composition of following percentage by weight:
The total amount of all the components is 100%;
Described preparation method is: (1) takes each component raw material by above-mentioned percentage by weight, first former methidathion medicine and organic solvent, partial emulsifier A is stirred and is dissolved, and under ultrasonic, shakes 5-20 minute, makes first-phase; (2) again by water-soluble to remaining emulsifier B, cosolvent, thickener, antifreeze, defoamer generation second-phase; (3) second-phase, under the stirring of 700-2000 rev/min of rotating speed, is slowly added dropwise to second-phase by first-phase, continues to stir 30-60 minute, makes described methidathion nanoemulsion;
Described organic solvent is toluene;
Described cosolvent is PEG-200, PEG-400 or PEG-600;
Described emulsifier is the summation of emulsifier A and emulsifier B; Described emulsifier A is agriculture breast 500, Arlacel-60 or Arlacel-80, and described emulsifier B is Tween-60 or Tween-80;
Described antifreeze is one or more any combination in ethylene glycol, propane diols or glycerine.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008032328A2 (en) * | 2006-09-14 | 2008-03-20 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Pesticide nanoparticles obtained from microemulsions and nanoemulsions |
| CN101683593A (en) * | 2008-08-15 | 2010-03-31 | 赢创戈尔德施米特有限公司 | Nano-emulsions and method of producing them, and their use |
| CN102113514A (en) * | 2010-01-05 | 2011-07-06 | 海南正业中农高科股份有限公司 | Pesticide composition containing chlorpyrifos and methidathion |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008032328A2 (en) * | 2006-09-14 | 2008-03-20 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Pesticide nanoparticles obtained from microemulsions and nanoemulsions |
| CN101683593A (en) * | 2008-08-15 | 2010-03-31 | 赢创戈尔德施米特有限公司 | Nano-emulsions and method of producing them, and their use |
| CN102113514A (en) * | 2010-01-05 | 2011-07-06 | 海南正业中农高科股份有限公司 | Pesticide composition containing chlorpyrifos and methidathion |
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