CN103598200B - Insecticidal composition containing clothianidin and pirimicarb - Google Patents
Insecticidal composition containing clothianidin and pirimicarb Download PDFInfo
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- CN103598200B CN103598200B CN201310629363.7A CN201310629363A CN103598200B CN 103598200 B CN103598200 B CN 103598200B CN 201310629363 A CN201310629363 A CN 201310629363A CN 103598200 B CN103598200 B CN 103598200B
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Abstract
The invention discloses an insecticidal composition containing clothianidin and pirimicarb, the weight ratio of the active component clothianidin to the active component pirimicarb is 1-30:1-40, the total active components account for 1%-70% by weight of the composition, and the forms of the insecticidal composition comprise wettable powders, water-soluble granules, suspending agents, emulsions in water and microcapsule suspending agents. The insecticidal composition is based on dual function mechanism of two insecticides such as clothianidin and pirimicarb, has the two characteristics of being quick-acting and long-acting, so that the insecticidal composition is increased in application scope, enlarged in insecticidal spectrum, not only can control leafhopper, but also has substantial control effect on cotton aphid, is obvious in synergy, causes no contradiction, and is long in lasting effect, reduced in drug applying frequency and reduced in drug applying cost.
Description
Technical field
The present invention relates to clothianidin and Aphox is the Pesticidal combination of active ingredient.
Background technology
Clothianidin, chemical name is (E)-1-(the chloro-1,3-thiazoles of 2--5-ylmethyl)-3-methyl-2-2-nitroguanidine, is jointly to carry out world market exploitation by Beyer Co., Ltd and Japanese Takeda Wu Tian company.
Its structural formula is:
Clothianidin is the anabasine insecticide of a class highly effective and safe, high selectivity, and its effect is similar with nAChR, have tag, stomach toxicity and systemic activity.To be mainly used on paddy rice, vegetables, fruit tree and other crops anti-ly eliminating aphis, leafhopper, thrips, the Semiptera such as plant hopper, coleoptera, diptera and some Lepidoptera class pest insecticide, have efficient, wide spectrum, consumption are few, toxicity is low, the drug effect lasting period long, to crop without poisoning, use safety and conventional pesticide without advantages such as cross resistances, having remarkable interior suction and osmosis, is the another kind of alternative high-toxic organic phosphorus agricultural chemicals.Its novel structure, special, performance is more excellent compared with traditional nicotinic insecticide.
Aphox (Pirimicarb) is now widely used broad spectrum activity carbamate insecticide.Aphox has tags, fumigates, permeates the modes of action such as blade face, is generally used as foliar spray.Main control Diptera pest, can be used on fruit tree, cereal, soft fruits, beans, wild cabbage, rape, lettuce, beet, potato, flowers and some ornamental plantss, to crop safety, quick-acting is good, persistence is not long, but substantially invalid to cotten aphid.
Different cultivars active ingredient is carried out composite, is the common solution delaying pest pesticide resistance, expanding prevention object, raising quick-acting, raising control efficiency.Heterogeneity is carried out composite, according to the composite effect of reality, judges that composite is synergy, addition or antagonism.Have not yet to see about clothianidin and the composite relevant report of Aphox.
Summary of the invention
The object of the invention is the controlling object in order to expand clothianidin and Aphox, control efficiency, delaying drug resistance, reduce drug cost, a kind of agricultural insecticide composition containing insecticidal active ingredient clothianidin and insecticidal active ingredient Aphox is provided, wherein the weight ratio of active ingredient clothianidin and active ingredient Aphox is 1 ~ 30 ︰ 1 ~ 40, and the gross weight of active ingredient accounts for 1% ~ 70% of composition total weight.
Pesticidal combination of the present invention, is processed into wetting powder, water dispersible granules, suspending agent, aqueous emulsion, micro-capsule suspension by this area current techique.
When said composition makes wetting powder, each constituent content is:
The concrete procedure of processing of this Pesticidal combination wetting powder is: by above-mentioned formula by clothianidin and Aphox and the mixing of dispersant, wetting agent and filler, uniform stirring in stirred tank, mix after airslide disintegrating mill, the wetting powder of the present composition can be obtained.
When said composition makes water dispersible granules, each constituent content is:
The concrete procedure of processing of this Pesticidal combination water dispersible granules is: clothianidin, Aphox and dispersant, wetting agent, disintegrant and filler are mixed by above-mentioned formula, pulverize with micro jet, through mediating, then add in fluidized-bed granulation dryer and carry out granulation, drying, screening, the water dispersible granules containing clothianidin and Aphox Pesticidal combination obtained of the present invention.
When said composition is processed into suspending agent, each constituent content is:
The concrete procedure of processing of this Pesticidal combination suspending agent is first mixed by auxiliary agent, mix through high speed shear, add clothianidin and the former medicine of Aphox, ball milling 2-3 hour in ball mill, make diameter of particle all below 5 μm, the aqueous suspension formulations containing the Pesticidal combination of clothianidin and Aphox obtained of the present invention.
When said composition is processed into aqueous emulsion, each constituent content is:
The concrete procedure of processing of this Pesticidal combination aqueous emulsion is for be added together former medicine clothianidin and Aphox, solvent and emulsifier, it is made to be dissolved into uniform oil phase, other insecticides adjuvants such as part water, antifreezing agent are mixed into uniform aqueous phase, in a kettle. while high-speed stirred, oil phase is added in aqueous phase, slowly add water until arrive phase inversion point, open clipper and carry out high speed shear, and add remaining water, shear 30min.The i.e. aqueous emulsion preparation containing the Pesticidal combination of clothianidin and Aphox obtained of the present invention.
When said composition is processed into micro-capsule suspension, constituent content is:
The processing method of this Pesticidal combination micro-capsule suspension has two kinds:
Method one: the preparation of (1) urea resin prepolymer: by formalin (mol ratio=1:1.5-2) mix and blend of urea and 37% mass percent, pH to 8.5 is regulated with triethylamine, be warming up to 70 DEG C, with 450 revs/min of stirring reactions 1 hour, obtain the urea resin prepolymer aqueous solution; (2) micro-capsule suspension preparation: under normal temperature, clothianidin, Aphox are dissolved in solvent, dispersant, urea-formaldehyde resin aqueous solution, emulsifier is added under stirring condition, high speed homogenizing 5 minutes, reduce rotating speed to 450 rev/min after forming oil-in-water emulsion, regulate pH, react 1 hour under acid catalysis, to reaction end, adjust pH to neutral; Add thickener, stir and namely make micro-capsule suspension.
Method two: clothianidin, Aphox are dissolved in solvent by (1), adds capsule leather material and stirs and obtain oil phase; (2) in water, add emulsifier for mixing and evenly obtain aqueous phase; (3) aqueous phase joins in oil phase, high speed homogenizing formation stabilized oil-in-water emulsion; (4) under 450 revs/min, add pH adjusting agent and participate in interface polymerization reaction, reaction temperature rises to 25 DEG C-70 DEG C, keeps solidifying encystation in 2-24 hour; (5) add dispersant, thickener, stir and namely make micro-capsule suspension.
Described emulsifier is one or more in alkylbenzene naphthalene sulfonate, alkylphenol polyoxyethylene phosphate, diphenyl phenol polyethenoxy polyethenoxy ether, styrenated phenol APEO, alkylphenol polyoxyethylene formaldehyde condensation products, diphenyl phenol polyethenoxy polyformaldehyde condensation product, castor oil ethylene oxide adduct, NNO, NP, agriculture breast 500, agriculture breast 600, Tween-80, polyvinyl alcohol.
Described dispersant is one or more in lignosulfonates, fatty acid amide N methyl taurine sodium salt, alkylphenol polyoxyethylene sulphate, polyoxyethylene polyoxypropylene block copolymer, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether.
Described wetting agent be selected from lauryl sodium sulfate, calcium dodecyl benzene sulfonate, Nekal BX, sodium alkyl benzene sulfonate, polyoxyethylene tri-styryl phosphenylic acid salt, spaonin powder one or more.
Described disintegrant be selected from bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, sodium bicarbonate one or more.
Described filler be selected from kaolin, diatomite, bentonite, attapulgite, white carbon, starch, precipitated calcium carbonate one or more.
Described thickener is one in aluminium-magnesium silicate, xanthans, CMC, gum Arabic, polyvinylpyrrolidone or several.
Described antifreezing agent is selected from one or more in ethylene glycol, propane diols, glycerine, polyethylene glycol.
Described defoamer is selected from silicone compound, C
10-20saturated fat acid compounds, C
8-10one or more in aliphatic alcohols compound and polyoxyethylene glycerol ether.
Described capsule leather material is one or more in tolyl isocyanate, the many toluene diisocyanates of polymethylene, methyl diphenylene diisocyanate, Lauxite.
Described solvent is one or more in toluene, dimethylbenzene, ethanol, DMF, chloroform, cyclohexanone, acetone.
Described pH adjusting agent mainly contains one or more in hydrochloric acid, glacial acetic acid, citric acid, sodium hydroxide, ammoniacal liquor, ethylenediamine, triethanolamine, triethylamine.
The present invention has the following advantages:
(1) clothianidin and Aphox are mutually composite, possess quick-acting and long-acting two major features.For anti-to eliminate aphis, leafhopper, thrips, Semiptera, coleoptera, diptera and some Lepidoptera class pest such as plant hopper, synergy is obvious, does not produce conflict, and dosage reduces.(2) clothianidin and Aphox mutually composite after use scope and increase, insecticidal spectrum expands, be applicable to the various crop such as paddy rice, vegetables, fruit tree, ornamental plants, can anti-eliminate aphis, leafhopper, thrips, Semiptera, coleoptera, diptera and some Lepidoptera class pest such as plant hopper, also have significant preventive effect to cotten aphid.
(3) after composite, there are clothianidin and Aphox two kinds of insecticide double action mechanism, the generation of pest resistance to insecticide can be delayed.Lasting period extends, and times for spraying reduces, and drug cost reduces.
Embodiment
Be elaborated the present invention below by embodiment, the percentage in embodiment is weight percentage, but the present invention is not limited thereto.
Embodiment 1:21% Aphox clothianidin wetting powder
Aphox 1%, clothianidin 20%, polyoxyethylene carboxylate 5%, lauryl sodium sulfate 5%, kaolin complement to 100%, after mixing in stirred tank uniform stirring, then pulverize through airslide disintegrating mill, obtained 21% Aphox clothianidin wetting powder.
Embodiment 2:70% Aphox clothianidin wetting powder
Aphox 40%, clothianidin 30%, lignosulfonates 7%, spaonin powder 5%, bentonite complement to 100%, after mixing in stirred tank uniform stirring, then pulverize through airslide disintegrating mill, obtained 70% Aphox clothianidin wetting powder.
Embodiment 3:2% Aphox clothianidin wetting powder
Aphox 1%, clothianidin 1%, alkylsulfonate 4%, Nekal BX 3%, diatomite complement to 100%, after mixing in stirred tank uniform stirring, then pulverize through airslide disintegrating mill, obtained 2% Aphox clothianidin wetting powder.
Embodiment 4:50% Aphox clothianidin water dispersible granules
Aphox 40%, clothianidin 10%, alkylphenol polyoxyethylene 6%, lauryl sodium sulfate 4%, urea 5%, kaolin supply 100%, after mixing, pulverize with micro jet, through mediating, then add in fluidized-bed granulation dryer and carry out granulation, the rear obtained 50% Aphox clothianidin water-dispersible granules of dry, screening.
Embodiment 5:70% Aphox clothianidin water dispersible granules
Aphox 40%, clothianidin 30%, fatty alcohol-polyoxyethylene ether 9%, sodium alkyl benzene sulfonate 5%, ammonium sulfate 2%, diatomite supply 100%, after mixing, pulverize with micro jet, through mediating, then add in fluidized-bed granulation dryer and carry out granulation, the rear obtained 70% Aphox clothianidin water-dispersible granules of dry, screening.
Embodiment 6:2% Aphox clothianidin water dispersible granules
Aphox 1%, clothianidin 1%, fatty acid amide N methyl taurine sodium salt 3%, polyoxyethylene tri-styryl phosphenylic acid salt 3%, bentonite supply 100%; after mixing; pulverize with micro jet; through mediating; then add in fluidized-bed granulation dryer and carry out granulation, the rear 2% obtained Aphox clothianidin water-dispersible granules of dry, screening.
Embodiment 7:25% Aphox clothianidin suspending agent
Aphox 20%, clothianidin 5%, alkylphenol polyoxyethylene 6%, aluminium-magnesium silicate 4%, ethylene glycol 1%, polyoxyethylene glycerol ether 0.5%, water supply 100%, first by alkylphenol polyoxyethylene, alkylphenol polyoxyethylene, ethylene glycol, polyoxyethylene glycerol ether, water mix, mix through high speed shear, add clothianidin and the former medicine of Aphox, ball milling 2 hours in ball mill, obtained 25% Aphox clothianidin suspending agent
Embodiment 8:70% Aphox clothianidin suspending agent
Aphox 40%, clothianidin 30%, lignosulfonates 10%, xanthans 3%, polyethylene glycol 2%, silicone compound 1%, water supply 100%, first by lignosulfonates, xanthans, polyethylene glycol, silicone oil, water mix, mix through high speed shear, add clothianidin and the former medicine of Aphox, ball milling 3 hours in ball mill, obtained 70% Aphox clothianidin suspending agent.
Embodiment 9:2% Aphox clothianidin suspending agent
Aphox 1%, clothianidin 1%, fatty alcohol-polyoxyethylene ether 10%, polyvinylpyrrolidone 5%, propane diols 2%, C
8-10aliphatic alcohols compound 0.1%, water supply 100%, first by fatty alcohol-polyoxyethylene ether, polyvinylpyrrolidone, and propane diols, C
8-10aliphatic alcohols compound, water mix, and mix, add clothianidin and the former medicine of Aphox, ball milling 3 hours in ball mill through high speed shear, obtained 2% Aphox clothianidin suspending agent
Embodiment 10:51% Aphox clothianidin aqueous emulsion
Aphox 40%, clothianidin 11%, agriculture breast 5008%, dimethylbenzene 6%, aluminium-magnesium silicate 4%, ethylene glycol 1%, polyoxyethylene glycerol ether 0.5%, water supply 100%, Aphox, clothianidin, dimethylbenzene are mixed formation oil phase with agriculture breast 500, ethylene glycol, aluminium-magnesium silicate, polyoxyethylene glycerol ether, part water are formed aqueous phase, in a kettle. while high-speed stirred, oil phase is added in aqueous phase, open clipper and carry out high speed shear, and add remaining water, shear 30min, obtained 51% Aphox clothianidin aqueous emulsion.
Embodiment 11:70% Aphox clothianidin aqueous emulsion
Aphox 40%, clothianidin 30%, styrenated phenol APEO 10%, toluene 10%, xanthans 3%, polyethylene glycol 2%, silicone compound 1%, water supply 100%, Aphox, clothianidin, styrenated phenol APEO are mixed formation oil phase with toluene, polyethylene glycol, xanthans, silicone compound, part water are formed aqueous phase, in a kettle. while high-speed stirred, oil phase is added in aqueous phase, open clipper and carry out high speed shear, and add remaining water, shear 30min, 70% Aphox clothianidin aqueous emulsion obtained after mixing.
Embodiment 12:2% Aphox clothianidin aqueous emulsion
Aphox 1%, clothianidin 1%, Tween-80 1%, DMF 10%, polyvinylpyrrolidone 5%, propane diols 2%, C
8-10aliphatic alcohols compound 0.1%, water supply 100%, and Aphox, clothianidin, DMF are mixed formation oil phase with Tween-80, by propane diols, polyvinylpyrrolidone, C
8-10aliphatic alcohols compound, part water form aqueous phase, in a kettle. while high-speed stirred, are added by oil phase in aqueous phase, open clipper and carry out high speed shear, and add remaining water, shear 30min, obtained 2% Aphox clothianidin aqueous emulsion after mixing.
Embodiment 13:22% Aphox clothianidin micro-capsule suspension
Aphox 2%, clothianidin 20%, toluene 5%, Lauxite 3%, NP5%, sodium lignin sulfonate 3%, hydrochloric acid 2%, sodium hydroxide 1%, xanthans 5%, suitable quantity of water, prepare according to following processing technology: the preparation of (1) urea resin prepolymer: by urea and 37% formalin (mol ratio=1:1.5) mix and blend, pH to 8.5 is regulated with triethylamine, be warming up to 70 DEG C, with 450 revs/min of stirring reactions 1 hour, obtain the urea resin prepolymer aqueous solution; (2) micro-capsule suspension preparation: under normal temperature, clothianidin, Aphox are dissolved in toluene, sodium lignin sulfonate, urea-formaldehyde resin aqueous solution, NP is added under stirring condition, high speed homogenizing 5 minutes, reduce rotating speed to 450 rev/min after forming oil-in-water emulsion, regulate pH, react 1 hour under hydrochloric acid catalysis, to reaction end, sodium hydroxide adjusts pH to neutral; Add xanthans, stir and namely make 22% Aphox clothianidin micro-capsule suspension.
Embodiment 14:70% Aphox clothianidin micro-capsule suspension
Aphox 40%, clothianidin 30%, dimethylbenzene 5%, toluene di-isocyanate(TDI) 5%, Tween-80 5%, alkylphenol polyoxyethylene 5%, ethylenediamine 1%, aluminium-magnesium silicate 2%, suitable quantity of water, prepare according to following processing technology: clothianidin, Aphox are dissolved in dimethylbenzene by (1), add toluene di-isocyanate(TDI) and stir and obtain oil phase; (2) in water, add Tween-80 stir and obtain aqueous phase; (3) aqueous phase joins in oil phase, high speed homogenizing formation stabilized oil-in-water emulsion; (4) under 450 revs/min, add ethylenediamine and participate in interface polymerization reaction, reaction temperature rises to 25 DEG C-70 DEG C, keeps solidifying encystation in 2-24 hour; (5) add alkylphenol polyoxyethylene, aluminium-magnesium silicate, stir and namely make 70% Aphox clothianidin micro-capsule suspension.
Embodiment 15:2% Aphox clothianidin micro-capsule suspension
Aphox 1%, clothianidin 1%, N, dinethylformamide 1%, methyl diphenylene diisocyanate 0.5%, polyvinyl alcohol 2%, fatty acid amide N methyl taurine sodium salt 1%, triethanolamine 1%, gum Arabic 5%, suitable quantity of water, prepare according to following processing technology: clothianidin, Aphox are dissolved in N by (1), in dinethylformamide, add methyl diphenylene diisocyanate and stir and obtain oil phase; (2) in water, add polyvinyl alcohol stir and obtain aqueous phase; (3) aqueous phase joins in oil phase, high speed homogenizing formation stabilized oil-in-water emulsion; (4) under 450 revs/min, add triethanolamine and participate in interface polymerization reaction, reaction temperature rises to 25 DEG C-70 DEG C, keeps solidifying encystation in 2-24 hour; (5) add fatty acid amide N methyl taurine sodium salt, gum Arabic, stir and namely make 2% Aphox clothianidin micro-capsule suspension.
This experiment is the method adopting Toxicity Determination and field trial to combine.First by Toxicity Determination, the co-toxicity coefficient (CTC) after clear and definite two kinds of medicaments are composite by a certain percentage, CTC<80 is antagonism, 80≤CTC≤120 are summation action, CTC >=120 are synergistic effect, on this basis, then carry out field trial.
Table 1. Aphox, clothianidin are to the Toxicity Determination of rice fulgorid
As shown in Table 1, Aphox and the LC50 of clothianidin to rice fulgorid are respectively 10.16mg/L and 7.73mg/L.Aphox and clothianidin proportioning are when 40:1 to 1:30, and co-toxicity coefficient CTC is all greater than 120, illustrate that Aphox and clothianidin mixture in 40:1 to 1:30 scope all shows synergistic effect, and especially both synergistic effects when 10:1 are the most obvious.
The test of pesticide effectiveness of table 2 Aphox, clothianidin and composite control leafhopper thereof
As can be seen from Table 2, Aphox and clothianidin composite after effectively can prevent and treat leafhopper, control efficiency is all better than the preventive effect of single dose.In test scope of medication, Target crops is had no adverse effects.
The test of pesticide effectiveness of table 3 Aphox, clothianidin and composite prevention and control of aphides thereof
As can be seen from Table 3, Aphox and clothianidin composite after not only have good preventive effect to leafhopper, also have significant preventive effect to cotten aphid, control efficiency is better than the preventive effect of single dose, simultaneously can lower field rotating medicine number of times, delays pest resistance to insecticide and produces.Lasting period extends, and can reduce times for spraying, reduces cost accounting.And expand insecticidal spectrum.
Claims (3)
1. an agricultural insecticide composition, it is characterized in that insecticidal active ingredient is clothianidin and Aphox, the weight ratio of active ingredient clothianidin and active ingredient Aphox is 1 ~ 30 ︰ 1 ~ 40, the gross weight of active ingredient accounts for 1% ~ 70% of composition total weight, and Pesticidal combination formulation is wetting powder, water dispersible granules, suspending agent, aqueous emulsion, micro-capsule suspension.
2. a kind of agricultural insecticide composition according to claim 1, when it is characterized in that said composition is wetting powder, each constituent content is:
Clothianidin 1-30%
Aphox 1-40%
Dispersant 3-10%
Wetting agent 3-10%
Filler polishing to 100%
When said composition is water dispersible granules, each constituent content is:
Clothianidin 1-30%
Aphox 1-40%
Dispersant 3-10%
Wetting agent 3-10%
Disintegrant 2-5%
Filler polishing to 100%
When said composition is suspending agent, each constituent content is:
Clothianidin 1-30%
Aphox 1-40%
Dispersant 3-10%
Antifreezing agent 0.5-4%
Thickener 0.1-2%
Defoamer 0.1-1%
Water polishing to 100%
When said composition is aqueous emulsion, each constituent content is:
Clothianidin 1-30%
Aphox 1-40%
Emulsifier 2-10%
Solvent 3-10%
Thickener 0.1-5%
Antifreezing agent 0.5-2%
Defoamer 0.1-1%
Water polishing to 100%
When said composition is micro-capsule suspension, constituent content is:
Clothianidin 1-30%
Aphox 1-40%
Capsule leather material 0.5-5%
Solvent 1-5%
Dispersant 1-5%
Emulsifier 2-5%
Thickener 2-5%
PH adjusting agent 0-3%
Water polishing to 100%.
3. agricultural insecticide composition according to claim 2, is characterized in that:
Described emulsifier is one or more in alkylbenzene naphthalene sulfonate, alkylphenol polyoxyethylene phosphate, diphenyl phenol polyethenoxy polyethenoxy ether, styrenated phenol APEO, alkylphenol polyoxyethylene formaldehyde condensation products, diphenyl phenol polyethenoxy polyformaldehyde condensation product, castor oil ethylene oxide adduct, NNO, NP, agriculture breast 500, agriculture breast 600, Tween-80, polyvinyl alcohol;
Described dispersant is one or more in lignosulfonates, fatty acid amide N methyl taurine sodium salt, alkylphenol polyoxyethylene sulphate, polyoxyethylene polyoxypropylene block copolymer, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether;
Described wetting agent be selected from lauryl sodium sulfate, calcium dodecyl benzene sulfonate, Nekal BX, sodium alkyl benzene sulfonate, polyoxyethylene tri-styryl phosphenylic acid salt, spaonin powder one or more;
Described disintegrant be selected from bentonite, urea, ammonium sulfate, aluminium chloride, citric acid, succinic acid, sodium bicarbonate one or more;
Described filler be selected from kaolin, diatomite, bentonite, attapulgite, white carbon, starch, precipitated calcium carbonate one or more;
Described thickener is one in aluminium-magnesium silicate, xanthans, CMC, gum Arabic, polyvinylpyrrolidone or several;
Described antifreezing agent is selected from one or more in ethylene glycol, propane diols, glycerine, polyethylene glycol;
Described defoamer is selected from silicone oil, silicone compound, C
10-20saturated fat acid compounds, C
8-10one or more in aliphatic alcohols compound and polyoxyethylene glycerol ether;
Described capsule leather material is one or more in tolyl isocyanate, the many toluene diisocyanates of polymethylene, methyl diphenylene diisocyanate, Lauxite;
Described solvent is one or more in toluene, dimethylbenzene, ethanol, DMF, chloroform, cyclohexanone, acetone;
Described pH adjusting agent is one or more in hydrochloric acid, glacial acetic acid, citric acid, sodium hydroxide, ammoniacal liquor, ethylenediamine, triethanolamine, triethylamine.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101796960A (en) * | 2010-04-16 | 2010-08-11 | 陕西美邦农药有限公司 | Clothianidin-containing disinfestations composite |
| CN101796958A (en) * | 2010-04-16 | 2010-08-11 | 陕西美邦农药有限公司 | Insecticidal composition containing clothianidin and carbosulfan |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101796960A (en) * | 2010-04-16 | 2010-08-11 | 陕西美邦农药有限公司 | Clothianidin-containing disinfestations composite |
| CN101796958A (en) * | 2010-04-16 | 2010-08-11 | 陕西美邦农药有限公司 | Insecticidal composition containing clothianidin and carbosulfan |
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