Summary of the invention:
The present invention is intended to solve aforementioned technical problem, a kind of compound insecticidal aqueous emulsion that contains Hostathion and spiral shell mite ester and preparation method thereof is provided, with the pesticide resistance that solves Hostathion, insecticidal spectrum and quick-acting, the medication that has reduced spiral shell mite ester and the problem of drug cost that enlarges spiral shell mite ester, aspect the formulations of pesticide, optimize simultaneously.
Above-mentioned purpose of the present invention is to realize by following technological means.
A kind of compound insecticidal aqueous emulsion that contains Hostathion and spiral shell mite ester provided by the present invention, wherein contain following component by weight percentage:
Spiral shell mite ester 0.5-10%
Hostathion 10-40%.
The described compound insecticidal aqueous emulsion that contains Hostathion and spiral shell mite ester, preferably contain following component by weight percentage:
Spiral shell mite ester 2-5%
Hostathion 20-40%.
The described compound insecticidal aqueous emulsion that contains Hostathion and spiral shell mite ester, also contain following component by weight percentage: cosolvent 1-20%, and the content sum of Hostathion component described in the described by weight percentage aqueous emulsion, spiral shell mite ester component and co-solvent component is not more than 60%.
The described compound insecticidal aqueous emulsion that contains Hostathion and spiral shell mite ester also contains following component by weight percentage
Described emulsifier is selected from polyoxyethylene nonylphenol ether, alkylphenol polyoxyethylene, fat alcohol ethoxyl compound, styryl phenyl APEO, alkyl phenol formaldehyde resin polyoxyethylene ether, styrene phenol formaldehyde resin APEO, the polyoxyethylene polyoxypropylene block co-polyether, the secondary octyl phenol polyethenoxy ether, castor oil polyoxyethylene ether, fat alcohol alkoxy compound, tallow ethyoxyl amine salt, starch Sodium Octenyl Succinate, polyoxyethylene ether phosphate salt, alkyl phosphorus phosphate ester salt or naphthalene sulfonate salt; Described cosurfactant is selected from n-butanol, isobutanol, n-octyl alcohol; Described stabilizing agent is selected from epoxidized soybean oil, epoxychloropropane, triphenyl phosphite, glycidol ether or pentaerythrite.
Described cosolvent is selected from cyclohexanone, N, dinethylformamide, N,N-dimethylacetamide, dimethylbenzene, No. 1500 solvents, No. 2000 solvents; Described antifreezing agent is selected from ethylene glycol, PEG400, propane diols, glycerine, isopropyl alcohol; Described thickener is selected from xanthans, Magnesiumaluminumsilicate, sodium carboxymethylcellulose or organobentonite; Described water is deionized water or distilled water.
Cosurfactant, stabilizing agent, antifreezing agent, thickener consumption can be 0 when the emulsifier consumption is higher.
The present invention also provides a kind of preparation method who contains the compound insecticidal aqueous emulsion of Hostathion and spiral shell mite ester, it is characterized in that comprising following processing step:
A. with spiral shell mite ester, Hostathion, mix and obtain oil phase;
B. oil phase is mixed with water, regulate the pH value and make 4≤pH≤7, obtain containing the compound insecticidal aqueous emulsion of Hostathion and spiral shell mite ester;
Wherein by weight percentage, spiral shell mite ester content is that 0.5-10%, Hostathion content are 10-40% in the aqueous emulsion.
The described preparation method who contains the compound insecticidal aqueous emulsion of Hostathion and spiral shell mite ester, wherein:
Weight ratio according to spiral shell mite ester 0.5-10%, Hostathion 10-40%, emulsifier 5-12%, cosurfactant 0-5%, stabilizing agent 0-3%, solvent 1-20%, antifreezing agent 0-5%, thickener 0-3% and water surplus takes by weighing raw material;
Among the step a spiral shell mite ester, Hostathion, cosolvent, emulsifier and stabilizing agent mixed and obtain oil phase;
Among the step b oil phase is mixed with the water that is mixed gained by water, antifreezing agent, thickener, regulate the pH value and make 4≤pH≤7, obtain containing the compound insecticidal aqueous emulsion of Hostathion and spiral shell mite ester.
Described pH value is regulated by adding acidity or alkaline matter realizations such as acetate, formic acid, hydrochloric acid, sulfuric acid, benzoic acid, citric acid, ethylenediamine or triethylamine.
Wherein water and oil phase are to mix the compound insecticidal aqueous emulsion that obtains containing Hostathion and spiral shell mite ester under the high speed shear condition; Perhaps water and oil phase mix under mechanical agitation and obtain thick emulsion, with high pressure homogenizer thick emulsion homogeneous are obtained containing the compound insecticidal aqueous emulsion of Hostathion and spiral shell mite ester then.
The compound insecticidal aqueous emulsion that contains Hostathion and spiral shell mite ester provided by the present invention can reduce the pollution of aromatic hydrocarbon organic solvent to environment, avoid triazophos emulsifiable solution or the crystallization of spiral shell mite ester triazophos emulsifiable solution, thereby improve the product shelf life, and can solve the pesticide resistance problem of insect to triazophos emulsifiable solution, reduce simultaneously and use spiral shell mite ester cost problem of higher separately.
Hostathion and the spiral shell mite ester compound insecticidal aqueous emulsion outward appearance homogeneous of containing provided by the present invention; Easy mobility; Stability of emulsion is qualified; Cold and hot storage physical stability is qualified; In heat two weeks of storage under 54 ± 1 ℃ condition, spiral shell mite ester and Hostathion resolution ratio are all less than 5%, and storage back preparation stability of emulsion is qualified.
There are following technology of preparing difficult point in the compound insecticidal aqueous emulsion and the preparation thereof that contain Hostathion and spiral shell mite ester: the aqueous pesticide preparation of the outward appearance homogeneous that aqueous emulsion forms for the agricultural chemicals oil droplet suspends in water is a thermodynamic unstable system.Under action of gravity, the oil droplet of suspension can sink gradually, in addition because of there being model ylid bloom action power between the oil droplet, easily attracting each other and agglomeration takes place and further quickens sedimentation, produces and piles up.When piling up gently, it is denseer thick that the preparation outward appearance is the bottom, up weakens gradually; Then occur flocculation when crossing closs packing, even produce precipitation or breakdown of emulsion (analysing oil) phenomenon, cause and to disperse to form the homogeneous system again.Therefore the appearance stability that solves preparation is one of technological difficulties of development spiral shell mite ester aqueous emulsion of triazophos.And Hostathion, spiral shell mite ester all have in various degree hydrolysis, especially Hostathion in water, meets water and more easily decompose.Therefore when exploitation Hostathion spirodiclofen water emulsion, chemical stability has become another technological difficulties.
The present invention is the technological difficulties that solve aforementioned aqueous emulsion preparation by following approach:
1. adopt the surfactant that strong adsorption capacity is arranged on agricultural chemicals oil droplet surface,, form more stable sterically hindered effect, prevent coalescent on the oil droplet surface as the polyoxyethylene polyoxypropylene block co-polyether etc.;
2. it is composite to select suitable surfactant to carry out, and makes composite emulsifier form the higher compound interface film of mechanical strength on agricultural chemicals oil droplet surface, and interfacial film intensity is high more, is difficult for taking place coalescent increase when oil droplet collides mutually, and system is just more stable;
3. select the suitable anion auxiliary agent,, strengthen the Zeta potential gesture, make electrostatic repulsion forces enhancing between oil droplet, be difficult for taking place coalescent as tallow ethyoxyl amine salt, phosphates, naphthalene sulfonate salt etc.;
4. select suitable process route and technological parameter, make oil droplet or the particle grain size distribution scope is narrower, meso-position radius is less (1~5 μ m), slow down settling velocity, and significantly alleviate the Ostwald ripening phenomenon;
5. keeping under preparation good mobility and the dispersed situation, utilize thickener regulation system viscosity such as xanthans, Magnesiumaluminumsilicate, sodium carboxymethylcellulose, organobentonite, form tridimensional network, support disperse phase (Hostathion, spiral shell mite ester) quality, and then delayed fallout, prevent generation precipitation or demulsifying phenomenon in the shelf life phase;
6. solved the problem of the composite aqueous emulsion of Hostathion spiral shell mite ester by adjusting preparation PH scope, the suitable chemical stabilizer (as epoxychloropropane) of interpolation, improved the chemical stability of composite aqueous emulsion greatly owing to Hostathion, the hydrolysis in water of spiral shell mite ester.
Provided by the present inventionly contain Hostathion and spiral shell mite ester compound insecticidal aqueous emulsion has following characteristics under the use of reality:
1, the agricultural chemicals after the preparation had both overcome the shortcoming that the mite class easily develops immunity to drugs to Hostathion, had enlarged the insecticidal spectrum and the quick-acting of spiral shell mite ester again, and had obviously improved drug effect.
2, obvious synergistic effect is arranged, the evil mite is all had good control efficiency each breeding time; Delayed the pesticide resistance of harmful mite, it is bigger that the resistance of evil mite is prevented and treated meaning.
3, because reasonable mixture ratio has reduced the control cost when drug effect promotes.
4, abandon whole benzene class aromatic hydrocarbons organic solvents, saved workload and relevant expenses such as the purchasing of benzene class aromatic solvent, transportation, avoid the generation of inflammable and explosive problem, reduced the fire safety burden.
5, use water to replace organic solvent as medium, reduce environmental pollution, the conservation cost can be avoided the influence of international petroleum market price simultaneously again.
6, solvent-free smell to the eye nonirritant, significantly is lower than missible oil to people's dermal toxicity; The fruit outward appearance there is not influence.
7, make and when using safety and processing cost low.
8, solved the easy decomposition and crystallization of triazophos emulsifiable solution preparation, physical and chemical stability is poor, shelf life is short defective preferably, 2 years no crystalline polamers of storage at normal temperature have remarkable economic efficiency.
Embodiment:
In order better to understand essence of an invention, describe the technology contents of invention below in detail with regard to the better utilization example.But content of the present invention not only is confined to this, and all changes inseparable with essence of the present invention and scope, modification, distortion or other use and use, and all are regarded as falling within the scope of the present invention.
Example 1
Spiral shell mite ester 0.5%, Hostathion 10%, cyclohexanone 3%, dimethylbenzene 12%, polyoxyethylene nonylphenol ether 4%, castor oil polyoxyethylene ether 7%, epoxidized soybean oil 2% are put in the high speed shear Mixingemulsificationmachine, after high speed shear, promptly got oil phase.Input ethylene glycol 3%, xanthans 1%, deionized water are mended to 100% in another high speed shear Mixingemulsificationmachine, promptly get water after mixing, water is squeezed into head tank, and under the condition of high speed shear, be added drop-wise in the oil phase, finish the pH value and also continue to shear 10-30 minute, promptly get 10.5% and contain Hostathion and spiral shell mite ester disinsection aqueous emulsion to 5-6.
Example 2
With spiral shell mite ester 2%, Hostathion 20%, N, dinethylformamide 3%, No. 1500 solvents 15%, alkylphenol polyoxyethylene 6%, tallow ethyoxyl amine salt 4%, epoxychloropropane 3% are put in the high speed shear Mixingemulsificationmachine, promptly get oil phase after high speed shear.Input PEG400 3%, Magnesiumaluminumsilicate 2%, distilled water are mended to 100% in another high speed shear Mixingemulsificationmachine, promptly get water after mixing, water is squeezed into head tank, and under the condition of high speed shear, be added drop-wise in the oil phase, finish the pH value and also continue to shear 10-30 minute, promptly get 22% and contain Hostathion and spiral shell mite ester disinsection aqueous emulsion to 5-6.
Example 3
With spiral shell mite ester 5%, Hostathion 30%, N, N-dimethylacetylamide 5%, No. 2000 solvents 15%, fat alcohol ethoxyl compound 7%, alkyl phosphorus phosphate ester salt 4%, triphenyl phosphites 3% are put in the high speed shear Mixingemulsificationmachine, promptly get oil phase after high speed shear.Input propane diols 3%, sodium carboxymethylcellulose 3%, distilled water are mended to 100% in another high speed shear Mixingemulsificationmachine, promptly get water after mixing, water is squeezed into head tank, and under the condition of high speed shear, be added drop-wise in the oil phase, finish the pH value and also continue to shear 10-30 minute, promptly get 35% and contain Hostathion and spiral shell mite ester disinsection aqueous emulsion to 5-6.
Example 4
With spiral shell mite ester 3%, Hostathion 37%, N, dinethylformamide 3%, No. 1500 solvents 15%, styrene phenol formaldehyde resin APEO, 4%, fat alcohol alkoxy compound 6%, polyoxyethylene polyoxypropylene block co-polyether 2%, pentaerythrites 2% are put in the high speed shear Mixingemulsificationmachine, promptly get oil phase after high speed shear.Input isopropyl alcohol 3%, xanthans 1%, deionized water are mended to 100% in another high speed shear Mixingemulsificationmachine, promptly get water after mixing, water is squeezed into head tank, and under the condition of high speed shear, be added drop-wise in the oil phase, finish the pH value and also continue to shear 10-30 minute, promptly get 40% and contain Hostathion and spiral shell mite ester disinsection aqueous emulsion to 5-6.
Example 5
With spiral shell mite ester 5%, Hostathion 40%, N, dinethylformamide 5%, dimethylbenzene 15%, styryl phenyl APEO 6%, polyoxyethylene ether phosphate salt 6%, glycidol ether 3% are put in the high speed shear Mixingemulsificationmachine, promptly get oil phase after high speed shear.Input glycerine 3%, organobentonite 3%, deionized water are mended to 100% in another high speed shear Mixingemulsificationmachine, promptly get water after mixing, water is squeezed into head tank, and under the condition of high speed shear, be added drop-wise in the oil phase, finish the pH value and also continue to shear 10-30 minute, promptly get 45% and contain Hostathion and spiral shell mite ester disinsection aqueous emulsion to 5-6.
Example 6
With spiral shell mite ester 10%, Hostathion 20%, N, N-dimethylacetylamide 5%, No. 2000 solvents 15%, styrene phenol formaldehyde resin APEO 6%, starch Sodium Octenyl Succinate 5%, epoxychloropropane 3% are put in the high speed shear Mixingemulsificationmachine, promptly get oil phase after high speed shear.Input glycerine 3%, Magnesiumaluminumsilicate 2%, distilled water are mended to 100% in another high speed shear Mixingemulsificationmachine, promptly get water after mixing, water is squeezed into head tank, and under the condition of high speed shear, be added drop-wise in the oil phase, finish the pH value and also continue to shear 10-30 minute, promptly get 30% and contain Hostathion and spiral shell mite ester disinsection aqueous emulsion to 5-6.
Example 7
Spiral shell mite ester 10%, Hostathion 30%, N,N-dimethylacetamide 5%, dimethylbenzene 15%, secondary octyl phenol polyethenoxy ether 8%, naphthalene sulfonate salt 4%, epoxidized soybean oil 3% are put in the high speed shear Mixingemulsificationmachine, after high speed shear, promptly got oil phase.Input ethylene glycol 3%, xanthans 1%, deionized water are mended to 100% in another high speed shear Mixingemulsificationmachine, promptly get water after mixing, water is squeezed into head tank, and under the condition of high speed shear, be added drop-wise in the oil phase, finish the pH value and also continue to shear 10-30 minute, promptly get 40% and contain Hostathion and spiral shell mite ester disinsection aqueous emulsion to 5-6.
The indoor biological activity test and the land for growing field crops pharmacy test of the agent of spiral shell mite ester Triazoxide as built-up.
Embodiment one: spiral shell mite ester Hostathion mixture is to the indoor virulence test (this test is undertaken by Agricultural University Of Nanjing) of citrus red mite:
Test spiral shell mite ester: (spiral shell: three) composite proportioning is 3: 37,2: 38,1: 39,4: 36 and 5: the 35 o'clock indoor biologically actives to the female one-tenth mite of citrus to Hostathion, and the contrast medicament is 10% spiral shell mite ester EC and 20% Hostathion EC.The slide infusion process that test method adopts FAO to recommend, checkout facility result behind the 24h.According to co-toxicity coefficient (Co-Toxicity coefficient) computational methods that (1960) such as Sun Yunpei are introduced, calculate the co-toxicity coefficient of mixture; With co-toxicity coefficient>120 is synergistic effect, and 80~120 is summation action, and<80 is antagonism, determines whether synergy of mixture.Result of the test sees Table 1:
Table 1 spiral shell mite ester Hostathion mixture is to indoor virulence and the co-toxicity coefficient (24h) of citrus red mite
Test result shows: spiral shell mite ester Hostathion mixture active ingredient (AI) is respectively 172.41,82.02,221.15,118.51 and 103.95 than being respectively 1: 39,2: 38,3: 37,4: 36 and 5: 35 totally five proportionings to the co-toxicity coefficient for the female one-tenth mite of examination citrus red mite.According to the standard of estimating composite dose, spiral shell mite ester: Hostathion 1: 39 and 3: 37 two proportionings have notable synergistic effect (C.T.C>120), and 2: 38,4: 36 and 5: 35 three proportionings are summation action (C.T.C is between 80~120).Spiral shell mite ester wherein: virulence of 3: 37 proportionings of Hostathion (LC50=28.69mg a.i./L, it is worth minimum) and co-toxicity coefficient are the highest, are best proportioning.
The field control effectiveness test that embodiment was carried out in the citrus garden of Quzhou City by the Zhejiang Academy of Agricultural Science in two: 2008 years, result of the test see Table 2, table 3:
Table 2 control citrus red mite result of the test (one-tenth) if mite
5 tables 3 control citrus red mite result of the test (ovum)