CN106857557B - A kind of Synergistic mite killing composition of the mite of pyrrole containing nitrile ester - Google Patents
A kind of Synergistic mite killing composition of the mite of pyrrole containing nitrile ester Download PDFInfo
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- CN106857557B CN106857557B CN201710088569.1A CN201710088569A CN106857557B CN 106857557 B CN106857557 B CN 106857557B CN 201710088569 A CN201710088569 A CN 201710088569A CN 106857557 B CN106857557 B CN 106857557B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
Abstract
The invention discloses a kind of Synergistic mite killing compositions, with N- (5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (2,6- difluoro pyridine -4- base)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidine (TDCA-10) and nitrile pyrrole mite ester are that acceptable auxiliary element collectively constitutes in effective component, with pesticide, and wherein TDCA-10 and nitrile pyrrole mite ester weight ratio are 80:1 to 1:20.It is tested, is shown after two kinds of combination of active principles without antagonism, and there is significant synergistic effect, to crop safety by laboratory experiment and field efficacy.
Description
Technical field
The present invention relates to a kind of insecticide acaricide compositions, concretely relate to one kind mite ester of pyrrole containing nitrile and the substitution of N- tri--
The insecticide acaricide composition of 1,2,3- thiadiazoles -5- formamidine compound, belongs to field of pesticide preparation.
Background technique
Mite class belongs to Arthropoda, Arachnoidea, Acarina, and individual is smaller.There may be all ranks in a group
The mite of section, including ovum, deutonymph, young mite and adult mite.Fruit tree, vegetables, cotton, peanut and other crops and ornamental plant are intensively infested mostly
The vacuum side of blade of object, and its breeding is rapidly, high these of selfing degree all determine the more difficult prevention and treatment of mite class.On the other hand, Nong Minyou
The good single acaricide of habit continuous use miticidal effect, as a result causes acarid to generate resistance within many time and lose benefit
With value.Therefore, using different role mechanism, different types of acaricide be solve harmful mite be also easy to produce resistance effective way it
One.
Nitrile pyrrole mite ester chemical formula C24H31N3O2, CAS accession number 560121-52-0, chemical structural formula is shown below (formula
1), English abbreviation Cyenopyrafen, the novel pyrazoles acaricide released by the Nissan Chemical company of Japan in 2009, and
It is registered in the same year in Japan and South Korea.Entitled (E) -2- (the 4-tert-butylphenyl) -2-cyano- of English language Chemical
1-(1,3,4-trim -ethylpyrazol-5-yl)vinyl-2,2-dimethylpropionate.Chinese chemical name
(E) -2- (4- tert-butyl-phenyl) -2- cyano -1- (1,3,4- trimethylpyrazol -5- base) alkenyl -2,2- dimethyl propylene acid esters.System
Agent single dose trade name: Starmite, preparation mixture (mixture with pyridaben) trade name: Valuestar.It was obtained since 2009
After formal registration, sales volume goes up year by year, reaches ten million dollar in the sales volume of nitrile pyrrole mite esters in 2010 and pyridaben mixture.
Nitrile pyrrole mite ester raw medicine sterling be white solid, 106.7 ~ 108.2 DEG C of fusing point.Nitrile pyrrole mite ester vapour pressure 5.2 × 10-4 MPa(25
DEG C), relative density 1.11 (20 DEG C).It is insoluble in water, solubility (20 DEG C) 0.30 mg/L in water.Stability in air:
Stablize in 14 d at 54 DEG C.Nitrile pyrrole mite ester mechanism of action is commonly referred to be: nitrile pyrrole mite this life of ester does not prevent and treat acarid work
With, but nitrile pyrrole mite ester (ester hydrolysis occurs in animal body and forms hydroxy compounds) by metabolism, is converted to hydroxy compound
Object (formula 2).This hydroxy compounds inhibits line by upsetting Complex II (succinate dehydrogenase) on respiratory electron transport chain
Normal effect of plastochondria destroys oxidative phosphorylation process, reaches preventive and therapeutic effect.Pharmacy effect mechanism is novel, it is contemplated that with it is current
The main insecticidal/acaricidal agent no interactions resistance used.Nitrile pyrrole mite ester can be used for preventing and treating fruit tree, tealeaves, all kinds of harmful mites on vegetables.
Interior is 2.5 mg/L to Tetranychus cinnabarinus spraying treatment concentration, and the death rate can reach 100%.Field trial shows that nitrile pyrrole mite ester makes
With concentration be 50 mg/L when, preventive effect is up to 98.74%.Raw medicine acute toxicity: rat acute LD505 000 mg/kg of >.
The percutaneous LD of rat acute505000 mg/kg of >.Rat sucks LC505.01 mg/L of (4 h) >.Ecotoxicological: to Bobwhite urgency
The oral LD of property502 000 mg/kg of >；Rainbow trout LC50(96 h)18.3 μg/L.To Predatory Mites, green at 15 g/100 L
Color lacewing, flower bedbug, honeybee and hornet are non-toxic.Environment degradable: the medicament does not have bioconcentration, in animal body
It is interior mainly to pass through dejection degradation (degradation 95% ~ 99% in about 120 h)；It slowly degrades in plant.It can in soil and water
It degrades rapidly, the DT in the soil of field50For 2 ~ 5 d, DT90For 5 ~ 15 d.Cyenopyrafen can be effectively controlled fruit, citrus,
Various harmful mites on tealeaves, vegetables, foliage-spray.Interior is to Tetranychus cinnabarinus toxicity test the result shows that nitrile pyrrole mite ester
(Cyenopyrafen) there is very high acaricidal activity, and acaricidal activity is higher than its Z formula isomers.Field verification test result table
Bright nitrile pyrrole mite ester has preferable quick-acting and lasting effect to citrus red mite at 50 mg/L.As people are to environment, agricultural production
The increasingly raising of product safety requirements, the upgrading of Pesticidal products are also gradually accelerated, domestic some old acaricide kinds (such as three
Pure and mild Spanon of chlorbenside etc.) be prohibited from using due to its safety and resistance problem, and safety is relatively high, preventive effect more
Good acaricide (such as tebufenpyrad, pyridaben and clofentezine) kind, also because being used for a long time, resistance problem is also different degrees of
Show.Although also there are new acaricide research and development in recent years, since mite class is the evil object for easily generating resistance, therefore difference is needed
The acaricide of mechanism of action is used alternatingly.Nitrile pyrrole mite ester has the characteristics that low toxicity, low dosage and mite killing spectrum are wide, can be acaricide
Being used alternatingly for kind provides a kind of new selection.And its novel mechanism of action, it can more effectively prevent the danger of resistance harmful mite
Evil.
Nitrile pyrrole mite Lipase absobed route report is more, and representative synthetic route has several following.Route one: oxalic acid two
Ethyl ester is that starting material and acetone carry out condensation reaction and generates acetopyruvic acid ethylester, obtained acetopyruvic acid ethylester intermediate
Condensation ring closure reaction is carried out with hydrazine hydrate again and obtains 3- methylpyrazole -5- Ethyl formate, among 3- methylpyrazole -5- Ethyl formate
Body carries out methylation reaction with dimethyl suflfate again and obtains 1,3- dimethyl pyrazole -5- Ethyl formate, which carries out chlorine again
Methylation reaction obtains 1,3- dimethyl -4- chloromethyl pyrazole-5-ethyl formate, 1,3- dimethyl -4- chloromethyl pyrazoles -5- first
Acetoacetic ester intermediate carries out palladium carbon hydrogenation reduction again and obtains 1,3,4- trimethylpyrazol -5- Ethyl formates, 1,3,4- front three
Base pyrazole-5-ethyl formate intermediate again with condensation reaction carried out under basic conditions to tert-butyl benzene acetonitrile obtain hydroxy
Nitrile intermediate, hydroxy nitrile intermediate, then carry out esterification with pivaloyl chloride and finally obtain nitrile pyrrole mite ester.The conjunction of route two
It is similar with route one at method general thought, only slightly have difference in the synthesis of individual intermediates, route is summarized as follows: grass
Diethyl phthalate is starting material and acetone progress condensation reaction generation acetopyruvic acid ethylester, in obtained acetopyruvic acid ethylester
Mesosome carries out condensation ring closure reaction with hydrazine hydrate again and obtains 3- methylpyrazole -5- Ethyl formate, 3- methylpyrazole -5- Ethyl formate
Intermediate carries out methylation reaction with dimethyl suflfate again and obtains 1,3- dimethyl pyrazole -5- Ethyl formate, the intermediate again into
Row chloromethylation obtains 1,3- dimethyl -4- chloromethyl pyrazole-5-ethyl formate, 1,3- dimethyl -4- chloromethyl pyrazoles -
5- Ethyl formate intermediate carries out palladium carbon hydrogenation reduction again and obtains 1,3,4- trimethylpyrazol -5- Ethyl formates, and 1,3,4-
Trimethylpyrazol -5- Ethyl formate intermediate obtains 1,3,4- trimethylpyrazol -5- formic acid, 1,3,4- trimethyl pyrrole by hydrolysis
Azoles -5- carboxylic acid intermediates and thionyl chloride obtain 1,3,4- trimethylpyrazol -5- formyl chloromethylated intermediate again, should and acid chloride intermediate
Again with condensation reaction carried out under basic conditions to tert-butyl benzene acetonitrile obtain hydroxy nitrile intermediate, among hydroxy nitrile
Body, then carry out esterification with pivaloyl chloride and finally obtain nitrile pyrrole mite ester.The synthetic method general thought and route one of route three,
Two difference of route is larger, and route is simply summarized as follows: 4- tert-butylbenzene acetonitrile is raw material and N- methyl -3,4- dimethyl -5-
After the reaction of carboxylate pyrazoles, then it is obtained with tertiary butyl acyl chloride reaction.
(denomination of invention: application number CN2015100098343, January 9 2015 date of application contain three nitrogen to Chinese patent
1,2,3- thiadiazoles -5- formamidine the compound of heterocycle and synthesis) in report the artificial Xihua Univ (inventor of patent application
The town Wang Hui, Liu Ping, Yang Wei are clear etc.) general formula be TDCA the polysubstituted -1,2,3- thiadiazoles -5- formamidine compound of N- and its conjunction
At method (formula 3).Chinese patent reports patent in (application number CN2015100237806, January 19 2015 date of application)
Apply for the polysubstituted -1,2,3- thiadiazoles -5- of N- that artificial Xihua Univ (inventor Liu Ping, Yang Wei clear etc.) mutual-through type is TDCA
The novel synthesis of formamidine compound is reported that the new method uses the synthesis of target product and is first cyclized, finally upper first
The method of base obtains fine experiment effect.Chinese patent (application number CN2015103042053, June 9 2015 date of application
Day, denomination of invention: cyclization method synthesize polynitrogen heterocycle thiadiazoles -5- formamidine compound) in report the artificial Xihua of patent application
University's (inventor Yang Weiqing, Liu Ping etc.) mutual-through type is the polysubstituted -1,2,3- thiadiazoles -5- formamidine compound of N- of TDCA
Novel synthesis reported that the new method is to the synthesis of target product using first upper methyl, and the method being finally cyclized, this is new
The easy preparation of synthetic method high income, catalyst, catalyst is cheap, phosphorus-containing wastewater is few, to more environment-friendly.Chinese patent
(patent No. ZL201510277765.4, May 28 2015 date of application, 2016 Granted publication dates August 31st, invention
Title: 1,2,3- thiadiazoles -5- formamidine poly-heterocyclic compounds are as acaricidal purposes) in report patent application artificially western
The general formula of Hua Da (inventor Yang Weiqing, Liu Ping, Zhang Yuanyuan etc.) is the polysubstituted -1,2,3- thiadiazoles -5- first of N- of TDCA
Evil of the amidine compound as acaricidal purposes, especially for fruit tree, vegetables, cotton, peanut and other crops and ornamental plant
Acarid control.But murder by poisoning power of the polysubstituted -1,2,3- thiadiazoles -5- formamidine compound of N- to part adult that general formula is TDCA
It is not powerful enough, it needs to carry out interworking use from the acaricide for killing high, the different mite killing mechanism of adult activity.It is well known that desinsection, killing
Mite agent is all easy pest in the long-term use and develops drug resistance, excellent with other for the service life for extending a new varieties
It is a kind of common strategy that different insecticidal/acaricidal agent kind, which carries out interworking use,.
Summary of the invention
The main object of the present invention is against the above deficiency, by the acaricidal rational mixture of different role mechanism, to provide
One kind having synergistic effect, and miticidal effect is good, safety, while can reduce the miticide composition of use cost again.
Chinese patent (patent No. ZL201510277765.4, May 28 2015 date of application, Granted publication date
On August 31st, 2016, denomination of invention: 1,2,3- thiadiazoles -5- formamidine poly-heterocyclic compounds are as acaricidal purposes) in report
Road general formula is N- polysubstituted -1,2, the 3- thiadiazoles -5- formamidine compound of TDCA as acaricidal purposes, is especially used
In the control of pest mite of fruit tree, vegetables, cotton, peanut and other crops and ornamental plant.The TDCA-6 in the compound that general formula is TDCA
The detailed title of~TDCA-13(TDCA-6~TDCA-13 and structural formula refer to Chinese Patent Application No. CN2015100098343) tool
There is preferable acaricidal activity.In TDCA-6~TDCA-13 compound, under the same terms, miticidal effect most preferably TDCA-10
(formula 4)；From another angle, production cost, two factor of acaricidal activity, TDCA-6(formula 5 are comprehensively considered) it is in numerous compounds
In comparison better acaricide.For convenient for expression, in the following narrations of the present invention, mainly with TDCA-10 represent general formula as
Polysubstituted -1,2,3- thiadiazoles -5- formamidine the compound of the N- of TDCA.
What the object of the invention was realized in that:
Miticide composition of the present invention is N- (5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (2,6- bis- with Chinese
Chloropyridine -4- base)-N, [English name is N- (5-tert-butyl-1,3,4- to 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidine
thiadiazol-2-yl)-N'- (2, 6-difluoropyridin-4-yl)-N,4-dimethyl-1,2,3-
Hereinafter referred to as TDCA-10 in the thiadiazole-5-carboxam-idine(present invention)], structural formula such as 2 institute of formula
The compound and nitrile pyrrole mite ester shown is that acceptable auxiliary element collectively constitutes in effective component, with pesticide.
The permission weight ratio of TDCA-10 and nitrile pyrrole mite ester is 100:1 to 1:80 in miticide composition of the present invention, is preferably compared
Example is 80:1 to 1:20.
Miticide composition compound of the present invention has acaricidal purposes, is especially used for fruit tree, vegetables, cotton, peanut
The control of pest mite of equal crops and ornamental plant.It is raw that the present composition is applied on crop and/or ornamental plant harmful acarid
Long region can effectively prevent harmful mite.Present composition administration time can be in each growth phase in acarid, including
Ovum, deutonymph, young mite and adult mite.Be mentioned below be the harmful mite that the present composition can be prevented and treated some representatives, enumerate unlimited
Harmful mite on following certain crops and/or ornamental plant.
As the mite class for becoming present composition control object, it can enumerate: belong to the mite of Ying Pi section: Japanese blood mite,
Haemaphysalis longicornis, boophilus microplus, dermacentor reticulatus, dermacentor taiwanensis, haemaphysalis flava, ixodes persulcatus etc..Belong to the mite of Eriophyidae: tea point leaf
Save tick, tealeaves goitre mite, apple rust mite, grape leaf rust mite, tulip aceria, fructus lycii burrknot tick, pseudo- pears rust tick, Pi Shi skin goitre mite
Deng.Belong to the mite of Tyroglyphidae: hesperidium mite, ellipse dispersion, Acarus siro, river open country rouge mite, Rhizoylyphus echinopus etc..Belong to Tarsonemidae
Mite: Webster tarsonemid, Polyphagotarsonemus latus Banks, primrose herbivore mite, double leaf tarsonemid.Belong to the mite of Eupodidae: wheat leaf pawl mite,
Chinese cabbage mite.Belong to the mite of Tetranychidae: panonychus citri, panonychus ulmi, mulberry Panonychus citri, Tetranychus urticae, Tetranychus cinnabarinus, purplish red short
It must mite, priet mite, Liu Shi short hairs mite, Asia beginning tetranychid, knee beginning tetranychid, northern beginning tetranychid, Lee's beginning tetranychid, Eotetranychus smithi
Deng.
Although the present composition shows outstanding prevention and treatment activity to the acarid of various mite sections, to useful crop, such as
Fruit tree, vegetables, cotton, peanut and other crops and/or ornamental plant only have the damage of small degree or absolutely not damage, and take
The specific structure of each compound, amount of application, the useful crop object of application certainly in present composition general structure.Here it is this
Invention compound can be suitable for the basic reason of control of pest mite on crop and/or ornamental plant.
Acceptable auxiliary element in described pesticide, including used in pesticide at present, unfavorable shadow will not be generated
Loud all kinds of common solvents and/or inert filler and/or surfactant and/or preservative and/or antifreezing agent and/or agglomeration resistance
Agent and/or defoaming agent and/or cosolvent and/or the corresponding adding ingredient such as stabilizer and/or thickener, and can be according to being produced
Dosage form do corresponding selection or adjustment.
Agrochemical formulations generally comprise the miticide composition of the present invention of 0.1-99 weight %, especially 2-90 weight %.?
Miticide composition concentration is in wettable powder (WP), such as the rest part in 10-90 weight %, 100 weight % is by routinely making
Agent auxiliary element composition.Miticide composition concentration is in suspending agent (SC), such as 1-90 weight %, preferably 5-75 weight %, 100
Rest part in weight % is made of conventional formulation auxiliary element.Miticide composition concentration is in suspoemulsion (SE), such as 1-
90 weight %, preferably 5-75 weight %, the rest part in 100 weight % are made of conventional formulation auxiliary element.In water dispersant
(WDG) miticide composition concentration is in, such as 1-95 weight %, preferably 10-70 weight %, and the rest part in 100 weight % is by normal
Regulation agent auxiliary element composition.The preparation of other powder types includes 1-40 weight % reactive compound, and preferably 5-20 weight % is living
Property compound, the rest part in 100 weight % are made of conventional formulation auxiliary element.
Miticide composition of the present invention is needed according to different uses or application Huan Jing ∕ condition, raw by current conventional pesticide
TDCA-10 in the miticide composition and nitrile pyrrole mite ester effective component and corresponding auxiliary element are that raw material is sufficiently mixed by production mode
It closes, is prepared into various forms of available corresponding dosage forms.Possible dosage form includes: wettable powder, water dispersant, hangs
Floating agent, aqueous emulsion, suspoemulsion, microcapsule formulations etc..Such as several typical common dosage forms and preparation can be with:
Microcapsule formulations (CJ), which refer to, forms " core-shell structure copolymer " structure small container using natural or synthesis high molecular material, will
Pesticide coats wherein, and the formulations of pesticide in water that suspend.Micro-capsule suspension appearance is a thick working fluid, with water
Emulsion and aqueous suspension agent are similar.With micro- sem observation, its shape of microcapsules is spherical in shape, rugby shape, grain or other shapes.It is micro-
Capsule diameter is generally at 3-30 microns.Small rice grain and mung bean grain size are about as much as with the observation of 400 power microscopes.Due to micro- glue
Capsule pesticide has the characteristics that the lasting period is long, toxicity is low, safe ready, just becomes a developing direction of pesticides new formulation.Micro- glue
The customary preparation methods of capsule have complex coacervation, Simple coacervation, interfacial polymerization, situ aggregation method, orifice-coagulating bath method etc..Most
Occur some novel processing steps, such as molecular inclusion, microchannel emulsification method, supercritical fluid quick expansion again in recent years
Method, yeast microcapsule method, self-assembled multilayer film method.Microcapsules often have sodium alginate, chitosan, gelatin, porous-starch with wall material
Deng.Complex coacervation is most popular method in above-mentioned microcapsule preparation method.Complex coacervation preparation principle is with two kinds with phase
The substance of counter charges makees embedded object, and core material disperses wherein, to change change pH values, temperature or solution concentration, due to the effect between charge,
Make two kinds of wall material solubility declines and is condensed into microcapsules precipitation.A kind of positively charged colloidal solution and another kind are negatively charged
Colloidal solution mutually mix, since the interaction between xenogenesis charge forms compound polyelectrolyte and separate, be deposited on
Microcapsules are obtained around capsule-core.Complex coacervation is often capsule material with gelatin, Arabic gum.Gelatin is protein, in aqueous solution,
Contain-NH on strand2With-COOH and its accordingly dissociate group-NH3+With-COO-, but contain-NH+3With-COO-Ion is how much,
It is influenced by PH values.For gelatin solution in pH 4.0 or so, positive charge is most.Arabic gum is polysaccharide, water-soluble
In liquid ,-COOH and-COO is contained on strand-, there is negative electrical charge.Therefore in gelatin and Arabic gum mixed aqueous solutions,
PH is adjusted when being about 4.0, gelatin and Arabic gum form compound because charged phase neutralizes instead, solubility reduction, from system
Middle cohesion encystation is precipitated.Curing agent formaldehyde is added, formaldehyde and gelatin generate the condensation reaction of amine aldehyde, and gelatin molecule crosslinking reticulates
Structure keeps the shape of micro-capsule, becomes irreversible micro-capsule；Add 2% NaOH to adjust medium pH 8 ~ 9, it is anti-to be conducive to the condensation of amine aldehyde
It should carry out completely.
Water dispersant (WDG) can fater disintegration in water, and can be uniformly dispersed in formation higher suspension dispersion in water
A kind of granular preparation.The present composition and auxiliary element one can be reinstated to air-flow smashing or ultra-fine grinding, system when preparation
At wettable powder, this is dry method；The present composition, auxiliary agent, adjuvant etc. are ground in sand mill using water as medium,
Suspending agent is made, then re-dry is granulated, this is wet process.
Wettable powder (WP), i.e., solid powder preparation that in water can be evenly dispersed.It, can be according to conventional side when preparation
Formula is firstly added the composition of TDCA-10 and nitrile pyrrole mite ester of the present invention, and diatomite, clay, precipitated calcium carbonate, white is then added
The common diluent such as carbon black or inert substance add other common auxiliary elements, such as alkylnaphthalene sulfonate, alkyl benzene sulphonate
Salt, aliphatic alcohol sulfate, alkyl bromination ammonium, alkyl ammomium chloride, quaternary alkylphosphonium salt, alkyl polyoxyethylene base ether sulfate, sulfomethylated lignin
One of hydrochlorate, lignin, carboxymethyl cellulose, sodium carboxymethylcellulose, azone, thiophene ketone are several, and common steady
Determine the complementary auxiliary component such as agent, foam inhibitor, anticaking agent.
Suspoemulsion (SE) the i.e. hybrid dispersions of the insoluble pesticide of water in water, one such effective component is in suspension
State, other effective components are in emulsion state.It can be by the present composition and corresponding emulsion, wet point when being prepared when preparation
The auxiliary elements such as powder, thickener, stabilizer, antifreezing agent, pH adjusting agent, defoaming agent, conventionally, through wet process Ultramicro-powder
It is broken to be mixed to prepare.Wherein emulsifier is alkyl phenol polyoxyethylene ether class (agriculture breast 100#), alkylbenzene sulfonate (agriculture breast 500#), benzene
Ethyl phenol polyethenoxy ether class (agriculture breast 600#), alkyl phenol or aralkyl phenol polyethenoxy ether formaldehyde condensation species (Nongru-700 #)
Deng one of or it is several.Wherein Ricinate is lignosulfonates, lignin, phosphate polyethers, carboxymethyl fibre
Tie up element, sodium carboxymethylcellulose, crown ether, alkylnaphthalene sulfonate, alkylbenzene sulfonate, aliphatic alcohol sulfate, alkyl ammonium halide, season
One of phosphonium salt, alkyl polyoxyethylene base ether sulfate, azone, thiophene ketone are several；Thickener and stabilizer are polyethylene
One of alcohol, condensed phosphate, xanthan gum, aluminum magnesium silicate etc. are several；Antifreezing agent be sodium chloride, urea, ammonium sulfate,
One of ethylene glycol, glycerol etc. are several；PH adjusting agent be potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate,
One of potassium carbonate etc. is several.Organosilicon is commonly used as defoaming agent and foam inhibitor.
Suspending agent (SC) i.e. agricultural chemicals suspension agent (SC) is water insoluble solids pesticide or not mixed liquid pesticidal in water or oil
Dispersion.When preparation, with water or oil for decentralized medium, by TDCA-10 of the present invention and nitrile pyrrole mite ester composition and auxiliary at
(such as thickener, stabilizer, Ricinate, antifreezing agent, pH adjusting agent, defoaming agent) is divided to make through soybean dietary fiber (grinding)
?.Wherein Ricinate is phosphate polyethers, alkylnaphthalene sulfonate, alkylbenzene sulfonate, aliphatic alcohol sulfate, alkyl bromide
Change ammonium, alkyl ammomium chloride, crown ether, quaternary alkylphosphonium salt, alkyl polyoxyethylene base ether sulfate, lignosulfonates, lignin, carboxymethyl
One of cellulose, sodium carboxymethylcellulose, azone, thiophene ketone are several；Thickener and stabilizer are polyvinyl alcohol, condensation
One of phosphate, xanthan gum, aluminum magnesium silicate etc. are several；Antifreezing agent be sodium chloride, urea, ammonium sulfate, ethylene glycol,
One of glycerol etc. is several；PH adjusting agent is potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate, potassium carbonate etc.
One of or it is several.Organosilicon is commonly used as defoaming agent and foam inhibitor.
It should be noted that specific dosage form mentioned above is the representative dosage form that present composition object can be prepared, enumerate
It is not limited to these above-mentioned dosage forms.
Agrochemical formulations generally comprise the present composition object of 0.1-99 weight %, especially 0.5-95 weight %.?
Activity compound concentration is in wettable powder (WP), such as the rest part in 1-90 weight %, 100 weight % is by conventional formulation
Auxiliary element composition.Activity compound concentration is in suspending agent (SC), such as 1-90 weight %, preferably 5-75 weight %, 100 weights
Rest part in amount % is made of conventional formulation auxiliary element.Activity compound concentration is in suspoemulsion (SE), such as 1-90
Weight %, preferably 5-75 weight %, the rest part in 100 weight % are made of conventional formulation auxiliary element.In water dispersant
(WDG) activity compound concentration is in, such as 1-95 weight %, preferably 10-70 weight %, and the rest part in 100 weight % is by normal
Regulation agent auxiliary element composition.The preparation of other powder types includes 1-40 weight % reactive compound, and preferably 5-20 weight % is living
Property compound, the rest part in 100 weight % are made of conventional formulation auxiliary element.
To be administered, if appropriate formulation is diluted in a usual manner, such as wettable powder, water dispersant,
Suspending agent, aqueous emulsion, suspoemulsion are diluted with water.Usually no longer with other inert materials before the application such as pulvis, granule, microcapsule formulations
Matter dilution.
The amount of application of the compounds of this invention changes according to external condition, and the external condition especially prevents and treats acarid pair
As, temperature, humidity, preparation formulation.It can change in a wider range, such as 0.1-500g/667m2Or more chemical combination of the present invention
Object, preferably 1-50g/667m2。
Concrete mode by the following examples is again described in further detail above content of the invention.But it does not answer
This range for being interpreted as the above-mentioned theme of the present invention is only limitted to example below by this.The above-mentioned technical idea feelings of the present invention are not being departed from
Under condition, the various replacements or change made according to ordinary skill knowledge and customary means, should all include of the invention
In range.Each material composition ratio is weight % in embodiment.
Specific embodiment:
(1), example of formulations
(55% refers to original ingredient to the miticide composition TDCA-10 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 1:55%
The mass percent of active component than in, similarly hereinafter)
350 grams of TDCA-10,200 grams of nitrile pyrrole mite esters, 60 grams of lignin, 45 grams of acrylic acid minor matters polymer, 40 are weighed respectively
Gram dodecyl sodium sulfate, 55 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 2:50%
300 grams of TDCA-10,200 grams of nitrile pyrrole mite esters, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 are weighed respectively
Gram dodecyl sodium sulfate, 55 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-13 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 3:50%
300 grams of TDCA-13,200 grams of nitrile pyrrole mite esters, 70 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 are weighed respectively
Gram dodecyl sodium sulfate, 60 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 4:50%
200 grams of TDCA-10,300 grams of nitrile pyrrole mite esters, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 30 are weighed respectively
Gram dodecyl sodium sulfate, 40 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10TDCA-6 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 5:30%
100 grams of TDCA-10,100 grams of TDCA-6,100 grams of nitrile pyrrole mite esters, 30 grams of lignin, 40 grams of acrylic acid are weighed respectively
Minor matters polymer, 30 grams of dodecyl sodium sulfates, 40 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 6:60%
570.0 grams of TDCA-10,30.0 grams of nitrile pyrrole mite esters, 60 grams of lignin, 50 grams of acrylic acid minor matters polymerizations are weighed respectively
Object, 35 grams of dodecyl sodium sulfates, 25 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10 nitrile pyrrole mite ester microcapsule formulations (CJ) of embodiment 7:6%
Weigh respectively 30 grams of TDCA-10,30 grams of nitrile pyrrole mite esters, 30 grams of gelatin, 20 grams of poly-aspartates, 10 grams of Tween-60s,
50 grams of Arabic gums, 10 grams of polyethylene glycol, 50 gram of 20% formalin, 10% acetum are appropriate, and (titer is i.e. by preparation process
In titration operation determine usage amount, similarly hereinafter), 20% NaOH solution (titer), distilled water complementary to 1000 grams, it is spare；
It is prepared by preparation step (1) poly-aspartate and gelatin mixed solution: after gelatin is impregnated swelling with distillation appropriate amount of water,
It dissolves by heating, is heated to 50 DEG C, poly-aspartate is added, appropriate distilled water is added, and 50 DEG C of heat preservations are spare in stirring.(2) Arabic
The preparation of sol solution: being added appropriate distilled water in reaction unit, Arabic gum powder is added, is heated to 80 DEG C or so, gently stirs
Mixing makes to dissolve, and 80 DEG C of heat preservations are spare.(3) preparation of TDCA-10 and nitrile pyrrole mite ester effective component emulsion: by TDCA-10, nitrile pyrrole mite
Ester, Tween-60, polyethylene glycol, above-mentioned preparation gumwater, be placed in tissue mashing machine, emulsify 30 seconds to get cream
Agent.(4) it mixes: under the conditions of 50~55 DEG C, above-mentioned poly-aspartate and gelatin mixed solution is added, being gently mixed keeps mixing equal
It is even.(5) preparation of micro-capsule: under constant stirring, 10% acetum is added dropwise in Xiang Qianshu mixed liquor, adjusts pH to 3.8~4.0；
(6) solidification of micro-capsule: under constant stirring, about 30 DEG C of distilled water is added in micro-capsule liquid, micro-capsule liquid will be contained from 50~55 DEG C
It removes, is stirred continuously in water-bath, ice cube is added when temperature drops to 32~35 DEG C in natural cooling, and continuing stirring to temperature is 10
DEG C hereinafter, 20% formalin is added, continue 15~25min of stirring, then with its pH 8~9 of 20%NaOH solution tune, continues to stir
20~30min, observation stand and settle to micro-capsule until being precipitated.(7) filtering and drying of micro-capsule: completely to micro-capsule sedimentation, mistake
Supernatant is filtered out, micro-capsule distillation is washed to formaldehydeless taste, centrifugation, drying.
The miticide composition TDCA-10 nitrile pyrrole mite ester microcapsule formulations (CJ) of embodiment 8:6%
Weigh respectively 40 grams of TDCA-10,20 grams of nitrile pyrrole mite esters, 30 grams of gelatin, 20 grams of poly-aspartates, 10 grams of Tween-60s,
50 grams of Arabic gums, 20 grams of polyethylene glycol, 50 gram of 20% formalin, 10% acetum appropriate (titer), 20% NaOH are molten
Liquid (titer), distilled water complementary are spare to 1000 grams；
Preparation step is completely same as Example 1.
The miticide composition TDCA-10 nitrile pyrrole mite ester microcapsule formulations (CJ) of embodiment 9:6%
Weigh respectively 20 grams of TDCA-10,40 grams of nitrile pyrrole mite esters, 30 grams of gelatin, 20 grams of poly-aspartates, 10 grams of Tween-60s,
50 grams of Arabic gums, 8 grams of polyethylene glycol, 50 gram of 20% formalin, 10% acetum appropriate (titer), 20% NaOH solution
(titer), distilled water complementary are spare to 1000 grams；
Preparation step is completely same as Example 1.
The miticide composition TDCA-10 nitrile pyrrole mite ester microcapsule formulations (CJ) of embodiment 10:10%
Weigh respectively 50 grams of TDCA-10,50 grams of nitrile pyrrole mite esters, 40 grams of gelatin, 30 grams of poly-aspartates, 20 grams of Tween-60s,
60 grams of Arabic gums, 30 grams of polyethylene glycol, 100 gram of 20% formalin, 10% acetum appropriate (titer), 20% NaOH are molten
Liquid (titer), distilled water complementary are spare to 1000 grams；
Preparation step is similar to Example 1.
The miticide composition TDCA-10 nitrile pyrrole mite ester microcapsule formulations (CJ) of embodiment 11:10%
Weigh respectively 33 grams of TDCA-10,67 grams of nitrile pyrrole mite esters, 40 grams of gelatin, 30 grams of poly-aspartates, 20 grams of Tween-60s,
60 grams of Arabic gums, 25 grams of polyethylene glycol, 100 gram of 20% formalin, 10% acetum appropriate (titer), 20% NaOH are molten
Liquid (titer), distilled water complementary are spare to 1000 grams；
Preparation step is similar to Example 1.
The miticide composition TDCA-10 nitrile pyrrole mite ester microcapsule formulations (CJ) of embodiment 12:10%
Weigh respectively 67 grams of TDCA-10,33 grams of nitrile pyrrole mite esters, 40 grams of gelatin, 30 grams of poly-aspartates, 20 grams of Tween-60s,
60 grams of Arabic gums, 50 grams of polyethylene glycol, 100 gram of 20% formalin, 10% acetum appropriate (titer), 20% NaOH are molten
Liquid (titer), distilled water complementary are spare to 1000 grams；
Preparation step is similar to Example 1.
The miticide composition TDCA-10TDCA-6 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 13:50%
240 grams of TDCA-10,60 grams of TDCA-6,200 grams of nitrile pyrrole mite esters, 50 grams of lignin, 50 grams of acrylic acid branches are weighed respectively
Section polymer, 40 grams of dodecyl sodium sulfates, 60 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10TDCA-6TDCA-13 nitrile pyrrole mite ester water dispersible granules of embodiment 14:30%
(WDG)
Weigh respectively 110 grams of TDCA-10,90 grams of TDCA-6,50 grams of TDCA-13,50 grams of nitrile pyrrole mite esters, 50 grams of lignin,
50 grams of acrylic acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 60 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10TDCA-6TDCA-13 nitrile pyrrole mite ester water dispersible granules of embodiment 15:50%
(WDG)
Weigh respectively 250 grams of TDCA-10,50 grams of TDCA-6,50 grams of TDCA-13,150 grams of nitrile pyrrole mite esters, 50 grams of lignin,
50 grams of acrylic acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 60 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10TDCA-6TDCA-13 nitrile pyrrole mite ester water dispersible granules of embodiment 16:60%
(WDG)
Weigh respectively 100 grams of TDCA-10,50 grams of TDCA-6,50 grams of TDCA-13,400 grams of nitrile pyrrole mite esters, 60 grams of lignin,
40 grams of acrylic acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 50 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10TDCA-6TDCA-13 nitrile pyrrole mite ester water dispersible granules of embodiment 17:60%
(WDG)
Weigh respectively 100 grams of TDCA-10,100 grams of TDCA-6,100 grams of TDCA-13,300 grams of nitrile pyrrole mite esters, 60 grams it is wooden
Element, 40 grams of acrylic acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 50 grams of polyethylene glycol, bentonite complementary are standby to 1000 grams
With；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10TDCA-6TDCA-13 nitrile pyrrole mite ester water dispersible granules of embodiment 18:60%
(WDG)
Weigh respectively 150 grams of TDCA-10,150 grams of TDCA-6,150 grams of TDCA-13,150 grams of nitrile pyrrole mite esters, 60 grams it is wooden
Element, 40 grams of acrylic acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 50 grams of polyethylene glycol, bentonite complementary are standby to 1000 grams
With；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 19:30%
200 grams of TDCA-10,100 grams of nitrile pyrrole mite esters, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 are weighed respectively
Gram dodecyl sodium sulfate, 30 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 20:40%
250 grams of TDCA-10,150 grams of nitrile pyrrole mite esters, 60 grams of lignin, 50 grams of acrylic acid minor matters polymer, 40 are weighed respectively
Gram dodecyl sodium sulfate, 60 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-13 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 21:30%
200 grams of TDCA-13,100 grams of nitrile pyrrole mite esters, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 are weighed respectively
Gram dodecyl sodium sulfate, 40 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10 nitrile pyrrole mite ester wettable powder (WP) of embodiment 22:40%
360.0 grams of TDCA-10,40.0 grams of nitrile pyrrole mite esters, 30 grams of lignosulfonates calcium, 30 grams of carboxymethyl fibres are weighed respectively
Plain sodium, 30 grams of aluminum magnesium silicates, 20 grams of neopelexes, 20 grams of tetrabutylammonium bromide, kaolin complementary are tieed up to 1000 grams,
It is spare；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The miticide composition TDCA-10 nitrile pyrrole mite ester wettable powder (WP) of embodiment 23:30%
200 grams of TDCA-10,100 grams of nitrile pyrrole mite esters, 30 grams of lignosulfonates calcium, 30 grams of carboxymethyl celluloses are weighed respectively
Plain sodium, 30 grams of aluminum magnesium silicates, 20 grams of neopelexes, 20 grams of tetrabutylammonium bromide, kaolin complementary are standby to 1000 grams
With；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The miticide composition TDCA-10 nitrile pyrrole mite ester wettable powder (WP) of embodiment 24:20%
100 grams of TDCA-10,100 grams of nitrile pyrrole mite esters, 35 grams of lignosulfonates calcium, 30 grams of carboxymethyl celluloses are weighed respectively
Plain sodium, 40 grams of aluminum magnesium silicates, 20 grams of neopelexes, 20 grams of tetrabutylammonium bromide, kaolin complementary are standby to 1000 grams
With；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The miticide composition TDCA-10 nitrile pyrrole mite ester wettable powder (WP) of embodiment 25:30%
100 grams of TDCA-10,200 grams of nitrile pyrrole mite esters, 30 grams of lignosulfonates calcium, 30 grams of carboxymethyl celluloses are weighed respectively
Plain sodium, 30 grams of aluminum magnesium silicates, 20 grams of neopelexes, 20 grams of tetrabutylammonium bromide, kaolin complementary are standby to 1000 grams
With；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The miticide composition TDCA-10 nitrile pyrrole mite ester wettable powder (WP) of embodiment 26:50%
100 grams of TDCA-10,400 grams of nitrile pyrrole mite esters, 40 grams of lignosulfonates calcium, 40 grams of carboxymethyl celluloses are weighed respectively
Plain sodium, 40 grams of aluminum magnesium silicates, 30 grams of neopelexes, 20 grams of tetrabutylammonium bromide, kaolin complementary are standby to 1000 grams
With；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
Reactive compound (TDCA-10) water dispersible granules (WDG) of embodiment 27:20%
200 grams of TDCA-10,70 grams of lignin, 60 grams of acrylic acid minor matters polymer, 50 grams of dodecyl sodium sulfonates are weighed respectively
Sodium, 80 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 28:20%
200 grams of nitrile pyrrole mite esters, 70 grams of lignin, 60 grams of acrylic acid minor matters polymer, 50 grams of dodecyl sulphurs are weighed respectively
Sour sodium, 80 grams of polyethylene glycol, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The nitrile pyrrole mite ester suspending agent (SC) of embodiment 29:35%
350 grams of nitrile pyrrole mite esters, 40 grams of lignosulfonates calcium, 50 grams of sodium carboxymethylcelluloses, 30 grams of silicic acid are weighed respectively
Magnalium, 40 grams of neopelexes, 60 grams of polyethylene glycol, water complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, is then ground in sand mill
To effective component partial size at 2~5 μm.
The nitrile pyrrole mite ester wettable powder (WP) of embodiment 30:30%
300 grams of nitrile pyrrole mite esters, 40 grams of lignosulfonates calcium, 40 grams of sodium carboxymethylcelluloses, 50 grams of silicic acid are weighed respectively
Magnalium, 30 grams of neopelexes, 25 grams of tetrabutylammonium bromide, kaolin complementary are spare to 1000 grams；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The TDCA-10 wettable powder (WP) of embodiment 31:30%
300 grams of TDCA-10,35 grams of lignosulfonates calcium, 35 grams of sodium carboxymethylcelluloses, 30 grams of alumina silicate are weighed respectively
Magnesium, 25 grams of neopelexes, 25 grams of tetrabutylammonium bromide, kaolin complementary are spare to 1000 grams；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The nitrile pyrrole mite ester suspending agent (SC) of embodiment 32:10%
100 grams of nitrile pyrrole mite esters, 50 grams of TERSPERSE 2020 (Huntsman Corporation, U.S. product, alkylnaphthalene sulphurs are weighed respectively
Barbiturates), 80 grams of lignosulfonates calcium, 30 grams of sodium carboxymethylcelluloses, 70 grams of aluminum magnesium silicates, 55 grams of dodecyl benzene sulfonic acid
Sodium, 50 grams of polyethylene glycol, water complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, is then ground in sand mill
To effective component partial size at 2~5 μm.
The TDCA-10 suspending agent (SC) of embodiment 33:5%
50 grams of TDCA-10,50 grams of fatty alcohol polyoxyethylene ether, 40 grams of lignosulfonates calcium, 55 grams of carboxylic first are weighed respectively
Base sodium cellulosate, 75 grams of aluminum magnesium silicates, 60 grams of neopelexes, 60 grams of polyethylene glycol, water complementary are standby to 1000 grams
With；
Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, is then ground in sand mill
To effective component partial size at 2~5 μm.
The nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 34:50%
500 grams of nitrile pyrrole mite esters, 40 grams of sodium lignin sulfonates, 50 grams of acrylic acid minor matters polymer, 30 grams of poly- second are weighed respectively
Alkene pyrrolidone, 20 grams of ammonium sulfate, 40 grams of dodecyl sodium sulfates, 35 grams of polyethylene glycol, 25 grams of sodium carboxymethylcelluloses, 100
Gram diatomite, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The TDCA-10 water dispersible granules (WDG) of embodiment 35:50%
500 grams of TDCA-10,30 grams of sodium lignin sulfonates, 40 grams of acrylic acid minor matters polymer, 50 grams of polyethylene are weighed respectively
Pyrrolidones, 15 grams of ammonium sulfate, 50 grams of dodecyl sodium sulfates, 25 grams of polyethylene glycol, 30 grams of sodium carboxymethylcelluloses, 50 grams of silicon
Diatomaceous earth, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10 nitrile pyrrole mite ester water dispersible granules (WDG) of embodiment 36:40%
363.6 grams of TDCA-10,36.4 grams of nitrile pyrrole mite esters, 50 grams of sodium lignin sulfonates, 40 grams of acrylic acid minor matters are weighed respectively
Polymer, 40 grams of dodecyl sodium sulfates, 55 grams of polyethylene glycol, 45 grams of ammonium sulfate, bentonite complementary are spare to 1000 grams；
Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated,
It is drying to obtain water dispersible granules.
The miticide composition TDCA-10 nitrile pyrrole mite ester wettable powder (WP) of embodiment 37:20%
295 grams of TDCA-10,5 grams of nitrile pyrrole mite esters, 35 grams of lignosulfonates calcium, 60 grams of carboxymethyl celluloses are weighed respectively
Sodium, 70 grams of aluminum magnesium silicates, 50 grams of neopelexes, 45 grams of tetrabutylammonium bromide, kaolin complementary are standby to 1000 grams
With；
Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
By following experiment it can be shown that two effective component TDCA-10 and nitrile pyrrole in above-mentioned miticide composition of the invention
The compounding of mite ester can have apparent synergistic effect.
(2), biological Examples
Embodiment 38:TDCA-10 and nitrile pyrrole mite ester composite formula screening experiment
One, (A represents nitrile pyrrole mite ester to reagent agent in following reagents；B represents TDCA-10)
A agent: 50% nitrile pyrrole mite ester water dispersible granules (WDG) (being prepared by the method for embodiment 34)
B agent: 50% TDCA-10 water dispersible granules (WDG) (being prepared by the method for embodiment 35)
AB1: nitrile pyrrole mite ester TDCA-10(A:B=20:1)
AB2: nitrile pyrrole mite ester TDCA-10(A:B=10:1)
AB3: nitrile pyrrole mite ester TDCA-10(A:B=1:1)
AB4: nitrile pyrrole mite ester TDCA-10(A:B=1:10)
AB5: nitrile pyrrole mite ester TDCA-10(A:B=1:20)
AB6: nitrile pyrrole mite ester TDCA-10(A:B=1:40)
AB7: nitrile pyrrole mite ester TDCA-10(A:B=1:60)
AB8: nitrile pyrrole mite ester TDCA-10(A:B=1:70)
Two, for trying insect
For examination insect using the red spider adopted in the citrus trees of field, raised for 3 generations indoors as test worm.
Three, experimental method
Experiment uses dip slide method.Every kind of reagent tests 5 kinds of concentration (see Table 1 for details for the specific concentration of every kind of reagent), each repetition
Processing 4 times repeats 120 (four times, amount to 480) every time, and 72 hours microscopic examination results after medicine obtain the death for test worm
Rate calculates LC50With co-toxicity coefficient (CTC).
Four, calculation method
It is ordinate that the death rate of every kind of reagent, which is converted to corresponding probability value (y), and with the various concentration of various reagents
Logarithm lgx be that abscissa using least square method obtains coefficient a, b in virulence equation (y=a+blgx).According to virulence side
Journey calculates the LC of the reagent as y=5.000 (the probability value when death rate is 50%)50.It is calculated using Sun Yunpei equation
Out confection co-toxicity coefficient (CTC) (bibliography: Tan Genjia, wishing Jianping etc., " fungicide bioassay calculation method and
Using ", Anhui agronomy notification, 1998,4(1), 27-28).Using the calculated CTC value of Sun Yunpei equation, China is generally recognized
It is greater than 150 with synergistic effect (wherein: CTC, which is greater than 200, has significant synergistic effect) for CTC, CTC is addition 50~150
Effect, CTC are antagonism less than 50.
Five, result and analysis
TDCA-10 and nitrile pyrrole mite ester composition series proportion mixture are to citrus red mite The Toxicity Determination result, LC50With
Co-toxicity coefficient (CTC) is shown in Table 1, table 2.
Laboratory experiment the result shows that, TDCA-10 and nitrile pyrrole mite ester composition series proportion mixture do not have to citrus red mite
Show antagonism, major part has certain synergistic effect, and (the CTC value of AB4~AB6 is both greater than 180, shows there is synergy work
With), its CTC value of AB4, AB5 is all larger than 210, shows there is significant synergistic effect.Wherein the co-toxicity coefficient of AB4 mixture it is maximum (CTC=
225), illustrate its synergistic effect maximum.
Table 1, TDCA-10 and nitrile pyrrole mite ester proportion mixture are to citrus red mite The Toxicity Determination result
2 LC of table50With co-toxicity coefficient (CTC)
The death rate corresponding probit value when y represents composition series proportion mixture various concentration in table 2, x represent concentration (C)
Logarithm lgC(, that is, x=lgC).
Embodiment 39: nitrile pyrrole mite ester TDCA-10 composition for preventing and controlling citrus red mite field efficacy experiment
One, reagent agent
1,40% miticide composition nitrile pyrrole mite ester water dispersible granules (TDCA-10: nitrile pyrrole mite ester=10:1) (WDG) (are pressed
According to the method preparation of embodiment 36)；
2,20% miticide composition TDCA-10 nitrile pyrrole mite ester wettable powder (WP) (wherein TDCA-10: nitrile pyrrole mite
Ester=59:1) (being prepared according to the method for embodiment 37)；
3,10% nitrile pyrrole mite ester suspending agent (SC) (being prepared according to the method for embodiment 32)；
4,5% TDCA-10 suspending agent (SC) (being prepared according to the method for embodiment 33).
Two, experimental subjects
1, experimental period: June 21 2015 time started；
1, place: the area Mianyang City Nong Ke, Sichuan Province kwan-yin village Citrus Orchard living is tested；
2, crop: sweet orange is tested；
3, controlling object: citrus red mite.
Three, experimental method
1, processing item: 40% miticide composition TDCA-10 nitrile pyrrole mite ester water dispersible granules (WDG) dilute 8000 times；
20% miticide composition TDCA-10 nitrile pyrrole mite ester wettable powder (WP) dilutes 4000 times；10% nitrile pyrrole mite ester suspending agent
(SC) 2000 times are diluted；5% TDCA-10 suspending agent (SC) dilutes 1000 times.Blank control: clear water is used.
2, cell is arranged: each cell tree species, the age of tree, growing way and fertilizer and water management condition are almost the same.Each cell is 3 fixed
It sets, four repetitions, totally 24 cell；And cell is arranged according to random area.
3, spraying time and method: primary in citrus red mite peak of occurrence period (June 21) application.Using manual pressure
Contracting sprayer even spraying, to squirt blade as degree.
4, control time and method: before the application with 3 days after application, 10 days, 20 days, each investigation in 30 days it is primary.Method is
Each tree wins 30 leaves in four orientation at random, and every cell wins 360, records mite quantity living on blade, calculates mite mouthful and subtract
Move back rate and preventive effect.
Four, mite mouthful decline rate and preventive effect calculation method
PT=mite mouthful decline rate (%)=(mite number living after mite number-application of living before application)/(mite number living before application) * 100
Wherein CK is blank district mite mouthful decline rate to preventive effect (%)=(PT-CK)/(100-CK) * 100
Five, experimental result
40% miticide composition TDCA-10 nitrile pyrrole mite ester water dispersible granules (WDG) (TDCA-10: nitrile pyrrole mite ester=10:
1) 8000 times are diluted；20% miticide composition TDCA-10 nitrile pyrrole mite ester wettable powder (WP) (wherein TDCA-10: nitrile pyrrole
Mite ester=60:1) 4000 times of dilution, 3 days are respectively 98.37% and 97.19% to citrus red mite preventive effect after application；10 days after application
It is respectively 95.14% and 93.01% to citrus red mite preventive effect；20 days are respectively 87.98% He to citrus red mite preventive effect after application
86.64%；30 days are respectively 81.38% and 81.04% to citrus red mite preventive effect after application.The nitrile pyrrole mite ester of comparison medicament 10% is outstanding
Floating agent (SC) dilutes 2000 times, 3 days after application, 10 days, 20 days, 30 days four times investigation preventive effects be respectively 91.99%, 88.87%,
81.12%,71.53%.The TDCA-10 suspending agent (SC) of comparison medicament 5% dilutes 1000 times, 3 days after application, 10 days, 20 days, 30
It four times investigation preventive effects are respectively 89.61%, 84.70%, 78.96%, see Table 3 for details by 70.28%().It is observed according to field experiment, not
It was found that TDCA-10 nitrile pyrrole mite ester miticide composition generates phytotoxicity phenomenon to experiment crop.
3 TDCA-10 of table and nitrile pyrrole mite ester series proportion mixture are to citrus red mite field experiment result statistical form
Claims (3)
1. miticide composition, with N- (5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (2,6- difluoro pyridine -4- base)-N, 4-
Dimethyl -1,2,3- thiadiazoles -5- carbonamidine and nitrile pyrrole mite ester are that acceptable auxiliary element is common in effective component, with pesticide
It forms, wherein N- (5- tert-butyl -1,3,4- thiadiazoles -2- base)-N'- (2,6- difluoro pyridine -4- base)-N, dimethyl -1 4-,
2,3- thiadiazoles -5- carbonamidine and nitrile pyrrole mite ester weight ratio are 40:1 to 10:1.
2. miticide composition according to claim 1 is prepared into various forms of by current conventional pesticide production method
Available microcapsule formulations, suspoemulsion, water dispersible granules, wettable powder, aqueous emulsion, any dosage form in suspending agent.
3. miticide composition according to claim 1, the harmful mite for fruit tree, vegetables, cotton, peanut and ornamental plant is anti-
It controls.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530040A (en) * | 2015-01-19 | 2015-04-22 | 西华大学 | Novel method for synthesizing 1,2,3-thiadiazole-5-formamidine compound |
| CN104610250A (en) * | 2015-01-09 | 2015-05-13 | 西华大学 | 1,2,3-thiadiazole-5-formamidine compound containing three N-heterocycles and synthesis |
| CN104860938A (en) * | 2015-06-08 | 2015-08-26 | 西华大学 | Multi-nitrogen heterocycle thiadiazoles-5-formamidine compound by cyclization method |
| CN104886079A (en) * | 2015-05-28 | 2015-09-09 | 西华大学 | Application of 1,2,3-thiadiazole-5-formamidine heterocyclic compound as acaricide |
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2017
- 2017-02-20 CN CN201710088569.1A patent/CN106857557B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610250A (en) * | 2015-01-09 | 2015-05-13 | 西华大学 | 1,2,3-thiadiazole-5-formamidine compound containing three N-heterocycles and synthesis |
| CN104530040A (en) * | 2015-01-19 | 2015-04-22 | 西华大学 | Novel method for synthesizing 1,2,3-thiadiazole-5-formamidine compound |
| CN104886079A (en) * | 2015-05-28 | 2015-09-09 | 西华大学 | Application of 1,2,3-thiadiazole-5-formamidine heterocyclic compound as acaricide |
| CN104860938A (en) * | 2015-06-08 | 2015-08-26 | 西华大学 | Multi-nitrogen heterocycle thiadiazoles-5-formamidine compound by cyclization method |
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