CN106962368A - A kind of Synergistic mite killing composition of containing spirodiclofen - Google Patents
A kind of Synergistic mite killing composition of containing spirodiclofen Download PDFInfo
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- CN106962368A CN106962368A CN201710216484.7A CN201710216484A CN106962368A CN 106962368 A CN106962368 A CN 106962368A CN 201710216484 A CN201710216484 A CN 201710216484A CN 106962368 A CN106962368 A CN 106962368A
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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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of Synergistic mite killing composition, with N (base of 51,3,4 thiadiazoles of the tert-butyl group 2) N'(2, the base of 6 disubstituted pyridines 4) N, the carbonamidine of 41,2,3 thiadiazoles of dimethyl 5（Abbreviation TDCA）Collectively constituted with Envidor for acceptable auxiliary element in active ingredient, with agricultural chemicals, wherein TDCA 6 and Envidor part by weight are 40:1 to 1:40.Tested, shown after two kinds of combination of active principles without antagonism by laboratory experiment and field efficacy, and with notable synergistic effect, to crop safety.
Description
Technical field
The present invention relates to a kind of insecticide acaricide composition, concretely relate to a kind of containing spirodiclofen and N- tri- replace -1,
The insecticide acaricide composition of 2,3- thiadiazoles -5- formamidine compounds, belongs to field of pesticide preparation.
Background technology
Mite class belongs to Arthropoda, and Arachnoidea, Acarina, individual is smaller.All ranks are there may be in a colony
The mite of section, including ovum, deutonymph, young mite and into mite.It is mostly intensive to infest fruit tree, vegetables, cotton, peanut and other crops and view and admire plant
The vacuum side of blade of thing, and its breeding is rapid, high these of selfing degree all determine the more difficult preventing and treating of mite class.On the other hand, Nong Minyou
The continuous single acaricide good using miticidal effect of custom, as a result causes acarid to produce resistance within many time and lose profit
With value.Therefore, using the different mechanisms of action, different types of acaricide be solve evil mite be also easy to produce resistance effective way it
One.
Envidor, molecular formula C21H24Cl2O4, chemical name：3- (2,4 dichloro benzene base) -2- oxo -1- oxaspiros [4,
5]-decyl- 3- alkene -4- base -2,2- dimethyl butyrate acid esters, English abbreviation Spirodiclofen, No. CAS：148477-71-8, is to visit
A kind of tetronic acid class acaricide of brand-new mechanism of action of ear crop science company exploitation.Envidor active compound sterling appearance white powder
Shape, no special odor, fusing point：94 ~ 96 DEG C, 20 DEG C of vapour pressures 3 × 10-7Pa, 20 DEG C of density 1.29g/cm3.Under the conditions of 20 DEG C, just
Dissolubility in dissolubility 20g/1000mL in hexane, dichloromethane>Dissolubility 47g/1000mL in 250g/1000mL, isopropanol,
Dissolubility in dimethylbenzene>Dissolubility is less than 1g/1000mL in 250g/1000mL, water（It is insoluble in water）.Toxicity：Rat acute is passed through
Mouth LD50>2500mg/kg, acute percutaneous LD50>4000mg/kg；Sunfish LC50>0.0455mg/L, rainbow trout LC50>
0.0351mg/L, water flea LC50>100mg/L；To honeybee LD50>100 μ g/ honeybees, to North America quail LD50>2000mg/
kg.Envidor has action of contace poison, there is higher preventive effect to multiple mites.It has broad spectrum activity, mite ovum it is simultaneous kill, lasting period length,
Toxicity is low, security is good, no interactions resistance many advantages, such as, available for each worm phase for preventing and treating phytophagous mite, and to beneficial insect without
Poison, to mammal low toxicity, residual life, is extremely short.Envidor is in terms of biochemical action mechanism substantially different from other acaricides.2002
Year Envidor enters Korea S, South Africa, Brazil, Colombia and Switzerland market.2003 Japan registration (using Daniemon as
Trade name, for preventing and treating citrus red mite and rust mite), and in Holland's registration.Enter within 2005 America ＆ Canada, 2007
Italy is introduced, enters Spain and Chile within 2008.The registration obtained in Europe for 2010.The market development speed of Envidor
Degree is very fast, obtains registration in nearly 50 countries at present, 2008, the sales volume of Beyer Co., Ltd's Envidor exceeded propargite, into
For sales volume highest kind in acaricide, afterwards, the sales volume of Envidor occupies first place in acaricide sales volume always.
1.1 hundred million dollars of Envidor sales volume in 2011, as kind maximum in global acaricide.Envidor has unique effect machine
Reason, the main Fatty synthesis for suppressing mite, blocks the energetic supersession of mite, has to each stage of development of many main evil mites
Effect, but it is different to each stage action effect.Although Envidor can not comparatively fast kill female into mite, have to the female breeding into mite
Certain inhibitory action.Envidor is mainly used in citrus, the operatic circle, drupe, grape and nut.
The synthetic method of Envidor is relatively fewer, mainly there is two kinds of synthetic routes.Route one：First using cyclohexanone as original
Material, with generating cyanalcohol after NaCN additions, cyan-hydrolysis is further esterified into carboxylic acid, carboxylic acid, then with 2,4- dichloro-benzenes second
Acyl chloride reaction generates cyclohexyl, and intramolecular ring-closing reaction then occurs again, key intermediate 3- (2,4- dichlorophenyl) -2- is obtained
Oxo -1- oxaspiros [4,5]-decyl- 3- alkene -4- alcohol, this key intermediate finally reacts to obtain Envidor with dimethyl-butyrylchlorine.Road
Line two：Equally first using cyclohexanone as raw material, with generating cyanalcohol after NaCN additions, then cyanalcohol and 2,4- dichloro phenyllacetyl chloride are anti-
Cyclohexyl should be generated, cyan-hydrolysis is further esterified into carboxylic acid, carboxylic acid, and intramolecular ring-closing reaction then occurs again, obtains
To key intermediate 3- (2,4- dichlorophenyl) -2- oxo -1- oxaspiros [4,5]-decyl- 3- alkene -4- alcohol, this key intermediate is most
Envidor is reacted to obtain with dimethyl-butyrylchlorine afterwards.
Although Envidor there are numerous distinctive advantages of tool, certain defect is still had in use：Spiral shell mite
The mite killing speed of ester is slower, and quick-acting is poor, should not be used when Agricultural Mites largely break out, and should not particularly be used alone.
Chinese patent（Application number CN2015100098343, January 9 2015 date of application, Granted publication date 2017
On March 21, in, denomination of invention：1,2,3- thiadiazoles -5- formamidines compound and synthesis containing three azacyclo-s）In report specially
The artificial Xihua Univ of profit application（Inventor Wang Hui towns, Liu Ping, Yang Wei are clear etc.）Formula be TDCA the polysubstituted -1,2,3- of N-
Thiadiazoles -5- formamidines compound and its synthetic method（Formula 1）.Chinese patent（Application number CN2015100237806, the applying date
January 19 2015 phase, January 11 2017 Granted publication date）In report the artificial Xihua Univ of patent application（Inventor
It is clear etc. for Liu Ping, Yang Wei）Mutual-through type is the new synthesis side of the TDCA polysubstituted -1,2,3- thiadiazoles -5- formamidine compounds of N-
Method is reported that the new method is to the synthesis of target product using being first cyclized, and finally the method for upper methyl, obtains experiment effect very well
Really.Chinese patent（Application number CN2015103042053, June 9 2015 date of application, denomination of invention：The synthesis of cyclization method is more
Azacyclo- thiadiazoles -5- formamidine compounds）In report the artificial Xihua Univ of patent application（Inventor Yang Wei is clear, Liu Ping
Deng）Mutual-through type is reported for the novel synthesis of the TDCA thiadiazoles -5- formamidine compounds of N- polysubstituted -1,2,3-, is somebody's turn to do
New method is to the synthesis of target product using first upper methyl, and the method being finally cyclized, the novel synthesis high income, catalyst hold
Easily prepare, catalyst is cheap, phosphorus-containing wastewater is few, to more environment-friendly.Chinese patent（The patent No.
ZL201510277765.4, May 28 2015 date of application, 2016 Granted publication dates August 31 days, denomination of invention：1,
2,3- thiadiazoles -5- formamidines poly-heterocyclic compounds are used as acaricidal purposes）In report the artificial Xihua Univ of patent application
（Inventor Yang Wei is clear, Liu Ping, Zhang Yuanyuan etc.）Formula be TDCA the polysubstituted -1,2,3- thiadiazoles -5- formamidines of N-
Compound is used as acaricidal purposes, the particularly control of pest mite for fruit tree, vegetables, cotton, peanut and other crops and ornamental plant.
But formula is not strong enough to the murder by poisoning power of part adult for the TDCA polysubstituted -1,2,3- thiadiazoles -5- formamidines compounds of N-
Greatly, it is necessary to the acaricide high with killing adult activity（Such as AVM, Envidor）Interworking is carried out to use.It is well known that desinsection,
Acaricide all easy insect during long-term use develops immunity to drugs, to extend the usage cycles of a new varieties, with other
Excellent insecticidal acaricide kind carries out interworking using being a kind of conventional strategy.
The content of the invention
The main object of the present invention be it is not enough for more than, by the acaricidal rational mixture of the different mechanisms of action there is provided
One kind has 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- formamidines poly-heterocyclic compounds are used as acaricidal purposes）Middle report
Road formula is TDCA N- polysubstituted -1,2,3- thiadiazoles -5- formamidine compounds（Formula 1）It is special as acaricidal purposes
It is not the control of pest mite for fruit tree, vegetables, cotton, peanut and other crops and ornamental plant.In formula in TDCA compound
TDCA-6~TDCA-13（TDCA-6~TDCA-13 detailed construction formulas are as shown in table 1, it is possible to reference to association patent, and China is specially
Sharp application number CN2015100098343）With preferable acaricidal activity.Described for ease of the present invention, it is main in the embodiment of the present invention
N- (the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (2,6- disubstituted pyridines -4- bases)-N, 4- bis- is represented with TDCA-6
Methyl isophthalic acid, the compound of 2,3- thiadiazoles -5- carbonamidines is illustrated.
Table 1：In the TDCA precursor structures of formula 1, the halogens that X, Y are referred in TDCA-6~TDCA-13
What the object of the invention was realized in that：
By N- (the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases) of Chinese, (2,6- bis- replaces-N'- miticide composition of the present invention
Pyridin-4-yl)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines（Hereinafter referred to as TDCA in the present invention）, structural formula is as originally
A class compound and Envidor shown in invention formula 1 collectively constitute for acceptable auxiliary element in active ingredient, with agricultural chemicals.
The compound that TDCA is referred to as in miticide composition of the present invention can be compound N-(the 5- tert-butyl group -1,3,4- thiophenes
Diazole -2- bases)-N'- (2,6- dichloropyridine -4- bases)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines（This invention simply if referred to as
TDCA-6, structural formula is as shown in Equation 3）, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (chloro- 6- fluorine pyrroles of 2-
Pyridine -4- bases)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines（This invention simply if referred to as TDCA-7）, compound N-(the tertiary fourths of 5-
Base -1,3,4- thiadiazoles -2- bases)-N'- (the chloro- 6- bromopyridines -4- bases of 2-)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines
（This invention simply if referred to as TDCA-8）, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (the chloro- 6- iodine pyridines of 2- -
4- yls)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines（This invention simply if referred to as TDCA-9）, compound N-(the 5- tert-butyl group -1,
3,4- thiadiazoles -2- bases)-N'- (2,6- difluoro pyridine -4- bases)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines（The present invention
Referred to as TDCA-10, structural formula is as shown in Equation 4）, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases) (2- is bromo- by-N'-
6- fluorine pyridin-4-yl)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines（This invention simply if referred to as TDCA-11）, compound N-
(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (the fluoro- 6- iodine pyridines -4- bases of 2-)-N, 4- dimethyl -1,2,3- thiadiazoles -
5- carbonamidines（This invention simply if referred to as TDCA-12）, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (2,6- dibromos
Pyridin-4-yl)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines（This invention simply if referred to as TDCA-13）In any one.
Miticide composition of the present invention can be TDCA-6, TDCA-7, TDCA-8, TDCA-9, TDCA-10, TDCA-11,
Any one in TDCA-12, TDCA-13 is common for acceptable auxiliary element in active ingredient, with agricultural chemicals with Envidor
Composition.
Miticide composition of the present invention can also be TDCA-6, TDCA-7, TDCA-8, TDCA-9, TDCA-10, TDCA-11,
Any two kinds in TDCA-12, TDCA-13 and the TDCA mixtures after two or more combinations be combined as again with Envidor effectively into
Point, collectively constituted with acceptable auxiliary element in agricultural chemicals.
TDCA and the permission part by weight of Envidor are 100 in miticide composition of the present invention:1 to 1:100, it is preferably in a proportion of
40:1 to 1:40, further preferred ratio is 1:5 to 20:1.
Miticide composition compound of the present invention has acaricidal purposes, particularly for fruit tree, vegetables, cotton, peanut
Deng the control of pest mite of crop and ornamental plant.The present composition is applied on crop and/or ornamental plant and is harmful to acarid life
Long region, can effectively prevent and treat evil mite.Present composition time of application can be in each growth phase in acarid, including
Ovum, deutonymph, young mite and into mite.Some representatives for the evil mite that can be prevented and treated for the present composition being mentioned below, enumerate and do not limit
Evil mite on following some crops and/or ornamental plant.
As the mite class as present composition control object, it can enumerate：Belong to the mite of Ying Pi sections：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, matrimony vine burrknot tick, pseudo- pears rust tick, Pi Shi skin goitre mites
Deng.Belong to the mite of Tyroglyphidae：Hesperidium mite, ellipse dispersion, Acarus siro, the wild fat mite in river, 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：It is panonychus citri, panonychus ulmi, mulberry Panonychus citri, Tetranychus urticae, Tetranychus cinnabarinus, purplish red short
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 preventing and treating 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 infringement of small degree or not damaged completely, take
Certainly in the present composition general structure concrete structure of each compound, amount of application, using useful crop object.Here it is this
Invention compound can be applied to the basic reason of control of pest mite on crop and/or ornamental plant.
Acceptable auxiliary element in described agricultural chemicals, including used at present in agricultural chemicals, unfavorable shadow will not be produced
Loud all kinds of common solvents and/or inert filler and/or surfactant and/or preservative and/or antifreezing agent and/or agglomeration resistance
The corresponding adding ingredient of agent and/or defoamer and/or cosolvent and/or stabilizer and/or thickener etc., it is possible to according to being produced
Dosage form do corresponding selection or adjust.
Agrochemical formulations generally comprise 0.1-99 weight %, particularly 2-90 weight % miticide composition of the present invention.
Wettable powder（WP）Middle miticide composition concentration is, such as 10-90 weight %, and the remainder in 100 weight % is by routinely making
Agent auxiliary element is constituted.In suspending agent（SC）Middle miticide composition concentration is, such as 1-90 weight %, preferably 5-75 weight %, 100
Remainder in weight % is made up of conventional formulation auxiliary element.In suspension emulsion（SE）Middle miticide composition concentration is, such as 1-
Remainder in 90 weight %, preferably 5-75 weight %, 100 weight % is made up of conventional formulation auxiliary element.In water dispersant
（WDG）Middle miticide composition concentration is, such as 1-95 weight %, preferably 10-70 weight %, and the remainder in 100 weight % is by normal
Regulation agent auxiliary element is constituted.The preparation of other powder types includes 1-40 weight % reactive compounds, and preferably 5-20 weight % lives
Remainder in property compound, 100 weight % is made up of conventional formulation auxiliary element.
Miticide composition of the present invention needs or applied Huan Jing ∕ conditions according to different uses, is given birth to by current conventional pesticide
Production mode, TDCA-6 in the miticide composition and Envidor active ingredient and corresponding auxiliary element are sufficiently mixed for raw material,
Preparing turns into various forms of available corresponding formulations.Possible formulation includes：Wettable powder, water dispersant, suspension
Agent, aqueous emulsion, suspension emulsion, microcapsule formulations etc..Such as several typical common dosage forms and prepare can be with：
Microcapsule formulations（CJ）Refer to using natural or synthesis high polymer material formation " core-shell structure copolymer " structure small container, by agricultural chemicals
Cladding wherein, and is suspended in the formulations of pesticide in water.Micro-capsule suspension outward appearance is a thick working fluid, with aqueous emulsion
And aqueous suspension agent is similar.Micro- sem observation is used, its profile of microcapsules is spherical in shape, rugby shape, grain or other shapes.Microcapsules
Diameter is general 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 microcapsules agriculture
The features such as medical instrument has low lasting period length, toxicity, safe ready, just as pesticides new formulation a developing direction.Microcapsules
Customary preparation methods have complex coacervation, Simple coacervation, interfacial polymerization, situ aggregation method, orifice-coagulating bath method etc..It is several recently
There are some novel processing steps, such as molecular inclusion, microchannel emulsification method, supercritical fluid quick expansion method, ferment again in year
Female microcapsule method, self-assembled multilayer film method.Microcapsules often have sodium alginate, chitosan, gelatin, porous-starch etc. with wall material.
Complex coacervation is most popular method in above-mentioned microcapsule preparation method.Complex coacervation preparation principle is to carry opposite charges with two kinds
Material make embedded object, core is scattered wherein, changes change pH values, temperature or solution concentration, due to the effect between electric charge, makes two kinds
Wall material solubility declines and is condensed into microcapsules precipitation.A kind of positively charged colloidal solution and another negatively charged colloid
Solution is mixed, and because the interaction between xenogenesis electric charge forms compound polyelectrolyte and is separated, and is deposited on capsule-core week
Enclose and obtain microcapsules.Complex coacervation is often capsule material with gelatin, Arabic gum.Gelatin is protein, in aqueous, strand
It is upper to contain-NH2With-COOH and its corresponding dissociation group-NH3 +With-COO-, but contain-NH3 +With-COO-How much is ion, by medium
The influence of pH value.Gelatin solution is in pH 4.0 or so, and its positive charge is most.Arabic gum is polysaccharide, in aqueous, point
Contain-COOH and-COO in subchain-, with negative electrical charge.Therefore in the aqueous solution that gelatin is mixed with Arabic gum, regulation pH is about
For 4.0 when, gelatin and Arabic gum neutralize to form compound on the contrary because of charged phase, the reduction of its solubility, are condensed into from system
Capsule is separated out.Curing agent formaldehyde is added, formaldehyde produces amine aldehyde condensation reaction with gelatin, and gelatin molecule is cross-linked into network structure, protects
The shape of micro-capsule is held, as irreversible micro-capsule；Plus 2% NaOH regulations medium pH 8 ~ 9, be conducive to the condensation reaction of amine aldehyde to carry out
Completely.
Water dispersant（WDG）Can in water fater disintegration, and can be uniformly dispersed in water formation higher suspension dispersion
A kind of granular preparation.The present composition and auxiliary element one can be reinstated to air-flow during preparation to smash or ultra-fine grinding, system
Into wettable powder, this is dry method；By the present composition, auxiliary agent, adjuvant etc., using water as medium, ground in sand mill,
Suspending agent is made, then re-dry is granulated, and this is wet method.
Wettable powder（WP）, i.e., solid powder preparation that can be dispersed in water., can be according to conventional side during preparation
Formula, is firstly added TDCA-6 of the present invention and the composition of Envidor, then adds diatomite, clay, precipitated calcium carbonate, white carbon
Etc. conventional diluent or inert substance, other conventional auxiliary elements, such as alkylnaphthalene sulfonate, alkylbenzenesulfonate, fat are added
Fat alcohol sulfate, alkyl bromination ammonium, alkyl ammomium chloride, quaternary alkylphosphonium salts, alkyl polyoxyethylene base ether sulfate, lignosulfonates,
One or several kinds in lignin, carboxymethyl cellulose, sodium carboxymethylcellulose, azone, thiophene ketone, and conventional stabilizer,
The complementary auxiliary component such as foam inhibitor, anticaking agent.
Suspension emulsion（SE）That is a kind of hybrid dispersions of the insoluble agricultural chemicals of water in water, active ingredient therein is in suspension
State, other active ingredients are in emulsion state.Can be by the present composition and corresponding emulsion, moistening point when being prepared during preparation
The auxiliary elements such as powder, thickener, stabilizer, antifreezing agent, pH adjusting agent, defoamer, conventionally, through wet method Ultramicro-powder
It is broken to be mixed to prepare.Wherein emulsifying agent is APES class（Agriculture breast 100#）, alkylbenzenesulfonate（Agriculture breast 500#）, benzene
Ethyl phenol polyethenoxy ether class（Agriculture breast 600#）, alkyl phenol or aralkyl phenol polyethenoxy ether formaldehyde condensation species（Nongru-700 #）
One or several kinds in.Wherein Ricinate is lignosulfonates, lignin, phosphate polyethers, carboxymethyl fibre
Tie up element, sodium carboxymethylcellulose, crown ether, alkylnaphthalene sulfonate, alkylbenzenesulfonate, aliphatic alcohol sulfate, alkyl ammonium halide, season
One or several kinds in phosphonium salt, alkyl polyoxyethylene base ether sulfate, azone, thiophene ketone；Thickener and stabilizer are polyethylene
One or several kinds in alcohol, condensed phosphate, xanthan gum, Magnesiumaluminumsilicate etc.；Antifreezing agent be sodium chloride, urea, ammonium sulfate,
One or several kinds in ethylene glycol, glycerine etc.；PH adjusting agent be potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate,
One or several kinds in potassium carbonate etc..Conventional organosilicon is used as defoamer and foam inhibitor.
Suspending agent（SC）That is agricultural chemicals suspension agent（SC）, it is water insoluble solids agricultural chemicals or does not mix liquid pesticidal in water or oil
Dispersion.During preparation, with water or oil for decentralized medium, by TDCA-6 of the present invention and Envidor composition and auxiliary element
（Such as thickener, stabilizer, Ricinate, antifreezing agent, pH adjusting agent, defoamer）Through soybean dietary fiber（Grinding）System
.Wherein Ricinate is phosphate polyethers, alkylnaphthalene sulfonate, alkylbenzenesulfonate, aliphatic alcohol sulfate, alkyl bromide
Change ammonium, alkyl ammomium chloride, crown ether, quaternary alkylphosphonium salts, alkyl polyoxyethylene base ether sulfate, lignosulfonates, lignin, carboxymethyl
One or several kinds in cellulose, sodium carboxymethylcellulose, azone, thiophene ketone；Thickener and stabilizer are polyvinyl alcohol, condensation
One or several kinds in phosphate, xanthan gum, Magnesiumaluminumsilicate etc.；Antifreezing agent be sodium chloride, urea, ammonium sulfate, ethylene glycol,
One or several kinds in glycerine etc.；PH adjusting agent is potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate, potassium carbonate etc.
In one or several kinds.Conventional organosilicon is used as defoamer and foam inhibitor.
It should be noted that specific formulation mentioned above is the representative formulation that present composition thing can be prepared, enumerate
It is not limited to these above-mentioned formulations.
To be administered, if by appropriate formulation, diluted in a usual manner, for example for wettable powder, water dispersant,
Suspending agent, aqueous emulsion, suspension emulsion are diluted with water.Pulvis, granule, microcapsule formulations etc. generally no longer use other inert materials before applying
Matter dilutes.
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 relative broad range, such as 0.1-500g/667m2Or more chemical combination of the present invention
Thing, preferably 1-50g/667m2。
To represent N- (the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases), (2,6- bis- takes-N'- the main TDCA-6 of following examples
For pyridin-4-yl)-N, 4- dimethyl -1,2, the compound of 3- thiadiazoles -5- carbonamidines is further described, but should not be by
This is interpreted as the present invention can only be using TDCA-6 and Envidor progress interworking.Concrete mode by the following examples is again to this hair
Bright the above is described in further detail.But this should not be interpreted as the scope of above-mentioned theme of the invention be only limitted to
Under example.Without departing from the idea case in the present invention described above, done according to ordinary skill knowledge and customary means
The various replacements or change gone out, all should be included within the scope of the invention.Each material proportion of composing is weight % in embodiment.
Embodiment：
(1), example of formulations
Embodiment 1：40% miticide composition TDCA-6 Envidor wettable powders（WP）（40% refers to original ingredient ratio, similarly hereinafter）
Weigh respectively 350.0 grams of TDCA-6,50.0 grams of Envidors, 35 grams of lignosulfonates calcium, 40 grams of sodium carboxymethylcelluloses,
20 grams of Magnesiumaluminumsilicates, 25 grams of neopelexes, 30 grams of TBABs, kaolin complementaries are standby to 1000 grams；
Prepare：Each material is sequentially added in reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 2：30% miticide composition TDCA-6 Envidor wettable powders（WP）
200 grams of TDCA-6,100 grams of Envidors, 20 grams of lignosulfonates calcium, 25 grams of sodium carboxymethylcelluloses, 30 are weighed respectively
Gram Magnesiumaluminumsilicate, 20 grams of neopelexes, 20 grams of TBABs, kaolin complementaries are standby to 1000 grams；
Prepare：Each material is sequentially added in reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 3：20% miticide composition TDCA-6 Envidor wettable powders（WP）
Weigh respectively 175 grams of TDCA-6,25 grams of Envidors, 40 grams of lignosulfonates calcium, 35 grams of sodium carboxymethylcelluloses, 46 grams
Magnesiumaluminumsilicate, 28 grams of neopelexes, 25 grams of TBABs, kaolin complementaries are standby to 1000 grams；
Prepare：Each material is sequentially added in reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 4：30% miticide composition TDCA-6 Envidor wettable powders（WP）
100 grams of TDCA-6,200 grams of Envidors, 30 grams of lignosulfonates calcium, 30 grams of sodium carboxymethylcelluloses, 30 are weighed respectively
Gram Magnesiumaluminumsilicate, 20 grams of neopelexes, 20 grams of TBABs, kaolin complementaries are standby to 1000 grams；
Prepare：Each material is sequentially added in reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 5：50% miticide composition TDCA-6 Envidor wettable powders（WP）
100 grams of TDCA-6,400 grams of Envidors, 40 grams of lignosulfonates calcium, 40 grams of sodium carboxymethylcelluloses, 40 are weighed respectively
Gram Magnesiumaluminumsilicate, 30 grams of neopelexes, 20 grams of TBABs, kaolin complementaries are standby to 1000 grams；
Prepare：Each material is sequentially added in reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 6：7.5% TDCA-6 Envidor missible oil
Weigh respectively 50 grams of Envidors, 25 grams of TDCA-6,20 grams of monoethanolamines, 20 grams of agriculture breast 500# (calcium dodecyl benzene sulfonate,
By Jinan middle peasant Chemical Co., Ltd. produce, similarly hereinafter), 40 grams of agriculture breast 601#（Phenethyl phenol polyethenoxy ether, by Shandong Zibo forever
Chemical plant production is sent out, similarly hereinafter）, 80 grams of hexone, 60 grams of polyethylene glycol, 20 grams of ammonium sulfate, water complementaries to 1000 grams,
It is standby；
Prepare：Envidor, TDCA-6, solvent methyl isobutyl ketone, emulsifying agent, co-emulsifier are mixed into homogeneous oil phase；Will
Water, antifreeze are mixed into homogeneous aqueous phase, and under the stirring of high-speed shearing machine, oil phase is poured into aqueous phase, is sufficiently mixed.
Embodiment 7：10% TDCA-10 Envidor missible oil（Weight compares TDCA-10：Envidor=8:1）
11.1 grams of Envidors, 88.9 grams of TDCA-10,30 grams of monoethanolamines, 30 grams of agriculture breast 500#, 30 grams of agriculture breast 602# are weighed respectively
（Phenethyl phenol polyethenoxy ether, is produced, similarly hereinafter by Shandong Zibo Yongfa chemical plant）, 80 grams of methyl how, 60 grams of polyethylene glycol, 20
Gram ammonium sulfate, water complementary are standby to 1000 grams；
Prepare：By Envidor, TDCA-10, solvent methyl how, emulsifying agent, co-emulsifier be mixed into homogeneous oil phase；By water, freeze proof
Agent is mixed into homogeneous aqueous phase, and under the stirring of high-speed shearing machine, oil phase is poured into aqueous phase, is sufficiently mixed.
Embodiment 8：7.5% TDCA-6TDCA-10 Envidor missible oil
25 grams of Envidors, 25 grams of TDCA-10,25 grams of TDCA-6,30 grams of monoethanolamines, 30 grams of agriculture breast 500#, 30 grams of agricultures are weighed respectively
Newborn 602#（Phenethyl phenol polyethenoxy ether, is produced, similarly hereinafter by Shandong Zibo Yongfa chemical plant）, 80 grams of hexones,
60 grams of polyethylene glycol, 20 grams of ammonium sulfate, water complementaries are standby to 1000 grams；
Prepare：Envidor, TDCA-6, TDCA-10, solvent methyl isobutyl ketone, emulsifying agent, co-emulsifier are mixed into homogeneous
Oil phase；Water, antifreeze are mixed into homogeneous aqueous phase, under the stirring of high-speed shearing machine, oil phase is poured into aqueous phase, is sufficiently mixed
.
Embodiment 9：6% miticide composition TDCA-6 Envidor microcapsule formulations（CJ）
Weigh respectively 30 grams of TDCA-6,30 grams of Envidors, 30 grams of gelatin, 20 grams of poly-aspartates, 10 grams of Tween-60s, 50 grams Ah
Draw primary glue, 10 grams of polyethylene glycol, 50 gram of 20% formalin, 10% acetums appropriate（Titer is i.e. by the drop in preparation process
Fixed operation determines usage amount, similarly hereinafter）, 20% NaOH solution（Titer）, distilled water complementary to 1000 grams, it is standby；
Preparation process（1）Poly-aspartate is prepared with gelatin mixed solution：After gelatin distillation appropriate amount of water immersion is swelled, heating
Dissolving, is heated to 50 DEG C, adds poly-aspartate, and stirring adds appropriate distilled water, and 50 DEG C of insulations are standby.（2）Arabic peptization
The preparation of liquid：Appropriate distilled water is added in reaction unit, Arabic gum powder is added, is heated to 80 DEG C or so, being gently mixed makes
Dissolving, 80 DEG C of insulations are standby.（3）TDCA-6 and Envidor active ingredient emulsion preparation：By TDCA-6, Envidor, tween-
60th, polyethylene glycol, the gumwater of above-mentioned preparation, are placed in tissue mashing machine, emulsify 30 seconds, produce emulsion.（4）It is mixed
Close：Under the conditions of 50~55 DEG C, above-mentioned poly-aspartate and gelatin mixed solution are added, being gently mixed makes to be well mixed.（5）It is micro-
The preparation of capsule：In the case where being stirred continuously, 10% acetum is added dropwise into foregoing mixed liquor, pH to 3.8~4.0 is adjusted；（6）Micro-capsule
Solidification：In the case where being stirred continuously, about 30 DEG C of distilled water is added in micro-capsule liquid, micro-capsule liquid will be contained and taken from 50~55 DEG C of water-baths
Under, it is stirred continuously, natural cooling, when temperature drops to 32~35 DEG C, adds ice cube, it is less than 10 DEG C to continue to stir to temperature,
Add 20% formalin, continue to stir 15~25min, then its pH 8~9 is adjusted with 20%NaOH solution, continue to stir 20~
30min, observation is untill separating out, and standing treats that micro-capsule is settled.（7）The filtering and drying of micro-capsule：Treat that micro-capsule sedimentation is complete, cross and filter out
Fall supernatant, micro-capsule is washed to formaldehydeless taste, centrifugation, drying with distillation.
Embodiment 10：6% miticide composition TDCA-6 Envidor microcapsule formulations（CJ）
Weigh respectively 40 grams of TDCA-6,20 grams of Envidors, 30 grams of gelatin, 20 grams of poly-aspartates, 10 grams of Tween-60s, 50 grams Ah
Draw primary glue, 20 grams of polyethylene glycol, 50 gram of 20% formalin, 10% acetums appropriate（Titer）, 20% NaOH solution（Titration
Amount）, distilled water complementary to 1000 grams, it is standby；
Preparation process is completely same as Example 9.
Embodiment 11：6% miticide composition TDCA-6 Envidor microcapsule formulations（CJ）
Weigh respectively 20 grams of TDCA-6,40 grams of Envidors, 30 grams of gelatin, 20 grams of poly-aspartates, 10 grams of Tween-60s, 50 grams Ah
Draw primary glue, 8 grams of polyethylene glycol, 50 gram of 20% formalin, 10% acetums appropriate（Titer）, 20% NaOH solution（Titration
Amount）, distilled water complementary to 1000 grams, it is standby；
Preparation process is completely same as Example 9.
Embodiment 12：10% miticide composition TDCA-6 Envidor microcapsule formulations（CJ）
Weigh respectively 50 grams of TDCA-6,50 grams of Envidors, 40 grams of gelatin, 30 grams of poly-aspartates, 20 grams of Tween-60s, 60 grams Ah
Draw primary glue, 30 grams of polyethylene glycol, 100 gram of 20% formalin, 10% acetums appropriate（Titer）, 20% NaOH solution（Drop
It is quantitative）, distilled water complementary to 1000 grams, it is standby；
Preparation process is similar to Example 9.
Embodiment 13：10% miticide composition TDCA-6 Envidor microcapsule formulations（CJ）
Weigh respectively 33 grams of TDCA-6,67 grams of Envidors, 40 grams of gelatin, 30 grams of poly-aspartates, 20 grams of Tween-60s, 60 grams Ah
Draw primary glue, 25 grams of polyethylene glycol, 100 gram of 20% formalin, 10% acetums appropriate（Titer）, 20% NaOH solution（Drop
It is quantitative）, distilled water complementary to 1000 grams, it is standby；
Preparation process is completely same as Example 9.
Embodiment 14：10% miticide composition TDCA-6 Envidor microcapsule formulations（CJ）
Weigh respectively 67 grams of TDCA-6,33 grams of Envidors, 40 grams of gelatin, 30 grams of poly-aspartates, 20 grams of Tween-60s, 60 grams Ah
Draw primary glue, 50 grams of polyethylene glycol, 100 gram of 20% formalin, 10% acetums appropriate（Titer）, 20% NaOH solution（Drop
It is quantitative）, distilled water complementary to 1000 grams, it is standby；
Preparation process is similar to Example 9.
Embodiment 15：50% miticide composition TDCA-6TDCA-13 spirodiclofen water dispersible granules（WDG）
250 grams of TDCA-6,50 grams of TDCA-13,200 grams of Envidors, 50 grams of lignin, 50 grams of acrylic acid minor matters polymerizations are weighed respectively
Thing, 40 grams of dodecyl sodium sulfates, 60 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 16：30% miticide composition TDCA-6TDCA-10TDCA-13 spirodiclofen water dispersible granules
（WDG）
Weigh respectively 120 grams of TDCA-6,80 grams of TDCA-13,50 grams of TDCA-10,50 grams of Envidors, 50 grams of lignin, 50 gram third
Olefin(e) acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 60 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 17：50% miticide composition TDCA-6TDCA-10TDCA-13 spirodiclofen water dispersible granules
（WDG）
Weigh respectively 240 grams of TDCA-6,50 grams of TDCA-13,50 grams of TDCA-10,160 grams of Envidors, 50 grams of lignin, 50 gram third
Olefin(e) acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 60 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 18：60% miticide composition TDCA-6TDCA-10TDCA-13 spirodiclofen water dispersible granules
（WDG）
Weigh respectively 120 grams of TDCA-6,40 grams of TDCA-13,40 grams of TDCA-10,400 grams of Envidors, 60 grams of lignin, 40 gram third
Olefin(e) acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 50 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 19：60% miticide composition TDCA-6TDCA-10TDCA-13 spirodiclofen water dispersible granules
（WDG）
Weigh respectively 100 grams of TDCA-6,100 grams of TDCA-13,100 grams of TDCA-10,300 grams of Envidors, 50 grams of lignin, 30 grams
Acrylic acid minor matters polymer, 50 grams of dodecyl sodium sulfates, 50 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 20：60% miticide composition TDCA-6TDCA-10TDCA-13 spirodiclofen water dispersible granules
（WDG）
Weigh respectively 150 grams of TDCA-6,150 grams of TDCA-13,150 grams of TDCA-10,150 grams of Envidors, 60 grams of lignin, 40 grams
Acrylic acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 50 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 21：30% miticide composition TDCA-6 spirodiclofen water dispersible granules（WDG）
Weigh respectively 200 grams of TDCA-6,100 grams of Envidors, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 30 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 22：40% miticide composition TDCA-6 spirodiclofen water dispersible granules（WDG）
350 grams of TDCA-6,50 grams of Envidors, 75 grams of lignin, 62 grams of acrylic acid minor matters polymer, 53 grams of dodecanes are weighed respectively
Base sodium sulfonate, 85 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 23：30% miticide composition TDCA-13 spirodiclofen water dispersible granules（WDG）
Weigh respectively 200 grams of TDCA-13,100 grams of Envidors, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 40 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 24：20% reactive compound（TDCA-6）Water dispersible granules（WDG）
200 grams of TDCA-6,70 grams of lignin, 60 grams of acrylic acid minor matters polymer, 50 grams of dodecyl sodium sulfates, 80 are weighed respectively
Gram polyethylene glycol, bentonite complementary are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 25：20% spirodiclofen water dispersible granule（WDG）
200 grams of Envidors, 70 grams of lignin, 60 grams of acrylic acid minor matters polymer, 50 grams of dodecyl sodium sulfates, 80 are weighed respectively
Gram polyethylene glycol, bentonite complementary are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 26：35% Envidor suspending agent（SC）
350 grams of Envidors, 40 grams of lignosulfonates calcium, 50 grams of sodium carboxymethylcelluloses, 30 grams of Magnesiumaluminumsilicates, 40 are weighed respectively
Gram neopelex, 60 grams of polyethylene glycol, water complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, carries out just disperseing using high-speed shearing machine, has then been ground in sand mill
Grain diameter of components is imitated at 2~5 μm.
Embodiment 27：35% Envidor wettable powder（WP）
350 grams of Envidors, 45 grams of lignosulfonates calcium, 50 grams of sodium carboxymethylcelluloses, 40 grams of Magnesiumaluminumsilicates, 35 are weighed respectively
Gram neopelex, 30 grams of TBABs, kaolin complementaries are standby to 1000 grams；
Prepare：Each material is sequentially added in reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 28：35% TDCA-6 wettable powders（WP）
350 grams of TDCA-6,35 grams of lignosulfonates calcium, 40 grams of sodium carboxymethylcelluloses, 35 grams of Magnesiumaluminumsilicates, 28 are weighed respectively
Gram neopelex, 25 grams of TBABs, kaolin complementaries are standby to 1000 grams；
Prepare：Each material is sequentially added in reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 29：10% Envidor suspending agent（SC）
100 grams of Envidors, 50 grams of lignosulfonates calcium, 60 grams of sodium carboxymethylcelluloses, 85 grams of Magnesiumaluminumsilicates, 63 are weighed respectively
Gram neopelex, 57 grams of polyethylene glycol, water complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, carries out just disperseing using high-speed shearing machine, has then been ground in sand mill
Grain diameter of components is imitated at 2~5 μm.
Embodiment 30：10% TDCA-6 suspending agents（SC）
100 grams of TDCA-6,40 grams of lignosulfonates calcium, 30 grams of sodium carboxymethylcelluloses, 45 grams of Magnesiumaluminumsilicates, 68 are weighed respectively
Gram neopelex, 72 grams of polyethylene glycol, water complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, carries out just disperseing using high-speed shearing machine, has then been ground in sand mill
Grain diameter of components is imitated at 2~5 μm.
Embodiment 31：60% miticide composition TDCA-6 spirodiclofen water dispersible granules（WDG）
Weigh respectively 400 grams of TDCA-6,200 grams of Envidors, 60 grams of lignin, 45 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 55 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 32：50% miticide composition TDCA-10 spirodiclofen water dispersible granules（WDG）
Weigh respectively 300 grams of TDCA-10,200 grams of Envidors, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 55 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 33：50% miticide composition TDCA-9 spirodiclofen water dispersible granules（WDG）
Weigh respectively 300 grams of TDCA-9,200 grams of Envidors, 60 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 55 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 34：50% miticide composition TDCA-6 spirodiclofen water dispersible granules（WDG）
Weigh respectively 200 grams of TDCA-6,300 grams of Envidors, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 30 gram 12
Sodium alkyl sulfonate, 40 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 35：30% miticide composition TDCA-6TDCA-10 spirodiclofen water dispersible granules（WDG）
100 grams of TDCA-6,100 grams of TDCA-10,100 grams of Envidors, 30 grams of lignin, 40 grams of acrylic acid minor matters are weighed respectively to gather
Compound, 30 grams of dodecyl sodium sulfates, 40 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
Embodiment 36：60% miticide composition TDCA-6 spirodiclofen water dispersible granules（WDG）
Weigh respectively 571.4 grams of TDCA-6,28.6 grams of Envidors, 60 grams of lignin, 50 grams of acrylic acid minor matters polymer, 35 gram ten
Dialkyl sulfonates, 25 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams；
Each material is sequentially added in reactor, is well mixed, is then ground in sand mill, suitable quantity of water is added, granulated, is dried
Produce water dispersible granules.
By it is following experiment it can be shown that the present invention above-mentioned miticide composition in two active ingredient TDCA-6 and Envidor
Compounding can have obvious synergistic effect.
(2), biological Examples
Embodiment 37：TDCA-6 and Envidor composite formula screening experiment
First, reagent agent（A represents TDCA-6 in following reagents；B represents Envidor）
A agent：35% TDCA-6 wettable powders（WP）（Prepared by the method for embodiment 28）
B agent：35% Envidor wettable powder（WP）（Prepared by the method for embodiment 27）
AB1：TDCA-6 Envidors（A：B=1:40）
AB2：TDCA-6 Envidors（A：B=1:20）
AB3：TDCA-6 Envidors（A：B=1:10）
AB4：TDCA-6 Envidors（A：B=1:5）
AB5：TDCA-6 Envidors（A：B=5:1）
AB6：TDCA-6 Envidors（A：B=10:1）
AB7：TDCA-6 Envidors（A：B=20:1）
AB8：TDCA-6 Envidors（A：B=40:1）
2nd, for examination insect
For examination insect using the red spider adopted in the citrus trees of field, raised for 3 generations indoors as test worm.
3rd, experimental method
Experiment uses slide dip slide method（Slide-dip Method）：The FAO standard methods recommended with reference to FAO (Food and Agriculture Organization of the United Nation)-
Slide infusion process carries out various acaricidal Toxicity Determinations.Two-sided tape is cut into long 2-3 centimetres of band, load is pasted onto
One end of slide, the covering scraps of paper of two-sided tape are thrown off with tip tweezers, and it is fresh to select in the same size, body colour with No. zero writing brush writing brush
Gorgeous, action more it is active it is healthy it is female into mite as preferable examination mite, its back is bonded on the slide for having posted two-sided tape,
The mite foot, mite palpus and mouthpart of mite can not be clung, every adhesive tape glues 3 rows, and often row about glues 10-20 Tetranychus cinnabarinus.In temperature
To be placed in 26 ± 1 DEG C, the insect biochemical cultivation case that the photoperiod is 10h after 3h, sem observation is dissected with binocular, it is strict to reject dead
Or the less inappropriate examination mite of active and position is individual.On the basis of trial test, 5 gradients are configured to various reagent agents
Concentration, one end that slide pastes mite is immersed in for being taken out in reagent liquid after 5 seconds, unnecessary decoction is sopped up with blotting paper rapidly.Paving
One layer of moistening gauze is in white Porcelain Jar, and the slide of dipped decoction is positioned in big porcelain dish, and then one layer of paving is wet on Porcelain Jar
The sponge of profit, then one layer of moistening gauze is covered to reach preferable moistening effect, it is subsequently placed in above-mentioned biochemical cultivation case, and
Checking experiment result afterwards.Deionized water is impregnated as control treatment using band mite slide, each processing repetition time.And respectively in 24
Hour, 48 hours, the examination mite individual amount after 72 hours with binocular anatomical lens inspection result, respectively record survival and death.With
Writing brush touches examination mite individual, and using mite, motionless person is death enough, and the control treatment death rate is used in combination below 10% for efficiency test sample
The control death rate is corrected.Every kind of reagent tests 5 kinds of concentration（Every kind of specific concentration of reagent refers to table 1）, each reprocessing
Three times, 90 are repeated every time, 72 hours microscopy results after medicine obtain the death rate for test worm, calculate LC50And co-toxicity coefficient
（CTC）.
4th, computational methods
The death rate of every kind of reagent is converted to correspondence niqueMin（y）For ordinate, and with pair of the various concentrations of various reagents
Numerical value lgx is abscissa, using least square method, obtains virulence equation（y=a+blgx）Middle coefficient a, b.According to virulence equation,
As y=5.000（NiqueMin when i.e. the death rate is 50%）, calculate the LC of the reagent50.Calculated using the abundant equations of Sun Yun mixed
Close the co-toxicity coefficient of medicament（CTC）（Bibliography：Tan Genjia, wish Jianping etc., " fungicide bioassay computational methods and should
With ", Anhui agronomy circular, 1998,4（1）, 27-28）.The CTC values calculated using the abundant equations of Sun Yun, China is generally acknowledged that
CTC, which is more than 150, has synergistic effect（Wherein：CTC, which is more than 200, has notable synergistic effect）, CTC is addition work 50~150
With it is antagonism that CTC, which is less than 50,.
5th, result and analysis
TDCA-6 and Envidor composition series proportioning mixture are to citrus red mite Toxicity Determination result, LC50With common poison system
Number（CTC）It is shown in Table 2, table 3.Because length is limited, data only actually is the very little one of experimental data of the present invention in table 1
Point, for example, for TDCA-6 and the ratio of Envidor, from 100:1~1:100,5, intermediate data interval point, i.e., 100:1、95:
1、90:1……1:95、1:100, if necessary the data to minizone studied in detail again.Meanwhile, also do, in above-mentioned number
According to the ratio of TDCA-6 and Envidor, from 100:1~1:100,5, intermediate data interval point, i.e., 100:1、95:1、90:
1……1:95、1:In 100, TDCA-7, TDCA-8, TDCA-9, TDCA-10, TDCA-11, TDCA-12, TDCA- is respectively adopted
13 have carried out many experiments instead of TDCA-6, because the basically identical property of research method, result of study have similitude, this specialty
Field personnel have repeatability with reference to the technical inspiration of the present invention, so only listing fraction, representative number in the present invention
According to.
Laboratory experiment result shows that TDCA-6 and Envidor composition series proportioning mixture are not shown to citrus red mite
Go out antagonism, most of to have certain synergistic effect, its CTC value of AB5, AB6 is all higher than 200, shows there is notable synergistic effect.
The co-toxicity coefficient of wherein AB5 mixtures is maximum（CTC=206）, illustrate that its synergistic effect is maximum.
Table 2, TDCA-6 and Envidor match mixture to citrus red mite Toxicity Determination result
The LC of table 350And co-toxicity coefficient（CTC）
The death rate corresponding probit value when y represents composition series proportioning mixture various concentrations in table 3, x represents concentration（C）Pair
Numerical value lgC（That is x=lgC）.
Embodiment 38：TDCA-6 Envidor composition for preventing and controlling citrus red mites field efficacy is tested
First, reagent agent
1st, 40% miticide composition TDCA-6 spirodiclofen water dispersible granules（WDG）（Prepared according to the method for embodiment 22）, its
Middle active ingredient weight compares TDCA-6：Envidor=7:1；
2nd, 20% miticide composition TDCA-6 Envidor wettable powders（WP）（Prepared according to the method for embodiment 3）Wherein
Active ingredient weight compares TDCA-6：Envidor=7:1；
3rd, 10% Envidor suspending agent（SC）（Prepared according to the method for embodiment 29）；
4th, 10% TDCA-6 suspending agents（SC）（Prepared according to the method for embodiment 30）.
2nd, experimental subjects
1st, place is tested：Mianyang City Nong Ke areas of Sichuan Province live kwan-yin village Citrus Orchard；
2nd, crop is tested：Sweet orange；
3rd, controlling object：Citrus red mite.
3rd, experimental method
1st, processing item：40% miticide composition TDCA-6 spirodiclofen water dispersible granules（WDG）8000 times of dilution；20% kills
Acaricidal composition TDCA-6 Envidor wettable powders（WP）4000 times of dilution；10% Envidor suspending agent（SC）Dilution 2000
Times；10% TDCA-6 suspending agents（SC）2000 times of dilution.Blank control：Using clear water.
2nd, cell is set：Each cell seeds, the age of tree, growing way and rich water quality management condition are basically identical.Each cell is fixed 3
Set, four repetitions, totally 24 cell；And cell is arranged according to random area.
3rd, spraying time and method：In citrus red mite peak of occurrence period（June 16）Once, spray, which is worked as, to be become a fine day for dispenser
My god, 2~4 grades of wind-force, 26~33 DEG C of temperature, after medicine 2 days without rainfall, after medicine of short duration heavy rain, rainfall 10 had dropped in the 3rd day
Millimeter, has certain influence to the experiment of this field efficacy.It is positive and negative to squirt blade using manual compression sprayer even spraying
Face is degree.
4th, control time and method：Before dispenser and 3 days after dispenser, respectively investigate once within 10 days, 20 days, 30 days.Method is
Each tree wins 30 leaves at random in four orientation, and mite quantity living on 360, record blade is won per cell, mite mouthful is calculated and subtracts
Move back rate and preventive effect.
4th, experimental result
40% miticide composition TDCA-6 spirodiclofen water dispersible granules（WDG）8000 times of dilution；20% miticide composition
TDCA-6 Envidor wettable powders（WP）4000 times of dilution, 3 days are respectively 91.68% to citrus red mite preventive effect after dispenser
With 90.12%；10 days are respectively 89.09% and 88.37% to citrus red mite preventive effect after dispenser；After dispenser 20 days to the red spider of citrus
Spider preventive effect is respectively 81.60% and 80.01%；30 days are respectively 77.33% and 75.84% to citrus red mite preventive effect after dispenser.It is right
According to the Envidor suspending agent of medicament 10%（SC）2000 times of dilution, 3 days after dispenser, investigates preventive effects point in 10 days, 20 days, 30 days four times
Wei 88.58%, 86.17%, 77.25%, 67.92%.The TDCA-6 suspending agents of comparison medicament 10%（SC）2000 times of dilution, dispenser
It is respectively 80.59%, 75.58%, 73.64%, 69.29% that 3 days afterwards, 10 days, 20 days, 30 days four times, which investigate preventive effects,（Refer to table 4）.Root
Observed according to field experiment, do not find that TDCA-6 Envidors miticide composition produces poisoning phenomenon to experiment crop.
The TDCA-6 of table 4 and Envidor series proportioning mixture are to citrus red mite field experiment result statistical form
Claims (7)
1. miticide composition, with N- (5- tert-butyl groups -1,3,4- thiadiazoles -2- bases)-N'- (2,6- disubstituted pyridines -4- bases)-N,
4- dimethyl -1,2,3- thiadiazoles -5- formamidine compounds, abbreviation TDCA classes compound and Envidor are active ingredient, with agriculture
Acceptable auxiliary element is collectively constituted in medicine, and wherein TDCA and Envidor part by weight are 40:1 to 1:40.
2. miticide composition according to claim 1, it is characterized in that the active ingredient TDCA and Envidor part by weight are
1:5 to 20:1.
3. miticide composition, by the current conventional pesticide mode of production, is prepared as various forms of according to claim 1
Available microcapsule formulations（CJ）, suspension emulsion（SE）, water dispersible granules（WDG）, wettable powder（WP）, aqueous emulsion, suspension
Any of the preparation formulations such as agent formulation.
4. miticide composition, the evil for fruit tree, vegetables, cotton, peanut and other crops and ornamental plant according to claim 1
Acarid control.
5. miticide composition according to claim 1, it is characterized in that miticide composition of the present invention can be compound N-(uncle 5-
Butyl -1,3,4- thiadiazoles -2- bases)-N'- (2,6- dichloropyridine -4- bases)-N, 4- dimethyl -1,2,3- thiadiazoles -5- first
Amidine, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (the chloro- 6- fluorine pyridin-4-yls of 2-)-N, 4- dimethyl -1,
2,3- thiadiazoles -5- carbonamidines, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (chloro- 6- bromopyridines -4- of 2-
Base)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'-
(the chloro- 6- iodine pyridines -4- bases of 2-)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines, compound N-(the 5- tert-butyl groups -1,3,4-
Thiadiazoles -2- bases)-N'- (2,6- difluoro pyridine -4- bases)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines, compound N -
(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (the bromo- 6- fluorine pyridin-4-yls of 2-)-N, 4- dimethyl -1,2,3- thiadiazoles -
5- carbonamidines, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (the fluoro- 6- iodine pyridines -4- bases of 2-)-N, 4- diformazans
Base -1,2,3- thiadiazoles -5- carbonamidines, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (2,6- dibromo pyridines -
4- yls)-N, 4- dimethyl -1,2, any one in 3- thiadiazoles -5- carbonamidines is with Envidor can in active ingredient, with agricultural chemicals
Collectively constituted with the auxiliary element of receiving.
6. miticide composition according to claim 1, it is characterized in that miticide composition of the present invention can also be compound N-(5-
The tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (2,6- dichloropyridine -4- bases)-N, 4- dimethyl -1,2,3- thiadiazoles -5- first
Amidine, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (the chloro- 6- fluorine pyridin-4-yls of 2-)-N, 4- dimethyl -1,
2,3- thiadiazoles -5- carbonamidines, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (chloro- 6- bromopyridines -4- of 2-
Base)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'-
(the chloro- 6- iodine pyridines -4- bases of 2-)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines, compound N-(the 5- tert-butyl groups -1,3,4-
Thiadiazoles -2- bases)-N'- (2,6- difluoro pyridine -4- bases)-N, 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines, compound N -
(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (the bromo- 6- fluorine pyridin-4-yls of 2-)-N, 4- dimethyl -1,2,3- thiadiazoles -
5- carbonamidines, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (the fluoro- 6- iodine pyridines -4- bases of 2-)-N, 4- diformazans
Base -1,2,3- thiadiazoles -5- carbonamidines, compound N-(the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (2,6- dibromo pyridines -
4- yls)-N, any two kinds in 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines and the TDCA mixtures after two or more combinations
Active ingredient is combined as with Envidor again, is collectively constituted with acceptable auxiliary element in agricultural chemicals.
7. the miticide composition according to claim 4 containing TDCA-6 and Envidor is complete in preventing and treating citrus red mite, apple
Pawl is full, hawthorn Tetranychus urticae, the purposes on tetranychus vinenensis zacher.
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| 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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| 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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| WO2022259985A1 (en) * | 2021-06-10 | 2022-12-15 | 日本化薬株式会社 | Pest controlling agent |
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