The bactericidal composition of a kind of 2-cyano-3-amino-3-phenylancryic acetate-containing and own azoles alcohol
Technical field
The invention belongs to technical field of pesticide, relate to the composite application of bactericide on wheat and the common disease of paddy rice of a kind of 2-cyano-3-amino-3-phenylancryic acetate-containing and own azoles alcohol.
Technical background
2-cyano-3-amino-3-phenylancryic acetate was synthesized by China Jiangsu Prov. Inst. of Agricultural Chemicals in 1998, belonged to 2-cyanoacrylate bactericide, obtained the interim registration card of Ministry of Agriculture's Pesticidal products in 2007, and preparation belongs to little malicious pesticide species.Former medicine outward appearance is the white solid powder.Chemical name: 2-cyanic acid-3-aminoacrylic acid ethyl ester.Structural formula is:
2-cyano-3-amino-3-phenylancryic acetate is effective to the disease that the reaping hook mushroom causes, has protective effect and therapeutic action.Be absorbed through root, upwards transporting property arranged on blade, towards the blade bottom and interlobate transporting property relatively poor.The result shows through field control effectiveness test, and 2-cyano-3-amino-3-phenylancryic acetate 25% suspending agent has the better prevention effect to wheat scab.
Own azoles alcohol is the triazole bactericidal agent of new generation by Syngenta Co.,Ltd's exploitation, is one of safest bactericide in the present triazole type.Outward appearance is the ecru loose powder, 110~112 ℃ of fusing points, and chemical name: (RS)-2-(2,4 dichloro benzene base)-1-(1H-1,2,4-triazol-1-yl)-oneself-2-alcohol, structural formula is:
Own azoles alcohol is to stay pure demethylation inhibitor, has the efficient sterilizing effect, and the disease that fungi especially Basidiomycota and Ascomycota are caused has the protection and the therapeutic action of broad spectrum activity.Can be used for paddy rice, fruit tree, peanut and other crops, can prevent and treat banded sclerotial blight, powdery mildew, black viral disease, leaf spot.
Long-term practical application shows; Own azoles alcohol is desirable to preventive effects such as multiple diseases such as alternaria leaf spot of apple, rice sheath blight disease, wheat sharp eyespots, but use cost is higher separately, is unfavorable for that large tracts of land promotes the use of; And along with the increase of usage amount, tangible pesticide resistance has appearred in some local diseases; 2-cyano-3-amino-3-phenylancryic acetate has good preventive and therapeutic effect to wheat diseases especially head blight, and long-term the use is prone to develop immunity to drugs.
The field is given birth to survey and is shown, there is synergistic effect preferably the composite back of 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol to the disease on wheat and the paddy rice, and has delayed the generation of disease drug resistance.Do not see the relevant report of the composite product of relevant 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol up to now as yet.
Summary of the invention
A kind of bactericidal composition that The present invention be directed to the high problem of serious, the single agent agricultural chemicals of present disease drug resistance use cost and develop.Said composition effective active composition contains 2-cyano-3-amino-3-phenylancryic acetate-containing and own azoles alcohol, has obvious role in synergism after the two is composite.
The present invention realizes through following technical scheme:
The bactericidal composition that contains 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol; It is characterized in that: 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol percentage by weight are 10~80: 30~1; Effective active composition weight percentage is 11% to 80%, and the effective active composition adds auxiliary agent, filler or deionized water and processes wetting powder, water dispersible granules, suspending agent, aqueous emulsion or microemulsion.
When processing wetting powder, composition comprises following constituent content: 2-cyano-3-amino-3-phenylancryic acetate 10~80%, own azoles alcohol 1~30%, dispersant 3~15%, wetting agent 2~12%, filler 8~84%.
Above-mentioned formulation material is mixed, in mixed cylinder, mix, after airslide disintegrating mill is pulverized, mix again, promptly can be made into the own azoles alcohol of 2-cyano-3-amino-3-phenylancryic acetate wetting powder product.
When processing water dispersible granules, composition comprises following constituent content: 2-cyano-3-amino-3-phenylancryic acetate 10~80%, own azoles alcohol 1~30%, dispersant 3~12%, wetting agent 2~8%, disintegrant 0~8%, binding agent 0~5%, filler 8~84%.
Former medicine is obtained the particle diameter that needs with dispersant, wetting agent, disintegrant, filler etc. through comminution by gas stream, add other auxiliary agents such as adhesive again, obtain the materials of granulating.It is interior through after granulation and the drying to expect that article are quantitatively sent the fluidized bed granulation dryer to, makes 2-cyano-3-amino-3-phenylancryic acetate diniconazole water dispersible granule product.
When processing suspending agent, composition comprises following constituent content: 2-cyano-3-amino-3-phenylancryic acetate 10~50%, own azoles alcohol 1~15%, dispersant 3~12%, wetting agent 2~10%, antifoaming agent 0.1~0.5%, thickener 0~2%, antifreeze 0~8%, deionized water surplus.
Dispersant, wetting agent, antifoaming agent, thickener, antifreeze in the above-mentioned formulation material are mixed through high speed shear; Add former medicine; Ball milling is 2~3 hours in ball mill, makes diameter of particle all below 5 μ m, makes 2-cyano-3-amino-3-phenylancryic acetate hexaconazole suspending agent product.
When processing aqueous emulsion, composition comprises following constituent content: 2-cyano-3-amino-3-phenylancryic acetate 10~50%, own azoles alcohol 1~15%, solvent 5~25%, emulsifier 1~6%, dispersant 2~6%, antifoaming agent 0.01~0.5%, thickener 0~2%, antifreeze 0~6%, deionized water surplus.
Above-mentioned formulation material Central Plains medicine, solvent added with emulsifier be in the same place, make and be dissolved into even oil phase; Water, antifreeze, antifoaming agent etc. are mixed, become the homogeneous water; Under high-speed stirred, water is added oil phase or oil phase is added water, make 2-cyano-3-amino-3-phenylancryic acetate hexaconazole aqueous emulsion product behind the good dispersion.
When processing microemulsion, composition comprises following constituent content: 2-cyano-3-amino-3-phenylancryic acetate 10~50%, own azoles alcohol 1~15%, solvent 5~25%, emulsifier 1~15%, antifreezing agent 1~10%, deionized water surplus.
Above-mentioned prescription Central Plains medicine, solvent, emulsifier fully are mixed into the oil phase of homogeneous transparent; Under agitation slowly add deionized water; Form WO emulsion,, make it rapid phase inversion and become oil-in-water type again through agitating heating; Be chilled to room temperature and make it to reach balance, make stable 2-cyano-3-amino-3-phenylancryic acetate hexaconazole microemulsion product through filtering.
Described dispersant is selected from one or more in polycarboxylate, lignosulfonates, APES formaldehyde condensation products sulphate, alkyl benzene sulfonate calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, APES, aliphatic amine polyoxyethylene ether, polyoxyethylene carboxylate, the fatty acid glyceride APEO.
Described wetting agent is natural products wetting agent and cationic wetting agent, and available tea is withered, spaonin powder, silkworm excrement, soapberry powder, bay alcohol radical sodium sulphate, lauryl sodium sulfate, neopelex, washing powder, draw back in the powder one or more.
Described emulsifier is selected from: farming breast 500
#(alkyl benzene calcium sulfonate), OP series phosphate (NPE phosphate), 600
#Phosphate (phenyl phenol polyoxy ethyl ether phosphate), styrene polyoxyethylene ether ammonium sulfate salt, alkyl biphenyl ether disulfonic acid magnesium salts, triethanolamine salt, farming breast 400
#(benzyl dimethyl phenol polyoxy ethyl ether), farming breast 600
#(phenyl phenol polyoxy ethyl ether), Nongru-700
#(alkylphenol-formaldehyde resin polyoxy ethyl ether), farming breast 1600
#(phenethyl phenol polyoxy ethyl polypropylene-base ether), ethylene oxide-propylene oxide block copolymer, OP series (NPE), By series (castor oil polyoxyethylene ether), farming breast 33
#In (alkylaryl polyoxyethylene polyoxypropylene ether), sapn series (sorbitan monostearate), tween series (sorbitan fatty acid ester APEO), the AEO series (the pure APEO of fat) one or more.
Described solvent is selected from: N; Dinethylformamide, cyclohexanone, toluene, xylol, dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, 3-methyl cyclohexanol ketenes, N-octylpyrrolidone, N-pyrrolidones, N-Methyl pyrrolidone, N, one or more in N dimethyl formamide, propyl alcohol, butanols, ethylene glycol, diethylene glycol, EGME, butyl ether, ethyl acetate, vegetable oil, the acetonitrile.
Described disintegrant is selected from one or more in bentonite, ammonium sulfate, calcium chloride, urea, magnesium chloride, aluminium chloride, citric acid, succinic acid, the carbonic hydroammonium.
Described antifoaming agent is selected from one or more in silicone oil, silicone compound, C10-20 saturated fat acid compounds, the C8-10 aliphatic alcohols compound.
Described antifreeze is selected from: one or more in ethylene glycol, propane diols, the glycerine.
Described binding agent is selected from: one or more in gum Arabic, white dextrin, carboxy-propyl cellulose, xanthan gum, methylcellulose, PAA, polyvinylpyrrolidone, PVPP, polyethylene glycol, polyvinyl alcohol, anhydrous succinic acid-styrene copolymerized, the polyvinyl acetate.
Described thickener is selected from: one or more in xanthans, CMC, hydroxyethylcellulose, methylcellulose, Magnesiumaluminumsilicate, polyvinyl alcohol, the polyethylene glycol.
Described filler is selected from: one or more in kaolin, diatomite, bentonite, attapulgite, white carbon, starch, the precipitated calcium carbonate.
Described bactericidal composition is used to prevent and treat wheat sharp eyespot, wheat scab, rice sheath blight disease, bakanae disease of rice.
The invention has the advantages that (1) 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol have double action mechanism, germ is difficult for producing resistance; (2) indoor biometrics is tested the result and is shown: 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol is composite by a certain percentage that crop pest is had clearly synergistic effect; (3) enlarge fungicidal spectrum, 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol can be prevented and treated ring rot of apple, alternaria leaf spot of apple, rice sheath blight disease, rice blast, bakanae disease of rice, wheat sharp eyespot, wheat scab, have enlarged fungicidal spectrum; (4) reduce use cost, use cost is higher separately for own azoles alcohol, is mixed with lower-cost 2-cyano-3-amino-3-phenylancryic acetate and can reduces use cost; (5) belong to environment friendly agricultural.2-cyano-3-amino-3-phenylancryic acetate, own azoles alcohol all belong to low-toxin farm chemicals, its complex preparation, and high-efficiency low-toxicity to crop and Environmental security, helps the sustainable development of agricultural production.
Embodiment
Below in conjunction with embodiment the present invention is further explained, but the scope of application of the present invention is not limited to the following embodiment that lifts.
The own azoles alcohol of embodiment 1 80% 2-cyano-3-amino-3-phenylancryic acetate wetting powder
2-cyano-3-amino-3-phenylancryic acetate 65%, own azoles alcohol 15%, polycarboxylate 5%, soapberry powder 4%, kaolin 11%, mixture carries out comminution by gas stream, makes the own azoles alcohol of 80% 2-cyano-3-amino-3-phenylancryic acetate wetting powder.
The own azoles alcohol of embodiment 2 50% 2-cyano-3-amino-3-phenylancryic acetates wetting powder
2-cyano-3-amino-3-phenylancryic acetate 42%, own azoles alcohol 8%, polyoxyethylene carboxylate 5%, spaonin powder 4%, white carbon 8%, kaolin 33%, mixture carries out comminution by gas stream, makes the own azoles alcohol of 50% 2-cyano-3-amino-3-phenylancryic acetate wetting powder.
Embodiment 3 75% 2-cyano-3-amino-3-phenylancryic acetate diniconazole water dispersible granules
2-cyano-3-amino-3-phenylancryic acetate 60%, own azoles alcohol 15%, aliphatic amine polyoxyethylene ether 4%, soapberry powder 4%, urea 3%, starch 14%, the mixed 75% 2-cyano-3-amino-3-phenylancryic acetate diniconazole water dispersible granule that gets.
Embodiment 4 40% 2-cyano-3-amino-3-phenylancryic acetate diniconazole water dispersible granules
2-cyano-3-amino-3-phenylancryic acetate 35%, own azoles alcohol 5%, polycarboxylate 3%, spaonin powder 5%, ammonium sulfate 3%, starch 10%, precipitated calcium carbonate 39%, the mixed 40% 2-cyano-3-amino-3-phenylancryic acetate diniconazole water dispersible granule that gets.
Embodiment 5 50% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole suspending agents
2-cyano-3-amino-3-phenylancryic acetate 44%, own azoles alcohol 6%, alkyl benzene sulfonate calcium salt 5%, washing powder 3%, silicone oil 0.1%, deionized water add to 100%, the mixed 50% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole suspending agent that gets.
Embodiment 6 25% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole suspending agents
2-cyano-3-amino-3-phenylancryic acetate 22%, own azoles alcohol 3%, lignosulfonates 3%, soapberry powder 4%, silicone oil 0.1%, polyethylene glycol 0.2%, ethylene glycol 3%, deionized water add to 100%, the mixed 25% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole suspending agent that gets.
Embodiment 7 40% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole aqueous emulsions
2-cyano-3-amino-3-phenylancryic acetate 36%, own azoles alcohol 4%, cyclohexanone 20%, N; N dimethyl formamide 5%, phenethyl phenol polyoxy ethyl polypropylene-base ether 5%, lignosulfonates 4%, silicone oil 0.1%, deionized water add to 100%, the mixed 40% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole aqueous emulsion that gets.
Embodiment 8 20% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole aqueous emulsions
2-cyano-3-amino-3-phenylancryic acetate 17%, own azoles alcohol 3%, cyclohexanone 20%, phenyl phenol polyoxy ethyl ether 4%, phenyl phenol polyoxy ethyl ether phosphate 3%, polycarboxylate 3%, silicone oil 0.1%, xanthan gum 0.2%, ethylene glycol 3%, deionized water add to 100%, the mixed 20% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole aqueous emulsion that gets.
Embodiment 9 35% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole microemulsions
2-cyano-3-amino-3-phenylancryic acetate 30%, own azoles alcohol 5%, N-Methyl pyrrolidone 10%, cyclohexanone 5%, N; N dimethyl formamide 5%, alkyl benzene calcium sulfonate 5%, alkylphenol-formaldehyde resin polyoxy ethyl ether 8%, deionized water add to 100%, the mixed 35% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole microemulsion that gets.
Embodiment 10 11% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole microemulsions
2-cyano-3-amino-3-phenylancryic acetate 10%, own azoles alcohol 1%, N, N dimethyl formamide 10%, phenyl phenol polyoxy ethyl ether 4%, benzyl dimethyl phenol polyoxy ethyl ether 5%, deionized water add to 100%, the mixed 11% 2-cyano-3-amino-3-phenylancryic acetate hexaconazole microemulsion that gets.
We have carried out mutual composite synergy research with compositions such as 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol, and research is the method that adopts indoor bioassay and field trial to combine.Through indoor bioassay, the synergy ratio (SR) after clear and definite two kinds of medicaments are composite by a certain percentage on this basis, is carrying out field trial earlier.Draw final conclusion after data are analyzed.
Practice example one: 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol are mixed and supply the reagent agent to be provided by Shaanxi Pucheng County Meibang Pesticide Co., Ltd. to the rice sheath blight disease Toxicity Determination.
Supply the examination bacterial classification: rice sheath blight disease, adopt back by Hanzhong City Yang County, Shaanxi Province, separate activation through the laboratory, through subsequent use after twice switching.
Each active constituent content of test medicine is designed 5 concentration of treatment respectively, be treated to contrast, the inhibitory action of rice sheath blight disease germ is carried out indoor measurement with blank.The mycelial growth rate method is adopted in test, earlier each proportioning is become the series concentration gradient.Will the rice sheath blight disease germ after secondary separation is cultivated use diameter as the aseptic card punch of 0.5CM at the blade inlet edge place punching subsequent use, move then on pastille PDA plating medium, place in 25 ± 1 ℃ of incubators and cultivate, cultivate and measure colony diameter after 6 days.Every processing repetition 6 times.The result that surveys compare with contrast and calculate antibacterial percentage.5 proportionings are carried out synergism test by the synergism test method.Computing formula is following:
Clean amount of growth (mm)=measurement colony diameter-5
Mycelial growth inhibition rate is converted into probit value (y), and liquor strength (μ g/mL) converts logarithm value (x) to, tries to achieve virulence regression equation (y=a+bx) with method of least squares, and calculates the EC of every kind of medicament thus
50Value.Calculate the different proportioning synergy ratios (SR) of two medicaments according to the Wadley method simultaneously, SR<0.5 is an antagonism, and 0.5≤SR≤1.5 are summation action, and SR>1.5 are synergistic effect.Computing formula is following:
Wherein: a, b are respectively 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol shared ratio in combination;
A is a 2-cyano-3-amino-3-phenylancryic acetate;
B is own azoles alcohol;
The virulence regression equation of the 2-cyano-3-amino-3-phenylancryic acetate that is obtained, own azoles alcohol and composite comparison rice sheath blight disease, suppress in concentration and synergy ratio (SR) like following table:
The own azoles alcohol of table 1 2-cyano-3-amino-3-phenylancryic acetate is to the rice sheath blight disease Toxicity Determination
Can know by table 1; 2-cyano-3-amino-3-phenylancryic acetate of the present invention and own azoles alcohol are composite; To the rice sheath blight disease Toxicity Determination; When 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol proportioning is that 1: 1,4: 1,7: 1,10: 1,13: 1 synergy ratio is respectively 1.35,1.50,1.73,170,1.48, wherein when 2-cyano-3-amino-3-phenylancryic acetate: own azoles alcohol shows as synergistic effect when being 4: 1,7: 1,10: 1, explain 2-cyano-3-amino-3-phenylancryic acetate and own azoles pure both be mixed in the scope at 4: 1~10: 1 comparatively reasonable.
Practice example two: the 2-cyano-3-amino-3-phenylancryic acetate and the composite rice disease test of pesticide effectiveness of preventing and treating of own azoles alcohol
This EE is Changan District Wang Mang township in the Xian City, Shanxi Province, and test medicine is researched and developed, provided by Shaanxi Pucheng County Meibang Pesticide Co., Ltd., contrast medicament 25% 2-cyano-3-amino-3-phenylancryic acetate suspending agent (commercial), 10% own azoles alcohol missible oil (commercial).
Investigation paddy rice disease index before rice sheath blight disease and the bakanae disease of rice initial stage of origination, medicine, August 14, the second time and dispenser were for the third time carried out in dispenser for the first time respectively on August 21, August 28, and dispenser is 3 times altogether, 50 kilograms of mu spraying volumes.Behind 7 days, dispenser for the third time after the dispenser for the third time, investigated disease index and calculation correction preventive effect in 14 days respectively.Result of the test such as following table:
The own azoles alcohol composition of table 2 2-cyano-3-amino-3-phenylancryic acetate is prevented and treated the rice disease test of pesticide effectiveness
Can find out that by table 2 the composite back of 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol is to bakanae disease of rice, rice sheath blight disease controlling test, the invention medicament to bakanae disease of rice last medicine after 7 days preventive effects, 14 days preventive effects reach 70.38~77.25%, 85.91~92.72% respectively; 7 days preventive effects, 14 days preventive effects behind the rice sheath blight disease last medicine are reached 67.46~74.55%, 81.72~90.75% respectively; 25% 2-cyano-3-amino-3-phenylancryic acetate suspending agent to bakanae disease of rice last medicine after 7 days preventive effects, 14 days preventive effects be respectively 73.24%, 82.42%; 7 days preventive effects, 14 days preventive effects behind the rice sheath blight disease last medicine are respectively 57.75%, 60.45%; 10% own azoles alcohol missible oil to bakanae disease of rice last medicine after 7 days preventive effects, 14 days preventive effects be respectively 42.09%, 44.87%; 7 days preventive effects, 14 days preventive effects behind the rice sheath blight disease last medicine are respectively 68.24%, 72.88%.In trial stretch, handle medicament to rice safety, have no adverse effects.Simultaneously, the inventor finds that preparation of the present invention also has certain preventive effect to rice blast.
Practice routine three 2-cyano-3-amino-3-phenylancryic acetates and own azoles alcohol composite prevent and treat wheat scab test of pesticide effectiveness test arrangement in the Xian City, Shanxi Province Changan District.
Supply the reagent agent: the composite product of the own azoles alcohol of 2-cyano-3-amino-3-phenylancryic acetate is provided by Shaanxi Pucheng County Meibang Pesticide Co., Ltd.; Contrast medicament 25% 2-cyano-3-amino-3-phenylancryic acetate suspending agent (commercial), 10% own azoles alcohol missible oil (commercial).
Dispenser is 2 times altogether, dispenser for the first time on April 2, and dispenser for the second time on July 9 was investigated disease indexs in 7 days, 14 days after the dispenser for the second time and is calculated preventive effect.Result of the test is as follows:
Table 3 2-cyano-3-amino-3-phenylancryic acetate and the composite wheat scab field control effectiveness test of preventing and treating of own azoles alcohol
Find out by table 3, prevent and treat the wheat scab effect after 2-cyano-3-amino-3-phenylancryic acetate and own azoles alcohol are composite and be superior to contrasting medicament, can effectively prevent and treat the generation of wheat scab, in trial stretch,, handle medicament and wheat sharp eyespot is had certain preventive effect the target crop safety.