Embodiment
Below in conjunction with instance the present invention is described further.But the present invention only limits to these examples absolutely not.Percentage or proportioning is weight percentage or weight ratio in all prescriptions.The processing technology of the various preparations of the present composition and equipment are that the public is known.
1, the preparation of aqueous emulsion
Active component is used dissolution with solvents, add emulsifier for mixing, will stablize antifreezing agent and water mixing homogeneous as water to transparent as oil phase.Under 3000~6000 rev/mins of shear conditions, oil phase slowly is added to aqueous phase stirred 20~50 minutes, form the aqueous emulsion of favorable dispersibility.
FORMULATION EXAMPLE 1:10% piperazine worm pyridine abamectin aqueous emulsion
Piperazine worm pyridine (active component) 1%
AVM (active component) 9%
Trimethylbenzene (solvent) 15%
Sodium alkyl benzene sulfonate (emulsifier) 8%
Glycerine (stablizing antifreezing agent) 5%
Water complements to 100%
FORMULATION EXAMPLE 2:10% piperazine worm pyridine abamectin aqueous emulsion
Piperazine worm pyridine (active component) 5%
AVM (active component) 5%
Xylol (solvent) 10%
Sodium alkyl benzene sulfonate (emulsifier) 5%
Glycerine (stablizing antifreezing agent) 4%
Water complements to 100%
FORMULATION EXAMPLE 3:10% piperazine worm pyridine emamectin-benzoate aqueous emulsion
Piperazine worm pyridine (active component) 9.9%
Emamectin-benzoate (active component) 0.1%
Toluene (solvent) 15%
Castor oil polyoxyethylene ether (emulsifier) 5%
Urea (antifreezing agent) 1%
Water complements to 100%
2, the preparation of microemulsion
Active component with the dissolving of solvent, cosolvent, is added emulsifier for mixing to transparent in oil phase, will stablize antifreezing agent and water mixing homogeneous as water.Oil phase slowly is added drop-wise to aqueous phase, stirs the microemulsion that formed favorable dispersibility in 30~60 minutes.
FORMULATION EXAMPLE 4:22% piperazine worm pyridine avermectin micro-emulsion
Piperazine worm pyridine (active component) 20%
AVM (active component) 2%
Acetone (solvent) 15%
DMF (cosolvent) 5%
Phenethyl phenol polyethenoxy ether (emulsifier) 10%
The newborn 500# of farming (emulsifier) 5%
Ethylene glycol (stablizing antifreezing agent) 2%
Water complements to 100%
FORMULATION EXAMPLE 5:15.5% piperazine worm pyridine emamectin benzoate microemulsion
Piperazine worm pyridine (active component) 15%
Emamectin-benzoate (active component) 0.5%
Acetone (solvent) 15%
Pyrrolidones (cosolvent) 8%
APES formaldehyde condensation products (emulsifier) 10%
The newborn 500# of farming (emulsifier) 5%
Ethylene glycol (stablizing antifreezing agent) 1%
Water complements to 100%
3, the preparation of suspending agent
Active component, dispersant, wetting agent, thickener and the water mixed by prescription successively is even,, sand mill obtains suspending agent after grinding.
FORMULATION EXAMPLE 6:21% piperazine worm pyridine AVM suspending agent
Piperazine worm pyridine (active component) 20%
AVM (active component) 1%
Sodium alkyl benzene sulfonate (dispersant) 8%
APES (wetting agent) 4%
Xanthans (thickener) 0.3%
Water complements to 100%
FORMULATION EXAMPLE 7:15.5% piperazine worm pyridine AVM suspending agent
Piperazine worm pyridine (active component) 15%
AVM (active component) 0.5%
Sodium alkyl benzene sulfonate (dispersant) 8%
APES (wetting agent) 5%
Magnesiumaluminumsilicate (thickener) 0.8%
Water complements to 100%
FORMULATION EXAMPLE 8:11% piperazine worm pyridine emamectin benzoate suspending agent
Piperazine worm pyridine (active component) 10%
Emamectin-benzoate (active component) 1%
Sorbitan fatty acid ester APEO (dispersant) 6%
APES (wetting agent) 5%
Sodium carboxymethylcellulose (thickener) 0.2%
Water complements to 100
4, the preparation of wetting powder
Active component, dispersant, wetting agent and filler etc. are fully mixed in the ratio of prescription, below ultrafine crusher is crushed to 20 μ m, obtain wetting powder.
FORMULATION EXAMPLE 9:41% piperazine worm pyridine AVM wetting powder
Piperazine worm pyridine (active ingredient) 40%
AVM (active ingredient) 1%
Sodium lignin sulfonate (dispersant) 5%
Lauryl sodium sulfate (wetting agent) 2%
Kaolin (filler) complements to 100%.
FORMULATION EXAMPLE 10:8% piperazine worm pyridine emamectin-benzoate wetting powder
Piperazine worm pyridine (active ingredient) 4%
Emamectin-benzoate (active ingredient) 4%
NPE formaldehyde condensation products sodium sulfonate (dispersant) 5%
Lauryl sodium sulfate (wetting agent) 2%
Bentonite (filler) complements to 100%.
5, the preparation of water dispersible granules
Successively add in blender in the ratio of filling a prescription active component, dispersant, wetting agent, binding agent, disintegrant and filler; Mix; Become the following WP of particle diameter 10 μ m through comminution by gas stream; Add 5%~15% water extrusion again and make material, after dry screened, obtain water-dispersible granules.
FORMULATION EXAMPLE 11:50.5% piperazine worm pyridine AVM water dispersible granules
Piperazine worm pyridine (active component) 50%
AVM (active component) 0.5%
Sodium lignin sulfonate (dispersant) 3%
Rope uncle SOPA (dispersant) 3%
Sldium lauryl sulfate (wetting agent) 2%
Sodium silicate (binding agent) 1.5%
Calcium chloride (disintegrant) 5%
Precipitated calcium carbonate (filler) complements to 100
FORMULATION EXAMPLE 12:5.5% piperazine worm pyridine emamectin-benzoate water dispersible granules
Piperazine worm pyridine (active component) 0.5%
Emamectin-benzoate (active component) 5%
Polyoxyethylene polyoxypropylene block copolymer (dispersant) 5%
Draw back powder (dispersant) 3%
Sldium lauryl sulfate (wetting agent) 2%
Carboxymethyl cellulose (binding agent) 0.5%
Ammonium sulfate (disintegrant) 5%
Precipitated calcium carbonate (filler) complements to 100
Biologicall test and test of pesticide effectiveness example:
1, pyridine of piperazine worm and abamectin compounded Toxicity Determination to brown planthopper
The former medicine that the former medicine of test medicine piperazine worm pyridine adopts Kesheng Group Co., Ltd., Jiangsu Prov. to produce, the former medicine that the former medicine of AVM adopts Hebei Weiyuan Biochemical Co., Ltd. to produce.After test method was mixed with mother liquor with reference to " the agricultural industry criteria NY/T 1154.11-2008 of the People's Republic of China (PRC) " with former medicinal organic solvent acetone, the soil temperature with 0.1%-80 aqueous solution was by 5 series mass concentration of method configuration of geometric ratio.The paddy rice brown planthopper nymph in 3 age that the examination worm is an indoor feeding, physiological status is consistent.Choose the healthy and strong consistent paddy rice seedling in tillering stage of laboratory cultures, grubbed out, clean; Be cut into the long band of 10cm root rice stem, it is anhydrous to the surface to dry in the air in the place, cool place, and the rice stem is flooded 30s in the medicament that configures; Taking-up is dried, and encases root with absorbent cotton and preserves moisture, the outsourcing preservative film; Place test tube, every test tube 3 strains.4 repetitions of every processing, and establish the processing that does not contain medicament and do blank.To try worm with pest sucking device and move in the test tube, 15 in every test tube, the mouth of pipe covers with gauze.Examination worm after the processing places temperature (25 ± 1) ℃, relative moisture 60%~80%, and periodicity of illumination is to raise under L: D=(16: 8) the h condition and observe.Carry out statistical analysis with the DPS data processing software, calculate the LC50 of each medicament, estimate with this and supply the activity of reagent agent the examination worm.Calculate co-toxicity coefficient (CTC) according to the abundant method of Sun Yun.
When CTC≤80, then the composition performance is for antagonism, and when 80<CTC<120, then the composition performance is for summation action, and when CTC>=120, then the composition performance is synergistic effect.
Actual measurement toxicity index (ATI)=(standard medicament LC
50/ confession reagent agent LC
50) * 100
The percentage composition of B in percentage composition+B medicament toxicity index * mixture of A in theoretical toxicity index (TTI)=A medicament toxicity index * mixture
Co-toxicity coefficient (CTC)=[mixture actual measurement toxicity index (the ATI)/theoretical toxicity index (TTI) of mixture] * 100
Mensuration result to the paddy rice brown planthopper: see table 1
Worm pyridine of table 1 piperazine and abamectin compounded joint toxicity measuring to the paddy rice brown planthopper
Supply reagent agent (active ingredient weight ratio) |
LC
50 (mg/l)
|
ATI |
TTI |
Co-toxicity coefficient CTC |
The pyridine of piperazine worm |
2.67 |
100.00 |
|
|
AVM |
4.59 |
58.17 |
|
|
Piperazine worm pyridine: AVM (100: 1) |
2.22 |
120.27 |
99.59 |
120.77 |
Piperazine worm pyridine: AVM (50: 1) |
2.01 |
132.84 |
99.18 |
133.93 |
Piperazine worm pyridine: AVM (30: 1) |
1.79 |
149.16 |
98.65 |
151.20 |
Piperazine worm pyridine: AVM (20: 1) |
1.32 |
202.27 |
98.01 |
206.38 |
Piperazine worm pyridine: AVM (10: 1) |
2.1 |
157.99 |
96.20 |
164.23 |
Piperazine worm pyridine: AVM (1: 1) |
3.75 |
113.62 |
79.08 |
143.66 |
Piperazine worm pyridine: AVM (1: 5) |
8.19 |
89.30 |
65.14 |
137.08 |
Piperazine worm pyridine: AVM (1: 10) |
11.87 |
68.99 |
61.97 |
111.33 |
Find out piperazine worm pyridine and abamectin compounded the paddy rice brown planthopper is had very high synergistic effect from table 1.Pyridine of piperazine worm and AVM proportioning are 30: 1, and 20: 1, co-toxicity coefficient was all more than 150 in 10: 1 o'clock.
2, the composite toxicity test of pyridine of piperazine worm and emamectin-benzoate to wheat aphid
The former medicine of test medicine piperazine worm pyridine derives from Kesheng Group Co., Ltd., Jiangsu Prov., and the former medicine of emamectin-benzoate derives from Hebei Weiyuan Biochemical Co., Ltd..Test method is carried out with reference to " the agricultural industry criteria NY/T 1154.9-2008 of the People's Republic of China (PRC) " spray-on process.After former medicinal organic solvent acetone was mixed with mother liquor, the soil temperature with 0.1%-80 aqueous solution was by 5 series mass concentration of method configuration of geometric ratio.The wheat aphid nymph in 3 age that the examination worm is an indoor feeding, physiological status is consistent.Choose 10 examination worms with writing brush and place culture dish, place Potter spray tower domain quantitatively to spray in culture dish again, spouting liquid is 1ml; Take out the examination worm behind the soup sedimentation 1min; To try worm with little writing brush and move in the test tube, 10 in every test tube, the mouth of pipe covers with gauze.4 repetitions of every processing, and establish the processing that does not contain medicament and do blank.Examination worm after the processing places temperature (25 ± 1) ℃, relative moisture 60%~80%, and periodicity of illumination is to raise under L: D=(16: 8) the h condition and observe.Method by biologicall test and test of pesticide effectiveness example 1 is calculated the toxicity index of each medicament and the co-toxicity coefficient (CTC value) of mixture.
The composite joint toxicity measuring of worm pyridine of table 2 piperazine and emamectin-benzoate to wheat aphid
Supply reagent agent (active ingredient weight ratio) |
LC
50 (mg/l)
|
ATI |
TTI |
Co-toxicity coefficient CTC |
The pyridine of piperazine worm |
4.03 |
100.00 |
|
|
Emamectin-benzoate |
2.18 |
184.86 |
|
|
Piperazine worm pyridine: emamectin-benzoate (100: 1) |
3.21 |
125.55 |
100.84 |
124.50 |
Piperazine worm pyridine: emamectin-benzoate (50: 1) |
3.01 |
133.89 |
101.66 |
131.70 |
Piperazine worm pyridine: emamectin-benzoate (30: 1) |
2.79 |
144.44 |
102.74 |
140.60 |
Piperazine worm pyridine: emamectin-benzoate (20: 1) |
1.22 |
330.33 |
104.04 |
317.50 |
Piperazine worm pyridine: emamectin-benzoate (10: 1) |
1.62 |
248.77 |
107.71 |
230.95 |
Piperazine worm pyridine: emamectin-benzoate (1: 1) |
1.85 |
217.84 |
142.43 |
152.94 |
Piperazine worm pyridine: emamectin-benzoate (1: 5) |
1.92 |
209.90 |
170.72 |
122.95 |
Piperazine worm pyridine: emamectin-benzoate (1: 10) |
2.01 |
200.50 |
177.15 |
113.18 |
Find out that from table 2 pyridine of piperazine worm and emamectin-benzoate are composite to have very high synergistic effect to wheat aphid.Pyridine of piperazine worm and emamectin-benzoate proportioning are 20: 1, and 10: 1, co-toxicity coefficient all reached more than 150 in 1: 1 o'clock.
3, the various proportionings of pyridine of piperazine worm and AVM are to the field efficiency test of paddy rice brown planthopper.
Trial crops is a paddy rice, and controlling object is the paddy rice brown planthopper.Embodiment 1,2,4,6,7,9,11 7 kind of medicament respectively to the processing of spraying after the even dilution of water, are established medicament contrast and the contrast of blank clear water.District's group arrangement at random between processing is handled three times for every kind and is repeated.1 day, 3 days and 7 days investigation number of pest behind medicine are calculated lethality and control efficiency respectively, and result of the test is as shown in table 3.
Table 3 different disposal is to the field test results (1d, 3d and 7d behind the medicine) of paddy rice brown planthopper
Annotate: data are 3 repetition mean values in the table.
Can find out that from result of the test (seeing table 3) what the 1st day preventive effect was best behind the medicine is formulation examples 4 (22% piperazine worm pyridine avermectin micro-emulsion, 12ml/ mu), preventive effect is 89.04%.What the 3rd day preventive effect was best behind the medicine is formulation examples 6 (21% piperazine worm pyridine AVM suspending agent, 15ml/ mu), and preventive effect is 97.19%.The 7th day formulation examples 4,6,7,9 preventive effect all are higher than the preventive effect of 10% piperazine worm pyridine suspending agent and the single agent of 1.8% AVM EC behind the medicine, show that two kinds of composite reagent synergy are obvious.
4, the various proportionings of pyridine of piperazine worm and emamectin-benzoate are to the field efficiency test of wheat aphid.
Test controlling object wheat aphid.With embodiment 3,5,8,10,12 totally five kinds of medicaments establish medicament contrast and blank clear water and contrast respectively to water processings of evenly spraying after the dilution.District's group arrangement at random between processing is handled three times for every kind and is repeated.1 day, 3 days and 7 days investigation number of pest behind medicine are calculated lethality and control efficiency respectively, and result of the test is as shown in table 3.
Table 4 different disposal is to the field test results (1d, 3d and 7d behind the medicine) of wheat aphid
Annotate: data are 3 repetition mean values in the table.
Can find out that from result of the test (seeing table 4) what the 1st, 3,7 day preventive effect was best behind the medicine is formulation examples 8 (11% piperazine worm pyridine emamectin benzoate suspending agent, 12ml/ mu), preventive effect is respectively to be 90.76%, 97.27%, 98.92%.The 7th day formulation examples 10 (8% piperazine worm pyridine emamectin-benzoate wetting powder behind the medicine; 10g/ mu) and embodiment 8 (11% piperazine worm pyridine emamectin benzoate suspending agent; 12ml/ mu) preventive effect all reaches more than 96%; Be higher than the preventive effect of the single agent of 10% piperazine worm pyridine suspending agent and 1.0% emamectin-benzoate EC far away, show that two kinds of composite reagent synergy are obvious.