Summary of the invention
An object of the present invention is to provide a kind of pesticide suspension concentrate that contains Difenoconazole.
Another object of the present invention provide a kind of contain the preparation method of Difenoconazole pesticide suspension concentrate and as bactericide in the application aspect the controlling plant diseases.For achieving the above object, technology contents disclosed by the invention is as follows:
A kind of pesticide suspension concentrate that contains Difenoconazole is characterized in that it is made up of following raw material:
Difenoconazole 40~50%,
Wetting dispersing agent 3.0~8.0%,
Thickener 0.1~5.0%,
Antifreezing agent 3~8.0%,
Defoamer 3.0%,
Water complements to 100%.
Wherein in the pesticide suspension concentrate suspension particle diameter at 2~5 μ m.
The pesticide suspension concentrate that the present invention is more preferably, it is made up of following raw material: 40.0% difenoconazole technical material, 3.5% alkylaryl polyoxyethylene ether phosphate, 0.16% thickener WJZ-04,3% defoamer, 8431,6.0% antifreeze glycols, water complements to 100%.Wherein in the pesticide suspension concentrate suspension particle diameter at 2~5 μ m.
Pesticide suspension concentrate of the present invention, wetting dispersing agent wherein is: alkylaryl polychloroprene APEO, calcium dodecyl benzene sulfonate, nonyl phenol formaldehyde resin APEO, calcium lignosulfonate, polyoxyethylene nonylphenol ether or alkylaryl polyoxyethylene ether phosphate.
Pesticide suspension concentrate of the present invention, thickener wherein is: xanthans XG, WJZ-04 or sodium carboxymethylcellulose (CMC).
Pesticide suspension concentrate of the present invention, antifreezing agent wherein is: glycerine or ethylene glycol; Defoamer is: organic silicone 8431.
The preparation method of pesticide suspension concentrate of the present invention is characterized in that being undertaken by following step:
(1) by the requirement of above-mentioned photograph prescription, former medicine Difenoconazole, wetting dispersing agent, antifreezing agent, defoamer and water mixing are sized mixing, pre-dispersed with high-shear emulsion machine;
(2) the gained slurry is moved into the sand milling jar, feeds cooling water and carry out sand milling, sand milling to the suspension particle diameter of material after 2~5 μ m reach 98% or more, filtration, standby;
(3) thickener is mixed with 1~2% the aqueous solution, joins in the slurry after the filtration, the qualified finished product that is is detected in the debugging back.
The present invention's preferred process of filling a prescription is as follows:
1 experiment material and method
1.1 experiment material
Difenoconazole technical material: white or off-white color pressed powder, effective component content 96.6%.
Wetting dispersing agent: alkylaryl polychloroprene APEO, calcium dodecyl benzene sulfonate, nonyl phenol formaldehyde resin APEO, fatty alcohol polyoxy ethyl ether, sodium metnylene bis-naphthalene sulfonate, polyoxyethylene nonylphenol ether, alkylaryl polyoxyethylene ether phosphate.
Thickener: xanthans XG, WJZ-04, CMC.
Antifreezing agent: glycerine, ethylene glycol.
Defoamer: 8431.
1.2 experimental instrument
Sand mill (0.1L, 0.3L, 1.5L), laboratory high speed shear mulser, NDJ-1 viscosimeter, PH meter, laboratory centrifuge, laser granulometry.
1.3 experimental technique
Adopt wet method sand milling ultramicro grinding.According to the prescription requirement, former medicine, auxiliary agent and water mixed sizes mixing, with high-shear emulsion machine pre-dispersed after, slurry is moved into the sand milling jar, feed cooling water and carry out sand milling, sand milling to the particle diameter of material qualified after, filter, standby.Thickener is mixed with the aqueous solution of different proportion, joins in the slurry after the filtration, the qualified finished product that is is detected in the debugging back.
1.4 the mensuration of aqueous suspension agent physicochemical property
The assay method of the dispersiveness of aqueous suspension agent, centrifugal stability, viscosity, pH value, pourability, suspensibility, cold storage stability, heat storage stability all carries out with reference to the suspending agent quality standard and the method for inspection in " formulations of pesticide processing book series " (third edition), and the Difenoconazole content analysis adopts liquid chromatography.
2 prescription screenings
2.1 the selection of wetting dispersing agent
The suspension system of pesticide suspension concentrate comes from a kind of thermodynamic unstable system between colloidal dispersion system and rough segmentation are loose.The particle diameter of aqueous suspension agent generally has several microns sizes, because particle diameter is very little, the surface free energy of particle is very big, easy adsorption-condensation between particle.In order to increase the stability of aqueous suspension agent; usually must add a certain amount of wetting dispersing agent; around dispersed phase particles, form firm diaphragm; or formation electric double layer; make the pesticide granules surface charging; mutually repel between charged particle and dispersion is tended towards stability, make it in storage process, not take place cohesion and knot end phenomenon.Even a small amount of layering is arranged, can become stable suspension system through shaking gently still, and have good in dispersiveness.
According to the physical and chemical performance of Difenoconazole and the research experience of similar products processing thereof, we select different nonionics and anion wetting dispersing agent to carry out screening (table 1)
Table 1 wetting dispersing agent is selected test (unit: %)
Project |
??1# |
??2# |
??3# |
??4# |
??5# |
??6# |
??7# |
??8# |
??9# |
Difenoconazole % |
??40.5 |
??40.5 |
??40.5 |
??40.5 |
??40.5 |
??40.5 |
??40.5 |
??40.5 |
??40.5 |
Sodium metnylene bis-naphthalene sulfonate |
??6 |
??4.5 |
??3.0 |
??2.5 |
|
|
|
|
|
Polyoxyethylene nonylphenol ether |
|
|
|
|
|
|
|
|
??6.6 |
The alkylaryl polyoxyethylene ether phosphate |
|
|
|
|
|
|
??3.5 |
|
|
Calcium dodecyl benzene sulfonate |
??2.0 |
??1.5 |
??2.5 |
|
??0.5 |
??1.0 |
|
|
|
Alkylaryl polyoxyethylene polyoxypropylene ether |
|
??2.0 |
|
??3.5 |
??2.5 |
??2.0 |
|
|
|
The nonyl phenol formaldehyde resin APEO |
??0.5 |
|
??1.0 |
|
??3.5 |
??2.0 |
|
|
|
Fatty alcohol polyoxy ethyl ether |
|
|
??2.5 |
|
|
|
|
??3.0 |
|
Project |
??1# |
??2# |
??3# |
??4# |
??5# |
??6# |
??7# |
??8# |
??9# |
Suspensibility |
??80 |
??85 |
??90 |
??89 |
??91 |
??85 |
??95 |
??88 |
??92 |
Dispersed |
Can |
Can |
Can |
Can |
Can |
Can |
Very |
Can |
Very |
Centrifugal stability |
Bad |
Very |
Bad |
Bad |
Bad |
Bad |
Very |
Bad |
Bad |
Heat storage stability |
Difference |
Difference |
Difference |
Difference |
Difference |
Difference |
Can |
Difference |
Can |
2.2 the selection of thickener
The viscosity of suspending agent is a key factor that influences the product bin stability.Viscosity is too little, product easily layering after placement a period of time, easy caking; Viscosity is too big, and it is serious that product is difficult for toppling over wall built-up, brings difficulty for processing and use.In order to improve the pourability of product, improve suspensibility and bin stability, must make product that a suitable viscosity is arranged.For this reason, according to the experience of developing suspending agent in the past, on the basis of 7# prescription, we screen several thickeners and have carried out stability test, find to select for use WJZ-04 thickener effect better, and it the results are shown in Table 2.
The centrifugal stability of preparation is best during from The selection result as can be known, with XG (0.4%) and WJZ-04.But preparation viscosity is higher when adding 0.4%XG, is difficult for flowing and sticking wall; When adding WJ-04, formulation flows is better, so the final thickener of determining WJZ-04 as 40% Difenoconazole SC, its consumption is 0.2%.
Table 2 thickener is selected test
The thickener kind |
Consumption |
Viscosity (mpa.s) |
Centrifugal stability |
??XG |
??0.15 |
??175 |
Bad |
??XG |
??0.4 |
??1400 |
Very |
??WJZ-04 |
??0.18 |
??1300 |
Bad |
??WJZ-04 |
??0.16 |
??1075 |
Excellent |
??WJZ-04 |
??0.12 |
??650 |
Bad |
??CMC |
??2.2 |
??370 |
Bad |
??CMC |
??5.0 |
??790 |
Very |
2.3 the selection of antifreezing agent
With water is the pesticide suspension concentrate of medium, and its prescription not only will be suitable for storing under the southern high-temperature condition and using, and will be suitable for storage and use under northern area cold.The former can add antifreezing agent less, and the latter must add an amount of antifreezing agent, to guarantee normal result of use.
We have done comparative trial to ethylene glycol, glycerine commonly used, and both are 6.0% by consumption.When test found to make antifreezing agent with glycerine, though aqueous suspension agent outward appearance no change during cold storage mobilely obviously descends, and there was not this situation in ethylene glycol.Therefore, this formulation selection ethylene glycol is as antifreezing agent, and its consumption is 6.0%.
2.4 the selection of defoamer
The production technology of agricultural chemicals suspension agent adopts the multistage sand milling superfine grinding of wet method more, and a large amount of air is brought and be dispersed into to the dispersion impeller of high speed rotating into atomic little bubble, and the suspending agent volume is expanded rapidly.These micro-bubbles not only can influence viscosity (mobile variation), metering and packing, and will reduce production efficiency significantly.If can not froth breaking, this may make the creeping type become dilatant fluid.So, in pharmaceutical formulation, add a certain amount of defoamer, and require defoamer good intermiscibility to be arranged with each component of preparation.This prescription is characterized in that with 8431 defoaming effect is good, and good with each component intermiscibility of preparation, consumption is few, dosage 3.0%, and price is low.
3 preferential determination of formula and checkings
The technical indicator of 3.140% Difenoconazole aqueous suspension agent
Table 4 technical indicator
Project |
Index |
Outward appearance |
White, can flow, thick liquid. |
Difenoconazole content, % |
40.0 ± 2.0 |
Suspensibility, % |
〉=90 |
The pH value |
5.0~8.0 |
Particle diameter (3~5 μ m) |
〉=90% |
Pourability |
Qualified |
Heat storage stability |
Qualified |
Cold storage stability |
Qualified |
3.2 preferential prescription is by intersection screening and heat storage stability test to former steps, obtained preferential prescription, its prescription is as follows: 40.0% difenoconazole technical material, 3.5% alkylaryl polyoxyethylene ether phosphate, 0.16% thickener WJZ-04,3% defoamer, 8431,6.0% antifreeze glycols, water complements to 100%.
Sample by preferential formulated detects its every technical indicator, its result such as table 4
Table 4 sample detection result
Sequence number |
The pH value |
Suspensibility (%) |
Particle diameter (μ m) |
Pourability |
Dispersed |
Cold storage stability |
Heat storage stability |
??1 |
??7.01 |
??96.0 |
??4.78 |
Very |
Very |
Qualified |
Qualified |
??2 |
??7.22 |
??95.9 |
??4.82 |
Very |
Very |
Qualified |
Qualified |
Sequence number |
The pH value |
Suspensibility (%) |
Particle diameter (μ m) |
Pourability |
Dispersed |
Cold storage stability |
Heat storage stability |
??3 |
??6.95 |
??96.3 |
??4.65 |
Very |
Very |
Qualified |
Qualified |
??4 |
??7.06 |
??95.8 |
??4.69 |
Very |
Very |
Qualified |
Qualified |
4. result
(1) obtained preferential prescription, its prescription is as follows:
40.0% difenoconazole technical material, 3.5% alkylaryl polyoxyethylene ether phosphate, 0.16% thickener WJZ-04,3% defoamer, 8431,6.0% antifreeze glycols, water complements to 100%.
(2) prescription detection effect is as follows:
Preparation is through low temperature and heat storage stability experiment, and outward appearance does not have obvious layering, favorable dispersibility in the water, and every index meets the suspending agent relevant criterion.
The present invention has following positive achievement:
(1) formulation of change Difenoconazole is a suspending agent, and during use, no dust harzard is to operator and Environmental security.
(2) formulation of change Difenoconazole can make the peasant more convenient when using this product, and is quick.
(3) suspending agent is dispersion medium with water, and the inflammable and drug injury problem that is produced by organic solvent can not take place.
(4) dispersiveness of suspending agent and plate-out ability are all relatively good, the suspensibility height, and the ability that sticks to the plant corpus surface is more intense, resistance of rainwater washing against, thereby drug effect significantly and also compares lastingly than wetting powder.
(5) change the Difenoconazole formulation, help the conservation of nature environment, alleviate the destruction that environment is caused.
Embodiment
In order to explain enforcement of the present invention more fully, provide following preparation method's embodiment.These embodiments only are to explain rather than limit the scope of the invention, raw materials used all have commercially available.
Embodiment 1
Prescription is formed: 40.0% Difenoconazole, and 3.5% alkylaryl polyoxyethylene ether phosphate, 0.16% thickener WJZ-04,3% defoamer, 8431,6.0% antifreeze glycols, water complements to 100%.
Embodiment 2
Prescription is formed: 45.0% Difenoconazole, and 5% alkylaryl polychloroprene APEO, 0.1% thickener xanthans XG, 3% defoamer, 8431,5.0% antifreeze glycols, water complements to 100%.
Embodiment 3
Prescription is formed: 50.% Difenoconazole, and 7% nonyl phenol formaldehyde resin APEO, 0.2% thickener WJZ-04,3% defoamer, 8431,4.0% antifreeze glycols, water complements to 100%.
Embodiment 4
Prescription is formed: 50.0% Difenoconazole, and 8% alkylaryl polychloroprene APEO, 4.5% thickener xanthans XG, 3% defoamer, 8431,6.0% antifreezing agent glycerine, water complements to 100%.
Embodiment 5
Prescription is formed: 50.0% Difenoconazole, and 5% polyoxyethylene nonylphenol ether, 5.0% thickener WJZ-04,3% defoamer, 8431,8.0% antifreezing agent glycerine, water complements to 100%.
The preparation method of embodiment 1-5:
(1) by the requirement of above-mentioned photograph prescription, former medicine Difenoconazole, wetting dispersing agent, antifreezing agent, defoamer and water mixing are sized mixing, pre-dispersed with high-shear emulsion machine;
(2) the gained slurry is moved into the sand milling jar, feeds cooling water and carry out sand milling, sand milling to the suspension particle diameter of material after 2~5 μ m reach 98% or more, filtration, standby;
(3) thickener is mixed with 1~2% the aqueous solution, joins in the slurry after the filtration, the qualified finished product that is is detected in the debugging back.
Embodiment 6 (Application Example)
Carry out efficacy testing by the obtained 40% Difenoconazole aqueous suspension agent of the embodiment of the invention 1 prescription respectively at these three areas of Hainan, Guangdong and Guangxi, the result is as follows:
Table 540% Difenoconazole SC prevents and treats sigatoka test of pesticide effectiveness statistical form (Hainan Province)
By table 5 as can be seen 40% Difenoconazole SC sigatoka is had the better prevention effect, continuation is better, 7 days preventive effect is 59.46%-72.21% behind the medicine for the third time, preventive effect that high concentration is handled and the suitable test medicine of contrast medicament in the test dose scope to crop safety, high, middle concentration is handled the generation that can control fragrant burnt leaf spot substantially, can use high concentration to handle so that reach better preventive effect when morbidity is heavier, test medicine can be applied on banana.
Table 640% Difenoconazole SC prevents and treats sigatoka test of pesticide effectiveness statistical form (Guangdong Province)
By table 6 as can be seen, each processing of 40% Difenoconazole aqueous suspension agent all has preventive effect preferably to sigatoka, remarkable with the equal difference of blank, but wherein 83.3mg/kg processing drug effect significantly is lower than contrast medicament (25% certainly will restrain missible oil) 100mg/kg processing, 104.2mg/kg handle suitable with contrast chemicals treatment drug effect, difference is not remarkable, and 125mg/kg handles drug effect and is significantly higher than the contrast chemicals treatment.
Preliminary observation in the process of the test, 3 of 40% Difenoconazole aqueous suspension agents supply the processing of examination concentration that the banana tender leaf is not seen poisoning, and the banana leaf growth is normal.
Table 740% Difenoconazole SC prevents and treats sigatoka test of pesticide effectiveness statistical form (Guangxi province)
By table 7 as can be seen, for examination 40% Difenoconazole aqueous suspension agent the burnt leaf spot of perfume (or spice) is had preventive effect preferably, when 125mg/kg handled, average preventive effect was higher than the contrast chemicals treatment, and difference is extremely remarkable.This medicament is to improve along with the increase of working concentration to the total trend of sigatoka preventive effect, and test period shows that it is to crop and other biological safety.
To the analysis showed that above drug effect is reported the result, gained Difenoconazole aqueous suspension agent of the present invention has preventive effect preferably to the burnt leaf spot of perfume (or spice), and drug effect all is higher than contrast medicament or suitable with the contrast medicament.
The present invention is after the preferred embodiment that describes in detail, being familiar with this technology personage can be well understood to, can carry out various variations and modification not breaking away under above-mentioned claim and the spirit, all foundations technical spirit of the present invention all belongs to the scope of technical solution of the present invention to any simple modification, equivalent variations and modification that above embodiment did.And the embodiment that the present invention also is not subject in the specification to be given an actual example.