CN1250075C - Aqueous nano pesticide suspension containing effective pesticidal component and its prepn process - Google Patents
Aqueous nano pesticide suspension containing effective pesticidal component and its prepn process Download PDFInfo
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- CN1250075C CN1250075C CN 03124704 CN03124704A CN1250075C CN 1250075 C CN1250075 C CN 1250075C CN 03124704 CN03124704 CN 03124704 CN 03124704 A CN03124704 A CN 03124704A CN 1250075 C CN1250075 C CN 1250075C
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Abstract
The present invention relates to an aqueous nanometer pesticide suspension containing an effective pesticidal component and a preparing method thereof, wherein the aqueous suspension comprises the following components in certain weight percentage: 1 to 20 percent of effective pesticidal component, 20 to 50 percent of nanometer inorganic material, 0 to 20 percent of solvent, 1 to 20 percent of surface-active agents, 1 to 5 percent of antifreezing agents, 0 to 5 percent of stabilizing agents, 0.1 to 2 percent of stiffening agents and 30 to 90 percent of water. The preparing method comprises the steps that a pesticide as the effective component is dissolved with the solvent and mixed with the surface-active agents and the nanometer inorganic material to obtain a uniform oil phase by stir, or the effective component and the surface-active agents are melted and mixed with the nanometer inorganic material to form the oil phase by stir, or water and the antifreezing agents are mixed after the effective component, the surface-active agents, the nanometer inorganic material are mixed, and a uniform water phase is formed; the oil phase is added to the water phase, or the water phase is added to the oil phase to form the aqueous suspension with good dispersion at normal temperature and by stirring in high velocity shearing. The present invention has the characteristics that the bioactivity of the pesticide can be enhanced effectively, the residue of the pesticide in crops and environment can be reduced, etc., and the present invention provides a novel method for the chemical protection of plants in nuisance free agriculture.
Description
Technical field the present invention relates to a kind of composition and method of making the same of pesticide nano preparation.
The background technology nanometer technology is a 21 century material science and the forward position focus of Condensed Matter Physics research, and its development has caused the very big concern of countries in the world.Nanometer technology is that the research yardstick is preparation, character and the application of material in 1 to 200 nanometer range, and it comprises 4 main aspects: 1. nano material; 2. nanometer dynamics; 3. nanobiology and Nano medication are learned; 4. nanoelectronics.Wherein nano material is the basis and the core of nanometer technology, is the emphasis and the focus of current domestic and international research.Because the granular of particle, thereby its many physical propertys have played special variation, produced the physicochemical property of numerous brilliances, people are applied to fields such as chemical industry, electronics, composite, pottery, biotechnology, medical science, agricultural, solidify enzyme as nano material, be used for food processing and brewing industry and biogas fermentation, can enhance productivity greatly; Use the nanometer film technology, can separate multiple nutrients and functional materials in the food; The phosphate ore that utilizes nanoprocessing, crushing technology to pulverize can be directly used in crops, can save the sulfuric acid that a large amount of preparing phosphate fertilizers are used; Food, cosmetics, health products are produced in all available nanometer technology processing of agricultural byproducts such as animal chopped cooked entrails of sheep bone, pearl, silk, tealeaves; Sulphur, copper compound etc. are machined to 1 micron following fineness through nanometer technology, add suitable adjuvants, just become the good sterilization agent; Utilize the catalysis technique of nanometer technology, can eliminate the agricultural chemicals and other pollutions that residue in fruit, vegetable surface, can also utilize light, water, oxygen etc. to produce sterilization pesticide, because photocatalysis technology can make water, oxygen etc. become the material with extremely strong redox ability, can kill bacteria, fungi and virus, this agricultural chemicals is suitable for green, organic food production very much.But in organic agricultural chemicals, also do not adopt nanometer technology so far, no pesticide nano preparation.
Summary of the invention technical problem to be solved by this invention is to utilize the special physicochemical property of nano material, is introduced in the agricultural chemicals, and providing a kind of is the nano pesticide water slurry and preparation method thereof of active ingredient with the insecticide.
Technical scheme of the present invention is: a kind of nano pesticide water slurry that contains insecticidal active ingredient, the percentage by weight that it is characterized in that each component is insecticidal active ingredient 1%-20%, nano inorganic material 1～20%, solvent 0%-20%, surfactant 1%-20%, antifreeze 1%-5%, stabilizing agent 0～5%, thickener 0.1%-2% and water 30%-90%.
Active ingredient of the present invention can be any the former medicine in organic phosphates (as basudin, Hostathion, pirimiphos-methyl, malathion, sumithion, chlopyrifos etc.), carbamates (as carbofuran, Bassa, carbaryl, unden, Mobucin etc.), chrysanthemum ester class (as cypermethrin, decis, allethrin, Permanone, sumicidin etc.), other insecticide (as desinsection list, fine, the sharp strength spy of bromine worm, cartap etc.).
Nano inorganic material of the present invention comprises titanium dioxide, silica, iron oxide, aluminium oxide, mix in the titanium dioxide etc. of metal ion any, and preferred inorganic material is titanium dioxide or the titanium dioxide that mixes metal ion.
The surfactant that the present invention selects for use has the mixture of oxirane-propylene oxide block copolymer, the salt of the condensation product of the cyclisation product of formaldehyde and polycyclic aromatic hydrocarbon compounds, polyacrylic salt, in molecule, contain the fatty acid of at least ten two carbon atoms or the condensation product of fatty amine and oxirane expoxy propane, glycerine, sorbierite, the condensation product of the fatty acid ester of sucrose and they and oxirane expoxy propane, the condensation product of fatty alcohol or induced by alkyl hydroxybenzene and oxirane expoxy propane and their sulphate or nitrate, naphthalene sulfonic acid-formaldehyde condensation product, the alkyl naphthalene sulfonic acid formaldehyde condensation products, castor oil polyoxyethylene ether, lignosulfonates, the alkylphenol polyoxyethylene phosphate, polyoxyethylene nonylphenol ether, the mixture of one or more in the alkylbenzenesulfonate etc.
The solvent of the dissolving active ingredient that the present invention selects for use, its physicochemical property is stable, water insoluble, flash-point is high, volatility is little, ordorless, low toxicity, cheapness, as various aromatic hydrocarbons or aliphatic hydrocarbon or alicyclic or lower alcohol or ketone etc.
Thickener of the present invention can be natural thickener, as xanthans or gum Arabic etc.; Or semisynthetic thickener, as cellulose methyl compound or starch derivatives etc.; Or synthetic thickener, as polyacrylate etc.Preferred thickening is an xanthans.
Stabilizing agent of the present invention is epoxychloropropane or epoxidized soybean oil or urea or tributyl phosphate etc.;
Antifreeze of the present invention is the dihydroxylic alcohols of propane diols or ethylene glycol and so on, or glycerine.Preferred antifreeze is an ethylene glycol.
Water of the present invention is deionized water.
The preparation method who contains the nano pesticide water slurry of insecticidal active ingredient of the present invention is: earlier the active ingredient insecticide is dissolved, mixes with surfactant, nano inorganic material with a small amount of solvent, stir and obtain even oil phase; Also active ingredient can be mixed with the surfactant fusion and with nano inorganic material, stirring obtains oil phase, also active ingredient, surfactant, nano inorganic material can be mixed, then water, antifreeze etc. is mixed, form the homogeneous water, under normal temperature and high speed shear stir, oil phase is joined water or water joins oil phase, form finely disseminated water slurry.Measure below product average grain diameter 100 nanometers that obtain with the particle size distribution test instrument.The mixing speed that the present invention selects is 200 rev/mins-10000 rev/mins; Mixing time is 3-20 minute.
The invention has the beneficial effects as follows: can improve the biologically active of organic agricultural chemicals, and reduce agricultural chemicals residual in crop and environment, help environmental protection.
Embodiment
The present invention will be described in more detail below by embodiment and test of pesticide effectiveness example.
Embodiment 1
Taking by weighing basudin 10.8 gram, castor oil polyoxyethylene ether (n=40) and be 12 grams, nano titanium oxide 2 grams, ethylene glycol 3 grams, epoxychloropropane 1 gram, xanthans 0.1 gram, deionized water mends to 100 grams.Also under agitation be sprayed in the nano titanium dioxide powder basudin, castor oil polyoxyethylene ether (n=40) mixing, add deionized water (xanthans is dissolved in wherein in advance), obtain product through the high speed shear stirring, mixing speed is 2000 rev/mins, and mixing time is 3 minutes.Record product average grain diameter 96 nanometers through the Ma Erwen particle size analyzer.
Embodiment 2
Pirimiphos-methyl 10.6 grams, castor oil polyoxyethylene ether (n=15) 12 grams, epoxidized soybean oil 5 grams, nano titanium oxide 2 grams, propane diols 3 grams, xanthans 0.1 gram, deionized water is mended to 100 grams.Process processing by embodiment 1 obtains product.Product average grain diameter 95 nanometers.
Embodiment 3
Chlorfenapyr 10.8 grams, polyoxyethylene nonylphenol ether (n=20) 10 grams, cyclohexanone 5 grams, nano titanium oxide 2 grams, xanthans 0.1 gram, deionized water are supplemented to 100 grams, obtain product by the processing of embodiment 1 process.Record product average grain diameter 98 nanometers.
Embodiment 4
Bassa 20.5 grams, castor oil polyoxyethylene ether (n=35) 15 grams, ethanol 10 grams, nano titanium oxide 4 grams, polyvinyl alcohol 0.2 gram, deionized water 65.1 grams obtain product by the processing of embodiment 1 process.
Embodiment 5
Take by weighing 3 gram titanium tetrachlorides in the three-necked bottle of lucifuge, slowly drip, stir while dripping with 50 gram absolute ethyl alcohols.After waiting to dropwise, add the former medicine of 10 gram pirimiphos-methyls, 8 gram epoxychloropropane add 100 gram distilled water again, place 60 ℃ water bath with thermostatic control to stir 6 hours three-necked bottle, and mixing speed 120-300 rev/min, still aging 12 hours of room temperature.Promptly get 160 gram emulsus nanometer pirimiphos-methyl preparations.
Embodiment 6
Carbosulfan 10.8 grams, epoxidized soybean oil 3 grams, Nonyl pheno polyoxy third rare ether (m=15, n=20) nano titanium oxide 2 grams of 10 grams, silver-doped ion, xanthans 0.1 gram, deionized water are supplemented to 100 grams, obtain product by the processing of embodiment 1 step.
By sample was stored 14 days at 54 ℃, to store 7 days down for 0 ℃, its stable physical property testing result sees Table 1.Its chemical stability measurement result sees Table 2.
Table 1
| Sample | Outward appearance | 54 ℃ of storages (14 days) | 0 ℃ of storage (7 days) | Average grain diameter |
| Embodiment 1 | White emulsion evenly can flow | White emulsion evenly can flow | White emulsion evenly can flow | 96 |
| Embodiment 2 | White emulsion evenly can flow | White emulsion evenly can flow | White emulsion evenly can flow | 95 |
| Embodiment 3 | White emulsion evenly can flow | White emulsion evenly can flow | White emulsion evenly can flow | 98 |
| Embodiment 4 | White emulsion evenly can flow | White emulsion evenly can flow | White emulsion evenly can flow | 98 |
| Embodiment 5 | White emulsion evenly can flow | White emulsion evenly can flow | White emulsion evenly can flow | 97 |
| Embodiment 6 | White emulsion evenly can flow | White emulsion evenly can flow | White emulsion evenly can flow | 92 |
Table 2
| Sample | Active constituent content (%) | ||
| Initially | 54 ℃ (14 days) | 0 ℃ (7 days) | |
| Embodiment 1 | 10.60 | 10.45 | 10.60 |
| Embodiment 2 | 10.25 | 10.01 | 10.22 |
| Embodiment 3 | 10.26 | 10.18 | 10.25 |
| Embodiment 4 | 20.16 | 19.85 | 20.05 |
| Embodiment 5 | 5.86 | 5.61 | 5.78 |
| Embodiment 6 | 10.22 | 9.98 | 10.20 |
Embodiment is carried out biological activity determination, result such as table 3.
The toxicity test result of table 3 embodiment
| Reagent agent | The examination worm | Virulence regression equation formula (Y=a+bx) | Correlation coefficient (r) | LC (mg/l) | RT |
| The fine 20%EC embodiment 4 Bassa 20%EC embodiment of embodiment 1 basudin 50%EC embodiment 2 pirimiphos-methyl 50%EC embodiment, 3 bromine worms 6 granville carbosulfan 20%EC | Mythimna separata mythimna separata sitophilus zea-mais sitophilus zea-mais mythimna separata mythimna separata rice green leafhopper rice green leafhopper mythimna separata mythimna separata | Y＝1.8025+1.8112x Y＝1.7823+1.6364x Y＝2.0161+2.4999x Y＝2.3582+2.009x Y＝1.1041+4.0933x Y＝2.6338+2.0106x Y＝-1.6859+6.3603x Y＝-1.2403+4.9376x Y＝1.8011+2.4378X Y＝2.1046+1.8605x | 0.9186 0.9416 0.9807 0.9162 0.9996 0.9498 0.9805 0.9907 0.9515 0.9438 | 58.26 92.54 15.62 20.65 8.95 15.03 11.25 18.36 20.52 35.69 | 1.59 1.00 1.32 1.00 1.68 1.00 1.63 1.00 1.74 1.00 |
Carry out the residual test of crop with embodiment 3 as test medicine, the experiment situation is as follows:
Subjects: a variety of Chinese cabbage
Test medicine: 10% chlorfenapyr suspending agent (recording content 10.50%), 10% chlorfenapyr nanometer formulation
Experimental technique:, convert water 20ml/m by using dosage (12a.i. gram/mu) in a variety of Chinese cabbage 6-8 leaf phase
2Even spraying is on a variety of Chinese cabbage, and respectively at sampling respectively with five point samplings the same day behind the spray medicine (1-2 hour usually, soup is done the back), 1,3,5,7 day, 5 strains are adopted in each every sub-district, fetches to leave and take 500 grams with vertical quartering behind the laboratory and shred for surveying.
Experimental result sees Table 4.
The residual result of the test of table 4
| Sample | Concentration (mg/kg) | Resolution ratio % | |
| Dispenser same day | Blank suspending agent | 12.7730 | / |
| Nanometer formulation | 12.6154 | / | |
| Second day | Blank suspending agent | 9.0542 | 29.1 |
| Nanometer formulation | 7.8541 | 37.7 | |
| The 4th day | Blank suspending agent | 7.9876 | 37.5 |
| Nanometer formulation | 5.0012 | 60.4 | |
| The 6th day | Blank suspending agent | 6.0046 | 53.0 |
| Nanometer formulation | 2.6540 | 79.0 | |
| The 8th day | Blank suspending agent | 4.9513 | 61.2 |
| Nanometer formulation | 0.3468 | 97.3 |
As can be seen from the test results, the present invention can reduce agricultural chemicals residual on crop preferably.
Claims (3)
1, a kind of nano pesticide water slurry that contains insecticidal active ingredient, the percentage by weight that it is characterized in that each component is insecticidal active ingredient 1%-20%, nano titanium oxide or mix the nano titanium oxide 1-20% of argent ion, solvent 0%-20%, surfactant 1%-20%, antifreeze 1%-5%, stabilizing agent 0～5%, thickener 0.1%-2% and water 30%-90%, described surfactant is a kind of in castor oil polyoxyethylene ether, the Nonyl pheno polyoxy third rare ether, and described thickener is xanthans or polyvinyl alcohol.
2, according to the described nano pesticide water slurry that contains insecticidal active ingredient of claim 1, it is characterized in that: described active ingredient insecticide is any the former medicine in basudin, pirimiphos-methyl, chlorfenapyr, the carbosulfan; Described solvent is a cyclohexanone; Described stabilizing agent is epoxychloropropane or epoxidized soybean oil; Described antifreeze is propane diols or ethylene glycol; Described water is deionized water.
3, a kind of as containing the preparation method of the nano pesticide water slurry of insecticidal active ingredient as described in claims 1, it is characterized in that: earlier with the active ingredient insecticide with a small amount of solvent dissolving, mix with surfactant, nano titanium oxide or the nano titanium oxide that mixes the argent ion, stirring obtains even oil phase; Or mix with active ingredient and surfactant fusion and with nano titanium oxide or the nano titanium oxide that mixes the argent ion, stirring obtains oil phase, or active ingredient, surfactant, nano titanium oxide or the nano titanium oxide that mixes the argent ion mixed, then water, antifreeze are mixed, form the homogeneous water, under normal temperature and high speed shear stir, oil phase is joined water or water joins oil phase, form finely disseminated water slurry, mixing time is 3-20 minute, and mixing speed is 200-10000 rev/min.
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| CN 03124704 CN1250075C (en) | 2003-07-30 | 2003-07-30 | Aqueous nano pesticide suspension containing effective pesticidal component and its prepn process |
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| CN 03124704 CN1250075C (en) | 2003-07-30 | 2003-07-30 | Aqueous nano pesticide suspension containing effective pesticidal component and its prepn process |
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| CN1250075C true CN1250075C (en) | 2006-04-12 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102027989B (en) * | 2010-12-31 | 2013-09-11 | 沙隆达集团公司 | High content chlorpyrifos suspending agent and preparation method thereof |
| CN102626084A (en) * | 2012-03-23 | 2012-08-08 | 河南农业大学 | Azoxystrobin nano-water suspending agent and its preparation method |
| CN103053601A (en) * | 2013-01-06 | 2013-04-24 | 中国检验检疫科学研究院 | Nano-grade hygienic insecticide and preparation method thereof |
| CN103583549A (en) * | 2013-11-14 | 2014-02-19 | 安徽淮化股份有限公司 | Nanometer type pesticide |
| CN104042626A (en) * | 2014-07-01 | 2014-09-17 | 李绍明 | Bactericidal and bacteriostatic agent |
| CN104430308B (en) * | 2014-11-04 | 2016-06-29 | 广西大学 | A kind of Nano medication preventing and treating Citrus Huanglongbing pathogen and preparation method thereof |
| CN104430396B (en) * | 2014-11-04 | 2016-06-29 | 广西大学 | A kind of Nano medication of the preventing and treating Citrus Huanglongbing pathogen suitable in blade spraying |
| CN109006850A (en) * | 2017-06-10 | 2018-12-18 | 广东中迅农科股份有限公司 | A kind of pyraclostrobin nanometer formulation and preparation method thereof |
| CN110973152A (en) * | 2019-11-12 | 2020-04-10 | 南京华洲药业有限公司 | High-efficiency cypermethrin nano water aqua and preparation method and application thereof |
| CN111616156A (en) * | 2020-07-20 | 2020-09-04 | 硅羿科技（上海）有限公司 | Abamectin and spinosad nano suspending agent and preparation method thereof |
| CN113785837A (en) * | 2021-08-14 | 2021-12-14 | 广东中迅农科股份有限公司 | Acaricidal composition |
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Assignee: HAILI GUIXI CHEMICAL PESTICIDES CO.,LTD. Assignor: HUNAN Research Institute OF CHEMICAL INDUSTRY Contract fulfillment period: 2008.11.5 to 2008.11.4 Contract record no.: 2008360000054 Denomination of invention: Aqueous nano pesticide suspension containing effective pesticidal component and its prepn process Granted publication date: 20060412 License type: Exclusive license Record date: 20081106 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.11.5 TO 2008.11.4; CHANGE OF CONTRACT Name of requester: HAILI GUIXI CHEMICAL PESTICIDES CO., LTD. Effective date: 20081106 |
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Assignee: HAILI GUIXI CHEMICAL PESTICIDES CO.,LTD. Assignor: HUNAN Research Institute OF CHEMICAL INDUSTRY Contract fulfillment period: 2008.11.5 to 2013.11.4 Contract record no.: 2008360000054 Denomination of invention: Aqueous nano pesticide suspension containing effective pesticidal component and its prepn process Granted publication date: 20060412 License type: Exclusive license Record date: 20081106 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.11.5 TO 2013.11.4; CHANGE OF CONTRACT Name of requester: HAILI GUIXI CHEMICAL PESTICIDES CO., LTD. Effective date: 20081106 |
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