CN101461359A - Method for preparing controlled release type nano pesticide - Google Patents
Method for preparing controlled release type nano pesticide Download PDFInfo
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- CN101461359A CN101461359A CNA2009100771022A CN200910077102A CN101461359A CN 101461359 A CN101461359 A CN 101461359A CN A2009100771022 A CNA2009100771022 A CN A2009100771022A CN 200910077102 A CN200910077102 A CN 200910077102A CN 101461359 A CN101461359 A CN 101461359A
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Abstract
The invention discloses a method of preparing moderated nm-grade pesticide, comprising: cutting and emulsifying water-insoluble pesticide, unsaturated monomers, crosslinking agent and surface active agent, obtaining fine solution, triggering copolymerization through initiator, forming nm-grade microcapsule on a surface of the pesticide, obtaining the moderated nm-grade pesticide. The method not only eliminates pesticide burst in the pesticide, but also increases pesticide loading factor, thereby reducing application times of the pesticide, reducing pressure on environment and increasing utilization factor of the pesticide.
Description
Technical field
The present invention relates to a kind of method for preparing controlled release type nano pesticide, particularly a kind of method of utilizing fine emulsion polymerization to prepare controlled release type nano pesticide.
Background technology
Traditional application method because of wind, Exposure to Sunlight, the agricultural chemicals that causes of drenching with rain runs off and decompose and reach 60%～90% usually, therefore sprays repeatedly, dosage is doubled and redoubled, and causes huge waste and harm.Be conceived to the improvement of existing pesticide species processing formulation and prescription, new purposes is developed in the improvement of physical and chemical performance and application process, and particular importance just seems.Agricultural chemicals is made by necessary dosage, in the specific time, arrived sustainedly and stably and need the place, to keep the pesticide slow-releasing agent of enough lasting period, can use agricultural chemicals economically, agricultural chemicals is reduced to bottom line to the pollution of environment, thereby be the main direction of pesticidal preparations development.Nowadays, the pesticide micro capsule technology has had certain development, but still comes with some shortcomings.As: the particle diameter of micro-capsule is excessive, and the agricultural chemicals load factor is low, and the problems such as releasing phenomenon of dashing forward is arranged.
By literature search, roll up the 2nd phase 73-75 " agricultural chemicals " February the 43rd in 2004; " Pesticide Science journal " 2006 the 8th volumes the 1st phase 77-82; Roll up the 1st phase 16-19 " Yunnan chemical " February the 34th in 2007; " Scientia Agricultura Sinica " 2007 40 volume the 12nd phase 2753-2758 etc. have reported and have utilized interfacial polymerization, be the wall capsule material with Lauxite, melamine resin etc., have prepared the microcapsules of decis, Avermectin, chlopyrifos.The microcapsules form that this method forms is better, envelop rate is high, but the average grain diameter of the drop that forms is bigger.Patent CN 92104615, US6113935 have reported the method for preparing the agricultural chemicals micro-capsule by carbamide in agricultural chemicals surface polycondensation.US 5160529 has reported the self-condensation by polyurethane, forms the micro-capsule of acetamide-group herbicides.The microcapsules of above-described these method preparations can play the effect of slowly-releasing, but because particle diameter is bigger, in use, relatively poor to the tack and the infiltration capacity of target.
2007 34 volumes of article " Beijing University of Chemical Technology's journal " the 4th phase 337-340 has reported SiO
2Be slow-released carrier, utilize overcritical investment to prepare Avermectin solid powder nano slow release agent, this powder particle diameter after aqueous dispersion is 200-500nm, this class preparation has sustained release performance, and particle diameter reaches nanoscale, still, still has the low shortcoming of load factor.Among 2007 24 volumes of article " polymer material science and engineering " the 2nd phase 35-38, utilized the micro emulsion polymerization to prepare pesticide micro capsule, though microcapsule diameter reaches nanoscale, need to add a large amount of emulsifier, and pesticide concentration has been low, preparation cost is higher.
Summary of the invention
The object of the invention provides a kind of method for preparing controlled release type nano pesticide.
The method for preparing controlled release type nano pesticide provided by the invention, be that non-water-soluble agricultural chemicals, unsaturated monomer, crosslinking agent and surfactant are made miniemulsion through emulsification pretreatment, cause combined polymerization by initator, obtain controlled release type nano pesticide provided by the invention.
Described method is applicable to various nonpolar agricultural chemicals, as different types of water-insoluble agricultural chemicals such as Fluoxastrobin, prochloraz, propiconazole, uniconazole P, alkene azoles alcohol, Triadimenol, dimethomorph, brassin lactones, paclobutrazol, ether chrysanthemum ester, chlorfenapyr, Avermectin, beta-cypermethrin, Cyhalothrin, carbosulfans.
In the described method, monomer is a kind of of ethene, propylene, styrene, methyl styrene, acrylic acid, acrylamide, acrylate (as methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, hydroxy-ethyl acrylate, butyl methacrylate, hydroxypropyl acrylate etc.), acrylonitrile, methacrylonitrile or vinyl pyrrolidone or several arbitrarily mixture that mixes with arbitrary proportion.
In the described method, crosslinking agent is how vinyl-based material, as: one or more any combinations of diacrylate fourth diester, divinylbenzene, GDMA, allyl methyl acrylic acid, ethylene glycol diacrylate, diacrylate butanediol ester, tetramethylene dimethacrylate, dimethacrylate DOPCP, adipic acid dimethylacrylate, dimethacrylate triethylene glycol, dimethacrylate tetraethylene glycol or trimethylolpropane.
In the described method, initator is organic peroxy classes such as inorganic peroxy classes such as potassium peroxydisulfate, ammonium persulfate, dibenzoyl peroxide, cumyl peroxide, di-cyclohexylperoxy di-carbonate, azo classes such as azodiisobutyronitrile, ABVN, K
2S
2O
8/ Cu
+, K
2S
2O
8-Fe
2+Deng one or more any combinations in the oxidoreduction class initator.
In the described method, surfactant is an alkylbenzenesulfonate, aliphatic alcohol sulfate, alkylphenol-formaldehyde resin polyoxy ethyl ether, phenethyl phenyl polyoxyethyl propyl ether, castor oil polyoxyethylene ether, alkylphenol polyoxyethylene, the alkyl phenyl phenol polyethenoxy ether, the alkylphenol-polyethenoxy polyethenoxy ether, alkyl phenyl phenol polyethenoxy polyethenoxy ether, bitter edible plant sulfonic acid and formaldehyde, 1,2-di-n-butyl naphthalene-6-sodium sulfonate, to methoxyl group fatty acyl amido benzene sulfonic acid sodium salt, lignosulfonates, the carboxymethyl cellulose salt class, alkylsulfonate, aliphatic alcohol sulfate, alkyl sulfate, oleate, dioctyl sulfosuccinate, in dibutyl naphthalene sulfonate or the peregal any one or several arbitrarily mixture that mixes with arbitrary proportion.
Wherein, the mass fraction of surfactant, water, unsaturated monomer, crosslinking agent and nonpolar agricultural chemicals is 0.01-10:10-95:0.01-20:0.01-20:0.001-20, preferred 0.2-5:70-95:0.1-20:0.1-15:0.005-15, more preferably 0.2-10:70-90:2-20:1-10:0.005-5.
In the described method, the time of described emulsification pretreatment is 10-50min; Described unsaturated monomer compound and crosslinking agent copolymerization time are 1-8h, and preferred proportion is 2-5h; Described unsaturated monomer and crosslinking agent carry out stirring reaction, and reaction temperature is 0-80 ℃, preferred room temperature-70 ℃.It is 0.01%-10%, preferred 0.01%-4% that the consumption of described initator accounts for described copolymerization system mass percent.
Fine emulsion polymerization provided by the invention at first is prepared into miniemulsion with emulsification pretreatments such as non-water-soluble agricultural chemicals, one or more monomers, crosslinking agent, emulsifier, by the initator initiated polymerization, obtains the pesticide nano micro-capsule then.The present invention utilizes fine emulsion polymerization, forms a series of nanoscale droplets, and similar nano-reactor makes solvent monomer and crosslinking agent etc. better to coat agricultural chemicals at the drop surface aggregate.The polymerization efficiency height of this method is easy to control, and water is continuous phase, and heat-transfer effect is good, and the nano pesticide particle diameter that makes is at 50～500nm.This method has not only been eliminated the prominent appearance of releasing phenomenon of agricultural chemicals in some carriers, and can effectively improve the load factor of agricultural chemicals, thereby reduces the spraying times of agricultural chemicals, reduces the pressure to environment, improves the availability of agricultural chemicals.
Embodiment
The method for preparing controlled release type nano pesticide provided by the invention, concrete steps are as follows:
1) surfactant is added to the water, mixes.
2) monomer, crosslinking agent and nonpolar agricultural chemicals are mixed.
3) with step 2) oil phase join the aqueous phase of step 1), violent high speed shear stirs, and obtains miniemulsion.
4) miniemulsion is joined have thermometer, in the four-hole boiling flask of magnetic agitation, reflux condensation mode and nitrogen protection, add the initator initiated polymerization, obtain controlled release type nano pesticide provided by the invention.
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment 1
1) 0.2g lauryl sodium sulfate (SDS) is dissolved in the 90g deionized water, obtains 0.22% emulsifier aqueous solution;
2) 1.5g methyl acrylate, 6.0g styrene, 1.0g diacrylate fourth diester, 1.2g Avermectin mix;
3) water and oil phase are mixed, ice-water bath high speed emulsification pretreatment 10min obtains miniemulsion;
4) then miniemulsion is joined the flask that condensing unit, stirring, nitrogen inlet, charge door are housed, behind the logical nitrogen 30min, keep adding 0.1g azodiisobutyronitrile initiated polymerization simultaneously under 65 ℃ of water-baths, keep polymerization 2h, obtaining mass percent is 1.2% avermectin nanometer capsule.
By scanning electron microscopic observation is even spheroid, and its average grain diameter is 60nm.Detecting (HPLC) its suspensibility by high performance liquid chromatography is 96%, and load factor reaches 94%.
Embodiment 2
1) with 0.6g alkylphenol-formaldehyde resin polyoxy ethyl ether (700
#) and 0.2g calcium dodecyl benzene sulfonate (500
#) be dissolved in the 80g deionized water, obtain the aqueous solution of 1.0% emulsifier;
2) 3.6g methyl methacrylate, 4.0g divinylbenzene, 8g styrene, 3.5g dimethomorph mix;
3) water and oil phase are mixed, emulsification pretreatment 10min obtains miniemulsion in the ice-water bath;
4) then miniemulsion is joined the flask that condensing unit, stirring, nitrogen inlet, charge door are housed, behind the logical nitrogen 30min, keep adding 0.1g azodiisobutyronitrile initiated polymerization simultaneously under 70 ℃ of water-baths, keep polymerization 4h, obtaining mass percent is 3.5% dimethomorph Nano capsule.
By scanning electron microscopic observation is even spheroid, and its average grain diameter is 75nm.Detecting (HPLC) its suspensibility by high performance liquid chromatography is 94%, and load factor reaches 93%.
Embodiment 3
1) with 5g phenethyl phenyl polyoxyethyl propyl ether (1600
#) be dissolved in the 70g deionized water, obtain 7.0% emulsifier aqueous solution;
2) 10.0g ethyl acrylate, 10.0g methyl styrene, 2.0g ethylene glycol diacrylate, molten the mixing of 2.8g ether chrysanthemum ester;
3) water and oil phase are mixed, emulsification pretreatment 30min obtains miniemulsion in the ice-water bath;
4) then miniemulsion is joined the flask that condensing unit, stirring, nitrogen inlet, charge door are housed, behind the logical nitrogen 30min, keep adding 0.2g potassium peroxydisulfate initiated polymerization simultaneously under 50 ℃ of water-baths, keep polymerization 4h, obtaining mass percent is 2.8% ether chrysanthemum ester Nano capsule.
By scanning electron microscopic observation is even spheroid, and its average grain diameter is 65nm.Detecting (HPLC) its suspensibility by high performance liquid chromatography is 92%, and load factor reaches 91%.
Embodiment 4
1) 0.8g castor oil polyoxyethylene ether (EL-40) is dissolved in the 75g deionized water with the 0.2g lauryl sodium sulfate, obtains the aqueous solution of 1.3% emulsifier;
2) 5.0g EMA, 10g methyl styrene, 2.0g allyl methyl acrylic acid, 5.0g chlorfenapyr mix;
3) water and oil phase are mixed, emulsification pretreatment 30min obtains miniemulsion in the ice-water bath;
4) then miniemulsion is joined the flask that condensing unit, stirring, nitrogen inlet, charge door are housed, behind the logical nitrogen 30min, keep adding 2g benzoyl peroxide initiated polymerization simultaneously under 50 ℃ of water-baths, keep polymerization 4h, obtaining mass percent is 5.0% chlorfenapyr Nano capsule.
By scanning electron microscopic observation is even spheroid, and its average grain diameter is 65nm.Detecting (HPLC) its suspensibility by high performance liquid chromatography is 91%, and load factor reaches 90%.
Embodiment 5
1) 0.5g alkylphenol-polyethenoxy polyethenoxy ether is dissolved in the 80g deionized water, obtains the aqueous solution of 0.6% emulsifier;
2) 3.4g butyl methacrylate, 10g styrene, 2.0g GDMA, 4.0g beta-cypermethrin mix;
3) water and oil phase are mixed, emulsification pretreatment 30min obtains miniemulsion in the ice-water bath;
4) then miniemulsion is joined the flask that condensing unit, stirring, nitrogen inlet, charge door are housed, behind the logical nitrogen 30min, keep adding 0.1g azodiisobutyronitrile initiated polymerization simultaneously under 70 ℃ of water-baths, keep polyase 13 h, obtaining mass fraction is 4.0% beta-cypermethrin Nano capsule.
By scanning electron microscopic observation is even spheroid, and its average grain diameter is 60nm.Detecting (HPLC) its suspensibility by high performance liquid chromatography is 95%, and load factor reaches 87%.
Embodiment 6
1) 0.5g alkylphenol-polyethenoxy polyethenoxy ether is dissolved in the 78g deionized water, obtains the aqueous solution of 0.6% emulsifier;
2) 4.5g methyl acrylate, 10.0g diacrylate fourth diester, 3.0g alkene azoles alcohol mix;
3) water and oil phase are mixed, emulsification pretreatment 40min obtains miniemulsion in the ice-water bath;
4) then miniemulsion is joined the flask that condensing unit, stirring, nitrogen inlet, charge door are housed, behind the logical nitrogen 30min, keep adding 4g benzoyl peroxide initiated polymerization simultaneously under 50 ℃ of water-baths, keep polymerization 5h, obtaining mass percent is 3.0% alkene azoles alcohol Nano capsule.
By scanning electron microscopic observation is even spheroid, and its average grain diameter is 65nm.Detecting (HPLC) its suspensibility by high performance liquid chromatography is 94%, and load factor reaches 90%.
Embodiment 7
1) 1.0g alkylphenol-polyethenoxy polyethenoxy ether is dissolved in the 85g deionized water, obtains the aqueous solution of 1.2% emulsifier;
2) 5.9g hydroxy-ethyl acrylate, 5.0g dimethacrylate DOPCP, 3.0g Fluoxastrobin mix;
3) water and oil phase are mixed, emulsification pretreatment 40min obtains miniemulsion in the ice-water bath;
4) then miniemulsion is joined the flask that condensing unit, stirring, nitrogen inlet, charge door are housed, behind the logical nitrogen 40min, under the room temperature, add 0.1g potassium peroxydisulfate/FeSO
4Initiated polymerization keeps polyase 13 h, and obtaining mass percent is 3.0% Fluoxastrobin Nano capsule.
By scanning electron microscopic observation is even spheroid, and its average grain diameter is 70nm.Detecting (HPLC) its suspensibility by high performance liquid chromatography is 92%, and load factor reaches 91%.
Embodiment 8
1) with 0.5g phenethyl phenyl polyoxyethyl propyl ether (1600
#) be dissolved in the 95g deionized water, obtain 0.5% emulsifier aqueous solution;
2) 1.0g methyl acrylate, 1.0g butyl methacrylate, 2.49g divinylbenzene, 0.005g brassin lactones mix;
3) water and oil phase are mixed, emulsification pretreatment 50min obtains miniemulsion in the ice-water bath;
4) then miniemulsion is joined the flask that condensing unit, stirring, nitrogen inlet, charge door are housed, behind the logical nitrogen 30min, keep adding 0.01g potassium peroxydisulfate initiated polymerization simultaneously under 50 ℃ of water-baths, keep polymerization 4h, obtaining mass percent is 0.005% brassin lactones Nano capsule.
By scanning electron microscopic observation is even spheroid, and its average grain diameter is 65nm.Detecting (HPLC) its suspensibility by high performance liquid chromatography is 94%, and load factor reaches 90%.
Claims (10)
1, a kind of method for preparing controlled release type nano pesticide is that nonpolar agricultural chemicals, unsaturated monomer, crosslinking agent, surfactant and water are made miniemulsion through emulsification pretreatment, causes copolyreaction by initator, obtains described controlled release type nano pesticide.
2, method according to claim 1 is characterized in that: described nonpolar agricultural chemicals is Fluoxastrobin, prochloraz, propiconazole, uniconazole P, alkene azoles alcohol, Triadimenol, dimethomorph, brassin lactones, paclobutrazol, ether chrysanthemum ester, chlorfenapyr, Avermectin, beta-cypermethrin, Cyhalothrin or carbosulfan.
3, method according to claim 1 is characterized in that: described unsaturated monomer is the unsaturated compound with radical reaction activity; Described crosslinking agent is many vinyl compounds.
4, method according to claim 3 is characterized in that: described unsaturated monomer is any one or the arbitrarily several mixture that mixes with arbitrary proportion in ethene, propylene, styrene, methyl styrene, acrylic acid, acrylamide, acrylate, acrylonitrile, methacrylonitrile or the vinyl pyrrolidone;
Described many vinyl compounds are any one or the arbitrarily several mixture that mixes with arbitrary proportion in diacrylate fourth diester, divinylbenzene, GDMA, allyl methyl acrylic acid, ethylene glycol diacrylate, diacrylate butanediol ester, tetramethylene dimethacrylate, dimethacrylate DOPCP, adipic acid dimethylacrylate, dimethacrylate triethylene glycol, dimethacrylate tetraethylene glycol or the trimethylolpropane.
5, method according to claim 4 is characterized in that: described acrylate is methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, butyl methacrylate, hydroxy-ethyl acrylate or hydroxypropyl acrylate.
6, according to the arbitrary described method of claim 1-5, it is characterized in that: described initator is potassium peroxydisulfate, ammonium persulfate, dibenzoyl peroxide, cumyl peroxide, di-cyclohexylperoxy di-carbonate, azodiisobutyronitrile, ABVN, K
2S
2O
8/ Cu
+Or K
2S
2O
8-Fe
2+In any one or arbitrarily several mixture that mixes with arbitrary proportion.
7, according to the arbitrary described method of claim 1-6, it is characterized in that: described surfactant is an alkylbenzenesulfonate, aliphatic alcohol sulfate, alkylphenol-formaldehyde resin polyoxy ethyl ether, phenethyl phenyl polyoxyethyl propyl ether, castor oil polyoxyethylene ether, alkylphenol polyoxyethylene, the alkyl phenyl phenol polyethenoxy ether, the alkylphenol-polyethenoxy polyethenoxy ether, alkyl phenyl phenol polyethenoxy polyethenoxy ether, bitter edible plant sulfonic acid and formaldehyde, 1,2-di-n-butyl naphthalene-6-sodium sulfonate, to methoxyl group fatty acyl amido benzene sulfonic acid sodium salt, lignosulfonates, the carboxymethyl cellulose salt class, alkylsulfonate, aliphatic alcohol sulfate, alkyl sulfate, oleate, dioctyl sulfosuccinate, in dibutyl naphthalene sulfonate or the peregal any one or several arbitrarily mixture that mixes with arbitrary proportion.
8, according to the arbitrary described method of claim 1-7, it is characterized in that: the mass fraction of surfactant, water, unsaturated monomer, crosslinking agent and nonpolar agricultural chemicals is 0.01-10:10-95:0.01-20:0.01-20:0.001-20, preferred 0.2-5:70-95:0.1-20:0.1-15:0.005-15.
9, method according to claim 8 is characterized in that: the mass fraction of surfactant, water, unsaturated monomer, crosslinking agent and nonpolar agricultural chemicals is 0.2-10:70-90:2-20:1-10:0.005-5.
10, according to the arbitrary described method of claim 1-9, it is characterized in that: the time of described emulsification pretreatment is 10-50 minute; The temperature of described copolyreaction is 0-80 ℃, preferred room temperature-70 ℃; The time of described copolyreaction is 1-8 hour, preferred 2-5 hour; It is 0.01%-10% that the consumption of described initator accounts for described copolymerization system mass percent, preferred 0.01%-4%.
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| CN107306942B (en) * | 2017-06-23 | 2021-03-19 | 中国农业科学院农业环境与可持续发展研究所 | Preparation method of controlled release type nano pesticide preparation |
| CN107258802A (en) * | 2017-08-08 | 2017-10-20 | 浙江禾本科技有限公司 | A kind of water-soluble agricultural composite Nano bactericide and preparation method thereof |
| CN111117412A (en) * | 2019-12-19 | 2020-05-08 | 周雯 | Film type plant antitranspirant |
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