CN102057897B - Chlorpyrifos microcapsule suspension and preparation method thereof - Google Patents
Chlorpyrifos microcapsule suspension and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a chlorpyrifos microcapsule suspension. The chlorpyrifos microcapsule suspension mainly comprises the following components in percentage by weight: 10 to 45 percent of chlorpyrifos, 5 to 20 percent of solvent, 1 to 10 percent of capsule wall material, 0.1 to 3 percent of lacquer, 2 to 5 percent of emulsifier, 3 to 5 percent of dispersant, 0 to 14 percent of auxiliary agent and 10 to 80 percent of water. The invention also discloses a preparation method of the chlorpyrifos microcapsule suspension. The chlorpyrifos microcapsule suspension has the advantages of reducing acute toxicity of raw medicaments, reducing environmental pollution and stimulation to people and livestock, improving prevention and control effect on insect damages such as a citrus tree scale insect and the like, greatly prolonging duration of a pesticide and reducing pesticide application frequency and agricultural cost. Since microcapsule technology is adopted and water is used as a dispersing medium in the chlorpyrifos microcapsule suspension, the chlorpyrifos microcapsule suspension is difficult to flame and explode, and can be safely and reliably used and transported.
Description
Technical field
The invention belongs to formulations of pesticide manufacture field, be specifically related to a kind of microcapsules that wrap up take the organic phosphates methidathion pesticide as capsule-core, take carbamide resin as capsule casing material and the chlorpyrifos microcapsule suspension made take water as basic dispersion medium and preparation method thereof.
Background technology
Methidathion (chlorpyrifos) chemical name: S-2,3-dihydro-5-methoxyl group-2-oxo-1,3,4-thiadiazoles-3-ylmethyl 0,0-Methyl disulfide substituted phosphate.Physicochemical property: clear crystal, fusing point 39-40 ℃, vapour pressure 2.5 * 10^ (4) Pa (20 ℃), density 1.51 (20 ℃), KowlogP=2.2, solvability water 200mg/L (25 ℃), ethanol 150, acetone 670, toluene 720, hexane 11, n-octyl alcohol 14 (g/L, 20 ℃), be hydrolyzed in the strong bronsted lowry acids and bases bronsted lowry, stable in neutral and little acid environment.
Methidathion belongs to high malicious insecticide, is a kind of organophosphorus insecticide of wide spectrum, have tag, stomach toxicity and osmosis, can infiltrate in the plant tissue, chewing type and sucking pest are all had killing effect.Especially scale insect there is special efficacy, the moth class is also had certain control action.Be applicable to prevent and treat various scale insects on the crops such as fruit tree, cotton, tea tree, vegetables, doublely eliminate aphis, the various pests such as aleyrodid and lepidoptera pest, 10～20 days longevities of residure.
The mandarin tree coccid is the important pests on the Orange Producing, and a red-spotted lizard class that causes harm mainly contains arrowhead scales, chaff scale, brown garden a red-spotted lizard etc., according to each geo-statistic then take arrowhead scales as main.Arrowhead scales harm Citrus leaf and fruit cause tree vigo(u)r weak, serious cause that deadwood or whole strain are dead.After fruit was caused harm by coccid, fruit colour was poor, and fruity is light, and the surface forms mottled, had a strong impact on outward appearance, fruit level and the sale of navel orange.
Along with the forbidding of national policy to acephatemet, parathion, parathion-methyl, nuvacron and 5 kinds of high malicious organophosphorous pesticides of phosphamidon, methidathion is used by people more and more as the special effect agent that kills coccid.Present domestic methidathion mainly is processed into missible oil and uses, and preparation belongs to the hypertoxic type agricultural chemicals.The conventional dosage forms such as missible oil are used certain shortcoming, as: cream preparation uses a large amount of organic solvent such as toluene, dimethylbenzene etc., not only wastes industrial resources, and serious environment pollution, and user's health is had harmful effect.
Summary of the invention
The present invention is a kind of chlorpyrifos microcapsule suspension that provides for the problems referred to above that overcome the prior art existence and preparation method thereof, the chlorpyrifos microcapsule suspension of the novel environment friendly that the present invention produces by microencapsulation technology, when keeping the methidathion control efficiency outstanding to coccid, can reduce employed organic solvent in the conventional formulation missible oil (toluene, dimethylbenzene etc.), environmentally friendly, and effectively reduce the toxicity of preparation, thereby improve user's safety.
To achieve these goals, the invention provides a kind of chlorpyrifos microcapsule suspension, be characterized in, formed by the component of following weight percentage:
Described total weight percent is 100%.
Above-mentioned chlorpyrifos microcapsule suspension, wherein, described solvent is selected from a kind of in toluene, dimethylbenzene, aliphatic solvent oil, cyclohexanone, methylated vegetable oil, mineral oil, aromatic solvent naphtha, 1-METHYLPYRROLIDONE, carrene, methyl-sulfoxide, the benzinum.
Above-mentioned chlorpyrifos microcapsule suspension, wherein, described emulsifier is selected from lauryl sodium sulfate, Nonyl pheno (NP series), alkylphenol-polyethenoxy polyethers and sulphate thereof or phosphoric acid fat, fatty alcohol-polyoxyethylene ether (AEO series), the polyoxyethylene nonylphenol ether phosphate, polycarboxylate, alkylphenol-polyethenoxy formaldehyde condensation products sulphate, alkylphenol polyoxyethylene formaldehyde condensation products sulphate phosphate, styrene phenol formaldehyde resin polyoxyethylene ether phosphate salt, styryl phenol polyethenoxy polyethenoxy ether, the alkyl naphthalene formaldehyde condensate sulfonates, the dialkyl succinylsuccinate sulfonated ester, this coils SPAN, being used in combination more than two kinds or three kinds among the tween TWEEN.
Above-mentioned chlorpyrifos microcapsule suspension, wherein, described dispersant is selected naphthalenesulfonic acid-formaldehyde condensate, triphenyl vinyl phenol polyethenoxy ether class and derivative eater, fatty alcohol polyethenoxy ether class, the alkylphenol polyoxyethylene class, macromolecule EO-PO block copolymer, lignosulfonates, alkylphenol-polyethenoxy formaldehyde condensation products sulphate, alkylphenol polyoxyethylene formaldehyde condensation products sulphate phosphate, styrene phenol formaldehyde resin polyoxyethylene ether phosphate salt, styryl phenol polyethenoxy polyethenoxy ether, the alkyl naphthalene formaldehyde condensate sulfonates, macromolecule is dredged a dress copolymer of type, being used in combination more than two kinds or three kinds in the polymerization of carboxylic acid salt.
Above-mentioned chlorpyrifos microcapsule suspension, wherein, described protection glue is selected from a kind of in polyvinyl alcohol, gelatin, gum Arabic, the xanthans.
Above-mentioned chlorpyrifos microcapsule suspension, wherein, described cyst material is carbamide resin, is to be made by interface polymerization reaction by isocyanate-monomer and polyalcohol or polyamine; Isocyanates comprises: TDI toluene di-isocyanate(TDI), pure MDI4,4-methyl diphenylene diisocyanate, the many phenyl of polymeric MDI are methylene polyisocyanates, PAPI polyphenyl polymethylene polyisocyanates etc. repeatedly.
Above-mentioned chlorpyrifos microcapsule suspension, wherein, described adjuvant is selected from one or more the combination in antifreeze, viscosity modifier, PH conditioning agent, sterilization antiseptic, the defoamer; Wherein:
Described antifreeze is selected from a kind of of ethylene glycol, propane diols, glycerine, PEG400, isopropyl alcohol, urea, and it accounts for 3～10% of total weight percent;
Described viscosity modifier is selected from a kind of in xanthans, cellulose ether and derivative thereof, polyethylene glycol, polyvinyl alcohol, magnesium alumino metasilicate, bentonite, kaolin, diatomite, the attapulgite, and it accounts for 0.05%～3% of total weight percent;
Described pH acid-base modifier is selected from a kind of in glacial acetic acid, hydrochloric acid, ammoniacal liquor, monoethanolamine, the diethylenetriamine, and institute's expense is as the criterion in the stability range for the pH value with final products is adjusted to;
Described sterilization antiseptic is selected from a kind of in potassium sorbate, Sodium Benzoate, formaldehyde, the isothiazolinone, and it accounts for 0.1%～0.5% of total weight percent;
Described defoamer is selected from a kind of in silicon defoamer, polyethers defoamer, higher alcohols, tributyl phosphate, the polysiloxane defoamers, and it accounts for 0.5%～1.5% of total weight percent.
Above-mentioned chlorpyrifos microcapsule suspension, wherein, described water is deionized water or distilled water.
The preparation method of chlorpyrifos microcapsule suspension is characterized in, according to above-mentioned raw material components and ratio, may further comprise the steps:
Step 1: the former medicine of an amount of methidathion is dissolved in an amount of solvent, adds an amount of cyst material monomeric diisocyanate and stir, obtain oil phase;
Step 2: add in advance an amount of emulsifier and an amount of protection glue in water, stir, then add the pre-configured oil phase of step 1, the high speed homogenizing forms the stabilized oil-in-water emulsion;
Step 3: reducing speed of agitator, add cyst material monomer polyamine or polyatomic alcohol water solution and participate in interface polymerization reaction, is to keep 2 hours～24 hours under 30 ℃～80 ℃ the environment in reaction temperature, makes cyst material solidify encystation;
Step 4: after cyst material solidifies encystation fully, add an amount of pH acid-base modifier, be adjusted in the required pH value scope, add an amount of adjuvant, stir and namely make chlorpyrifos microcapsule suspension;
More than each step all under atmospheric pressure state, implement to finish.
The preparation method of above-mentioned chlorpyrifos microcapsule suspension, wherein, the granularity of the resulting methidathion micro-capsule suspension of described step 4 is controlled between 1um～50um.
The application of methidathion micro-capsule suspension is characterized in, is that 5%～45% methidathion micro-capsule suspension is watered Direct spraying and uses with content.
Because the present invention has adopted above technical scheme, the technique effect of its generation is obvious:
1, because the suspending agent of the tiny spherical shape microcapsules that micro-capsule suspension (CS) is comprised of the capsule-core that contains active substance and macromolecule cyst material, the capsule diameter of microcapsule suspending agent is generally 1～20 μ m, active substance in the capsule-core slowly discharges under the condition of control, to satisfy suitable preventive effect requirement.Spraying is used behind the microcapsule suspending agent dilute with water, and with respect to other formulations, it has the following advantages:
(1) because the control of active ingredient methidathion is discharged thereby the long lasting period is arranged; Reduce the number of times of dispenser
(2) active ingredient is wrapped in and has improved safety in the cyst wall, makes preparation reduce toxic grade;
(3) reduced by 30%～70% organic solvent use, thus more friendly to environment;
(4) methidathion belongs to organophosphorus insecticide, is wrapped in behind the capsule casing material that resolution ratio reduces greatly in environment;
(5) some unhappy smells and the skin irritation material can be effectively reduced;
(6) reduce because the loss that the steam volatilization brings active ingredient;
(7) minimizing is to the poisoning of crop;
2, many environmental factors such as light, heat, air, rainwater, soil, microorganism and other chemical substance have been suppressed behind the methidathion pesticide microencapsulation to the adverse effect of pesticide activity component, reduced the speed of volatilization, decomposition, oxidation, degraded and the loss of agricultural chemicals, thereby strengthened the stability of agricultural chemicals, enlarged the scope of application.
3, behind the methidathion pesticide microencapsulation, because capsule content is generally between 10%～45% in the microcapsules SC, all the other be WATER AS FLOW MEDIUM, and with the missible oil comparison, active ingredient concentrates on 30%～50% capsule at heart.Because the effect of suspending agent, adhesive force is strengthened, and has improved control efficiency.
4, because microcapsule formulations has the control releasability, high-toxic pesticide is low to be poisoned thereby can make, and reduces the acute toxicity of former medicine.Be processed into after the microcapsule formulations, the volatility of agricultural chemicals is subject to very large inhibition, and original peculiar smell is also masked, has reduced excitant to people and animals, to the pollution of environment with to the poisoning of crops, and preparation is also greatly alleviated the toxicity of fish.No matter namely to people and animals or ecotope, all safer reliable.
5, but its active ingredient is by the permeability manual control of cyst material behind the microencapsulation, and slow release speed can design in advance.Because the protection of capsule skin, the active ingredient degradation speed slows down, and the agricultural chemicals lasting period can prolong 3-10 times.Lasting period prolongs, and just can improve control efficiency, reduces spraying times, reduces agricultural cost.
6, behind the pesticide micro capsule, medium makes the organic solvents such as water rather than dimethylbenzene, thereby effectively reaches environmental contamination reduction and reduce the usage amount of organic solvent, environmental pollution fall cause minimum.And microcapsule formulations is nonflammable explosive take water as dispersion medium, transportation safety.
Embodiment
The present invention has adopted a kind of low cost, is convenient to methidathion microcapsule formulations preparation method and the process route of suitability for industrialized production.It is cyst material that the present invention adopts carbamide resin, prepare the methidathion micro-capsule suspension with the interfacial polymerization law technology, the prescription of this methidathion micro-capsule suspension forms as follows with weight percent content: methidathion 10～45%, solvent 5～20%, cyst material 1～10%, protection glue 0.1～3%, emulsifier 2～5%, dispersant 3～5%, adjuvant 0～14%, water 10～80%; The total weight percent of described each component is 100%.Wherein:
Described solvent is a kind of in toluene, dimethylbenzene, aliphatic solvent oil, cyclohexanone, methylated vegetable oil, mineral oil, aromatic solvent naphtha, 1-METHYLPYRROLIDONE, carrene, methyl-sulfoxide, the benzinum, preferred aromatic hydrocarbons solvent naphtha and dimethylbenzene.
Described emulsifier is selected lauryl sodium sulfate, Nonyl pheno (NP series), alkylphenol-polyethenoxy polyethers and sulphate thereof (or phosphoric acid fat), fatty alcohol-polyoxyethylene ether (AEO series), the polyoxyethylene nonylphenol ether phosphate, polycarboxylate, alkylphenol-polyethenoxy formaldehyde condensation products sulphate, alkylphenol polyoxyethylene formaldehyde condensation products sulphate phosphate, styrene phenol formaldehyde resin polyoxyethylene ether phosphate salt, styryl phenol polyethenoxy polyethenoxy ether, the alkyl naphthalene formaldehyde condensate sulfonates, the dialkyl succinylsuccinate sulfonated ester, this coils SPAN, being used in combination more than two kinds or three kinds among the tween TWEEN.
Described dispersant is selected naphthalenesulfonic acid-formaldehyde condensate, triphenyl vinyl phenol polyethenoxy ether class and derivative eater, fatty alcohol polyethenoxy ether class, the alkylphenol polyoxyethylene class, macromolecule EO-PO block copolymer, lignosulfonates, alkylphenol-polyethenoxy formaldehyde condensation products sulphate, alkylphenol polyoxyethylene formaldehyde condensation products sulphate phosphate, styrene phenol formaldehyde resin polyoxyethylene ether phosphate salt, styryl phenol polyethenoxy polyethenoxy ether, the alkyl naphthalene formaldehyde condensate sulfonates, macromolecule is dredged a dress copolymer of type, being used in combination more than two kinds or three kinds in the polymerization of carboxylic acid salt.
Described protection glue is selected from polyvinyl alcohol, gelatin, gum Arabic, xanthans, preferably polyethylene alcohol and xanthans.
Described cyst material is carbamide resin, is to be made by interface polymerization reaction by isocyanates and polyalcohol (perhaps polyamine); Isocyanates comprises: TDI toluene di-isocyanate(TDI), pure MDI4,4-methyl diphenylene diisocyanate, the many phenyl of polymeric MDI are methylene polyisocyanates, PAPI polyphenyl polymethylene polyisocyanates etc. repeatedly.
Described adjuvant is selected from one or more the combination in antifreeze, viscosity modifier, PH conditioning agent, sterilization antiseptic, the defoamer; Wherein:
Described antifreeze is selected from a kind of of ethylene glycol, propane diols, glycerine, PEG400, isopropyl alcohol, urea, and it accounts for 3～10% of total weight percent;
Described viscosity modifier is selected from a kind of in xanthans, cellulose ether and derivative thereof, polyethylene glycol, polyvinyl alcohol, magnesium alumino metasilicate, bentonite, kaolin, diatomite, the attapulgite, and it accounts for 0.05～3% of total weight percent;
Described pH acid-base modifier is selected from a kind of in glacial acetic acid, hydrochloric acid, ammoniacal liquor, monoethanolamine, the diethylenetriamine, and institute's expense is as the criterion in the stability range for the pH value with final products is adjusted to;
Described sterilization antiseptic is selected from a kind of in potassium sorbate, Sodium Benzoate, formaldehyde, the isothiazolinone, and it accounts for 0.1%～0.5% of total weight percent;
That described defoamer is selected from is silicone based, a kind of in the low-carbon alcohols, and it accounts for 0.5%～1.5%% of total weight percent.
Prescription provides according to the present invention raw material and ratio, methidathion microcapsule formulations of the present invention can prepare by following process route:
Step 1, the former medicine of methidathion is dissolved in an amount of solvent, adds an amount of isocyanates cyst material monomer oil phase that stirs;
Step 2, in water, add in advance emulsifier, protection glue stirs, and then adds pre-configured oil phase, the high speed homogenizing forms the stabilized oil-in-water emulsion;
Step 3, reduction rotating speed under the speed conditions that is fit to, add polyamine or polyatomic alcohol water solution and participate in interface polymerization reaction, and reaction temperature rises in the suitable interval, keep a period of time to make cyst material curing encystation; The solidification temperature of the cyst material that polymerisation is controlled in the mentioned saccilar process of the present invention is at 30 ℃～80 ℃; Become capsule material required hardening time between 2 hours～24 hours; The cyst wall that forms is rule, homogeneous, and quality is hard;
Step 4, after becoming capsule material to solidify encystation fully, add the pH acid-base modifier, be adjusted in the required pH value scope, add an amount of dispersant, viscosity-controlling agent, defoamer, antifreeze, preservative etc., stir and namely make chlorpyrifos microcapsule suspension.
Technical process of the present invention is all implemented to finish under atmospheric pressure state.The water that adopts in this production technology is deionized water or distilled water.
Between the granularity control 1um～50um of the resulting methidathion micro-capsule suspension of the present invention, possessed the characteristics of pesticide suspension concentrate, can be watered Direct spraying and use.Methidathion micro-capsule suspension content of the present invention can change between 5%～45%, formulates different content according to its different purposes.
Methidathion microcapsules SC of the present invention also is simultaneously a kind of controlled formulation that is shaped with effect composition rate of release, therefore according to its purposes, determines that the thickness of softgel shell is controlled rate of release, to reach required effect.
For better explanation the technology of the present invention, below, describe the present invention in detail with reference to some embodiment and experimental condition, but described embodiment and condition are not meaned, should be understood to limitation of the present invention yet.Any technical staff in the art is appreciated that, within not departing from the desired spirit and scope of claims of the present invention, all can be used for a variety of modifications and variations, so protection scope of the present invention is with being as the criterion that claims scope is defined.
Embodiment one:
The former medicine of the methidathion of 20g (97%) is dissolved in the dimethylbenzene (commercial material) of 15g, and the toluene di-isocyanate(TDI) TDI(that then adds 4g is the product of largeization of Cangzhou TDI Co., Ltd for example) (oil phase) stirs; The emulsifier fatty alcohol-polyoxyethylene ether AEO-9(of 2.0g is for example changed very much the product of Co., Ltd in Nanjing), the 10% PVAC polyvinylalcohol aqueous solution of 10g adds in the deionized water of 27.9g and stirs evenly (water); The oil phase that configures to entering water and opening the high speed homogenizing, is formed stable O/W emulsion, record the average grain diameter 2.65 μ m of emulsion; Open to stir (keep 600 turn/min), then the emulsion that homogenizing is good is warming up to 75 ℃, the diamines that slowly adds simultaneously 0.4g, kept stable cyst material solidification temperature 3 hours, xanthans (2%) aqueous solution of the rear adding dispersant 5.0g of wooden sodium sulfonate, ethylene glycol 5.0g, 10g, the glacial acetic acid of 0.1g are transferred about pH value to 7, isothiazolinone compound bactericidal agent KF88 0.1g, silicone defoaming agent 0.3g stir, and namely make 20% chlorpyrifos microcapsule suspension.
Embodiment two,
The former medicine of the methidathion of 32g is dissolved in the C9 aromatic solvent naphtha (for example product of Nanjing petrochemical industry Co., Ltd) of 15g, and the polyphenyl polymethylene polyisocyanates PAPI(that then adds 3g is the product of Bayer A.G for example) with the methyl diphenylene diisocyanate MDI(of the 2g product of Yantai Wanhua Polyurethane Co., Ltd for example) stirring is oil phase; With emulsifier tween-60(of 2g product of Hai'an, Jiangsu petrochemical industry Co., Ltd for example), gum Arabic (5%) aqueous solution of 10g adds to stir evenly in the deionized water of 19g and is water; The oil phase that configures to entering water and opening the high speed homogenizing, is formed stable O/W emulsion, record the average grain diameter 10.58 μ m of emulsion; Open to stir (keep 700 turn/min), then the emulsion that homogenizing is good is warming up to 50 ℃, the triethanolamine that slowly adds simultaneously 0.4g, kept stable cyst material solidification temperature 8 hours, the phosphoric acid ester dispersant NP-P(of rear adding 3g for example Nanjing changes very much the product of company) propane diols of 8g, the Magnesiumaluminumsilicate of 10g (2%) aqueous solution, an amount of diluted hydrochloric acid aqueous solution are transferred about pH value to 6.5, preservative formaldehyde 0.08g, silicone defoaming agent 0.3g stir, and namely make 32% chlorpyrifos microcapsule suspension.
Embodiment three,
In the dimethylbenzene of 8g, the polyphenyl polymethylene polyisocyanates PAPI(that then adds 5g is the product of Bayer A.G for example with the former medicine of the methidathion of 40g (97%) heat of solution) with the toluene di-isocyanate(TDI) TDI(of the 0.9g product of largeization of Cangzhou TDI Co., Ltd for example) stirring is oil phase; The emulsifier NP-10(of 2.0g is for example changed very much the product of Co., Ltd in Nanjing), xanthans (2%) aqueous solution of 5g adds to stir evenly in the deionized water of 32g and is water; The oil phase that configures to entering water and opening the high speed homogenizing, is formed stable O/W emulsion, record the average grain diameter 45.2 μ m of emulsion; Open to stir (keep 800 turn/min), then the emulsion that homogenizing is good is warming up to 35 ℃, the diethylenetriamine that slowly adds simultaneously 0.6g, kept stable cyst material solidification temperature 22 hours, the metal carboxylate dispersant TERSPERSE2700(of rear adding 3.0g is the product of Huntsman company for example), the glacial acetic acid of the glycerine of 5.0g, 0.15g transfers about pH value to 7, preservative sodium benzoate 0.1g, silicone defoaming agent 0.5g stir, and namely makes 40% chlorpyrifos microcapsule suspension.
The key technical indexes of the present invention such as following table:
Toxicity of the present invention and drug effect result
1. toxicological test result
1.1. test method: tested material is 32% chlorpyrifos microcapsule suspension (U.N. Nantong Pesticide Formulation Development Center provides).40 of SPF level SD rats are got in the test of rat acute Oral toxicity, body weight 180-220 gram, male and female half and half; The rat acute percutaneous toxicity test is got 32 of SPF level SD rats, body weight 210-270 gram, male and female half and half.Press acute oral toxicity test among the GBl5670-1995 " agriculture chemical registration toxicology test method ", acute dermal toxicity test (HornShi method) is carried out.Rat acute Oral toxicity test establishes 100,215,464, four dosage groups of 1000mg/kg, calculates the amount of tested material according to the weight of animals, and per os is gavage on an empty stomach; The rat acute percutaneous toxicity test establishes 201,432,930, four dosage groups of 2000mg/kg, calculates the amount of tested material according to the weight of animals, and stoste directly is coated with skin, calculates respectively LD
50Value and 95% credibility interval.
1.2. result and conclusion: rat acute Oral toxicity result of the test sees Table 1
Table 1 rats death number and LD thereof
50Value
The rat acute percutaneous toxicity test the results are shown in Table 2
Table 2 rats death number and LD thereof
50Value
Can find out from above-mentioned table 1 and table 2: SD rat acute per os LD
50Female is 369mg/kg, and 95% credibility interval is 271-501mg/kg, and male is 430mg/kg, and 95% credibility interval is 295-626mg/kg; The SD rat acute is through skin LD
50Female male all greater than 2000mg/kg.Comprehensive SD rat male and female impatient property per os and acute through skin LD
50It is moderately toxic insecticide that value can determine 32% chlorpyrifos microcapsule suspension.
2. field efficacy result
2.1. field control effectiveness test and method
2.1.1 test material
Reagent agent: 32% chlorpyrifos microcapsule suspension, U.N. Nantong Pesticide Formulation Development Center provides; The contrast medicament: 40% methidathion missible oil, Jiangsu Tenglong Biological Pharmaceutical Co., Ltd. provides; For studying thing: mandarin tree; Controlling object: coccid (arrowhead scales Unaapis Yanonensis).
2.1.2 test method
Test arrangement is divided into and carried out in two years in the two places, Jiangsu and Zhejiang Provinces, and five processing are established in every test site, and every processing repeats four times, and every residential quarter five strain mandarin trees are arranged in minizone at random district's group.Respectively at 3 days and investigation in 14 days borer population alive behind the investigation insect population cardinal sum medicine before the medicine, calculate the insect population decline rate and proofread and correct preventive effect, make corresponding investigation on the poisoning situation of mandarin tree with on the impact of primary pest natural enemy simultaneously.Control efficiency is carried out significance of difference analysis, represent 5% significance level with English lower case.Test medicine consumption and numbering see Table 3.
Table 3 reagent agent experimental scheme
2.2 results and analysis
2.2.1 the result of the test of 2 years two places sees Table 4
Table 432% methidathion CS control mandarin tree coccid result of the test
2.2.2 analyze
Three different amounts of 32% chlorpyrifos microcapsule suspension were processed behind the medicine 3 days, and more than 70%, wherein the control efficiency of high consumption reaches more than 80%, is significantly higher than low consumption to the preventive effect of mandarin tree coccid, between middle consumption and the contrast medicament without significant difference; Behind the medicine 14 days, the control efficiency of high consumption reached more than 84%, and middle and high consumption is significantly higher than low consumption and contrast medicament.Under test dose to mandarin tree without poisoning, and the primary pest natural enemy had no adverse effects.
The present invention shows by above-mentioned test:
1, toxicology test result: 32% chlorpyrifos microcapsule suspension is moderately toxic insecticide, and conventional formulation missible oil mostly is high malicious insecticide, compares with it, and toxicity significantly reduces.
2, field control effectiveness test result, 32% chlorpyrifos microcapsule suspension has good control efficiency to the mandarin tree coccid, has preferably quick-acting, and lasting effect is remarkable.Under the test dose, along with consumption increases, control efficiency increases.
3, chlorpyrifos microcapsule suspension and the methidathion missible oil with dosage is suitable to the quick-acting control efficiency of mandarin tree coccid, and the holding effect insecticidal effect is better than missible oil.Can find out that methidathion can play certain long-acting drug that prolongs after making microcapsule suspending agent, thereby improve the effect of pesticide supplying effect.
Claims (7)
1. chlorpyrifos microcapsule suspension is characterized in that, mainly the component by following weight percentage forms:
Described total weight percent is 100%;
Wherein:
Described emulsifier is selected from lauryl sodium sulfate, the Nonyl pheno of NP series, alkylphenol-polyethenoxy polyethers and sulphate thereof or phosphoric acid fat, the fatty alcohol-polyoxyethylene ether of AEO series, the polyoxyethylene nonylphenol ether phosphate, polycarboxylate, styrene phenol formaldehyde resin polyoxyethylene ether phosphate salt, styryl phenol polyethenoxy polyethenoxy ether, the alkyl naphthalene formaldehyde condensate sulfonates, the dialkyl succinylsuccinate sulfonated ester, this coils SPAN, being used in combination more than two kinds or three kinds among the tween TWEEN;
Described dispersant is selected naphthalenesulfonic acid-formaldehyde condensate, triphenyl vinyl phenol polyethenoxy ether class and derivative eater, fatty alcohol polyethenoxy ether class, the alkylphenol polyoxyethylene class, macromolecule EO-PO block copolymer, lignosulfonates, styrene phenol formaldehyde resin polyoxyethylene ether phosphate salt, styryl phenol polyethenoxy polyethenoxy ether, the alkyl naphthalene formaldehyde condensate sulfonates, macromolecule is dredged a dress copolymer of type, being used in combination more than two kinds or three kinds in the polymerization of carboxylic acid salt;
Described cyst material is carbamide resin, is to be made by interface polymerization reaction by isocyanates and polyalcohol or polyamine.
2. chlorpyrifos microcapsule suspension according to claim 1, it is characterized in that described solvent is selected from a kind of in toluene, dimethylbenzene, aliphatic solvent oil, cyclohexanone, methylated vegetable oil, mineral oil, aromatic solvent naphtha, 1-METHYLPYRROLIDONE, carrene, methyl-sulfoxide, the benzinum.
3. chlorpyrifos microcapsule suspension according to claim 1 is characterized in that, described protection glue is selected from a kind of in polyvinyl alcohol, gelatin, gum Arabic, the xanthans.
4. chlorpyrifos microcapsule suspension according to claim 1 is characterized in that, described adjuvant is selected from one or more the combination in antifreeze, viscosity modifier, pH adjusting agent, sterilization antiseptic, the defoamer; Wherein:
Described antifreeze is selected from a kind of of ethylene glycol, propane diols, glycerine, PEG400, isopropyl alcohol, urea, and it accounts for 3～10% of total weight percent;
Described viscosity modifier is selected from a kind of in xanthans, cellulose ether and derivative thereof, polyethylene glycol, polyvinyl alcohol, magnesium alumino metasilicate, bentonite, kaolin, diatomite, the attapulgite, and it accounts for 0.05～3% of total weight percent;
Described pH acid-base modifier is selected from a kind of in glacial acetic acid, hydrochloric acid, ammoniacal liquor, monoethanolamine, the diethylenetriamine, and institute's expense is adjusted in the stability range for the pH value with final products;
Described sterilization antiseptic is selected from a kind of in potassium sorbate, Sodium Benzoate, formaldehyde, the isothiazolinone, and it accounts for 0.1%～0.5% of total weight percent;
Described defoamer is selected from a kind of in silicon defoamer, polyethers defoamer, higher alcohols, tributyl phosphate, the polysiloxane defoamers, and it accounts for 0.5%～1.5% of total weight percent.
5. chlorpyrifos microcapsule suspension according to claim 1 is characterized in that, described water is deionized water or distilled water.
6. the preparation method of chlorpyrifos microcapsule suspension is characterized in that, according to claim 1～5 each described raw material components and ratio, may further comprise the steps:
Step 1: the former medicine of methidathion is dissolved in the solvent, adds the cyst material monomeric diisocyanate and stir, consist of oil phase;
Step 2: add in advance emulsifier and protection glue in water, stir, then add the pre-configured oil phase of step 1, the high speed homogenizing forms the stabilized oil-in-water emulsion;
Step 3: reducing speed of agitator, add cyst material monomer polyamine or polyatomic alcohol water solution and participate in interface polymerization reaction, is to keep 2 hours～24 hours under 30 ℃～80 ℃ the environment in reaction temperature, makes cyst material solidify encystation;
Step 4: after cyst material solidifies encystation fully, add an amount of pH acid-base modifier, be adjusted in the required pH value scope, add adjuvant, stir and namely make chlorpyrifos microcapsule suspension;
More than each step all under atmospheric pressure state, implement to finish.
7. the preparation method of chlorpyrifos microcapsule suspension according to claim 6 is characterized in that, the granularity of the resulting methidathion micro-capsule suspension of described step 4 is controlled between 1um～50um.
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| CN102669192A (en) * | 2012-05-14 | 2012-09-19 | 沈阳东大迪克化工药业有限公司 | Matrine microcapsule suspension agent and preparation method thereof |
| CN103222463B (en) * | 2013-03-26 | 2014-10-15 | 中国农业科学院烟草研究所 | Method for preparing 2-amino-5-thiol-1, 3, 4-thiadiazole copper controlled-release microcapsule and prepared microcapsule |
| CN103704251B (en) * | 2013-12-10 | 2015-12-02 | 储娟英 | Missible oil containing chlorfenapyr and application |
| JP6615121B2 (en) * | 2014-04-29 | 2019-12-04 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing microcapsules |
| CN104430310A (en) * | 2014-11-25 | 2015-03-25 | 北京农学院 | Controlled-release pesticide suspending agent and preparation method thereof |
| CN104892123A (en) * | 2015-05-19 | 2015-09-09 | 潍坊友容实业有限公司 | A microcapsule suspension fertilizer having sterilizing effects for saline-alkali land and applications thereof in plantation of Chinese scholar tree |
| CN104876719A (en) * | 2015-05-19 | 2015-09-02 | 潍坊友容实业有限公司 | Bactericidal microcapsule suspension fertilizer for saline-alkali soil and application thereof in Caryopteris clandonensis planting |
| CN107125241A (en) * | 2017-04-01 | 2017-09-05 | 西南大学 | Cyflumetofen capsule sustained-release and preparation method thereof |
| CN107980770A (en) * | 2017-11-20 | 2018-05-04 | 联合国南通农药剂型开发中心（江苏省农药新剂型及新助剂工程技术研究中心、南通精细化工生产力促进中心） | A kind of microcapsule suspending agent of propargite and its preparation method and application |
| CN114208831B (en) * | 2021-12-29 | 2024-02-02 | 河北农信生物科技有限责任公司 | Pesticide microcapsule suspending agent and application thereof |
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