CN101803599B - Method for preparing biological pesticide spinosad microcapsule preparation - Google Patents
Method for preparing biological pesticide spinosad microcapsule preparation Download PDFInfo
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- CN101803599B CN101803599B CN201010142711A CN201010142711A CN101803599B CN 101803599 B CN101803599 B CN 101803599B CN 201010142711 A CN201010142711 A CN 201010142711A CN 201010142711 A CN201010142711 A CN 201010142711A CN 101803599 B CN101803599 B CN 101803599B
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Abstract
The invention relates to a method for preparing biological pesticide spinosad microcapsule preparation, which comprises preparation of urea-formaldehyde prepolymer solution, preparation of spinosad mixture solution and preparation of spinosad microcapsule. The microcapsule preparation technique is simple and convenient, easy to control, stable in reaction, less in auxiliary additive, low in production cost and suitable for industrialized production. The spinosad prepared by the method has high coating efficiency, is not damaged by rainwater or does not have degradation phenomenon after being irradiated by light, has long slow release period, and prolongs the pest control period, thus not only improving the control effect, but also reducing the environmental pollution.
Description
Technical field
The present invention relates to a kind of method for preparing biological pesticide spinosad microcapsule preparation, this method belongs to the preparation technique of pesticide field.
Background technology
Whole world crops are annual because of receiving the threat of damage by disease and insect, and its loss is approximately 1/3.At present, chemical pesticide is still accounting for most of market aspect prevention and the control damage by disease and insect.Along with chemical pesticide use in a large number, for a long time and repeatedly, it has not only caused huge pollution to soil, water body and atmosphere, and simultaneously, because the increase of residue of pesticide in the agricultural byproducts, this has also directly endangered human health.Therefore, exploitation safety, ecological sustainable development and environmentally friendly biopesticide get more and more people's extensive concerning.
Pleocidin is the another class broad spectrum pesticide efficiently after AVM; It has the safety of biopesticide and the quick validity of chemical synthetic pesticide concurrently; And environmentally friendly, insect is difficult for developing immunity to drugs, and becomes the emphasis of domestic development in recent years.The conventional pesticide formulation is owing to exist active ingredient to be prone under the effect of external environment, lose efficacy, and the lasting period is short, reduces the control efficiency of agricultural chemicals, and therefore, the development of agricultural chemicals need be concentrated the problem that solves pesticides new formulation, to improve the control efficiency of agricultural chemicals.
Summary of the invention
The technical problem that the present invention will solve provides a kind of method for preparing biological pesticide spinosad microcapsule preparation; The spinosad microcapsule preparation that this preparation method processes overcomes existing pleocidin preparation and receives light degradation easily; Its drug effect is reduced; Increase formulation rate, to the disadvantageous shortcoming of ecotope.
For solving the problems of the technologies described above, the technical scheme that the present invention adopted is:
A kind of method for preparing biological pesticide spinosad microcapsule preparation, this method comprises the steps:
The preparation of a, urea-formaldehyde prepolymer: take by weighing urea and be dissolved in 30%～40% formalin, the mol ratio of urea and formaldehyde is 1: 1～2.5, is stirred well to urea and dissolves fully; Regulate pH to 7.0～9.0, be warming up to 60 ℃～80 ℃, insulation reaction 0.5～3.5h; Generate the transparency liquid of toughness, add distilled water diluting then, the volume ratio of formalin and distilled water is 1: 1～3; Obtain stable urea-formaldehyde prepolymer aqueous solution, in this preparation process, the control reaction temperature is very crucial; When being lower than above-mentioned range temperature, prepolymerization reaction is incomplete, can form the performed polymer deposition; When being higher than above-mentioned range temperature, more side reaction can take place;
The preparation of b, pleocidin mixture solution: pleocidin is dissolved in the organic solvent; The solid-to-liquid ratio of pleocidin and organic solvent is: weight: volume=1g: 20～50mL; Stirring is fully dissolved pleocidin, adds the quality percentage composition again and be 0.5%～2% emulsifier solution, and emulsifier solution is 2～4: 1 with the volume of organic solvent ratio; 1000～2000r/min then; Stir 10～50min, capsule-core is fully disperseed, get final product after the clarification of phase solution forms stable O/W (oil/water) emulsion when mixing;
The preparation of c, spinosad microcapsule: under the room temperature said urea-formaldehyde prepolymer aqueous solution is joined in the said pleocidin mixture solution, said urea-formaldehyde prepolymer aqueous solution is 1～8 with the volume of organic solvent ratio that said dissolving pleocidin uses: 1,1000～2000r/min; Continue to stir 10～50min, performed polymer is dissolved in the dispersion medium of emulsion, reduce mixing speed to 500～900r/min then; Slowly the pH value of regulator solution makes pH value of solution reduce to 1.5～5.0 in 20～90min, behind the polycondensation reaction 1-3h; Adding quality percentage composition is 0.1%～1% dispersant solution, and dispersant solution is 1～2.5: 1 with the volume of organic solvent ratio, and is warming up to 40 ℃～70 ℃; Continue insulation reaction 2～5h; Cancellation is heated, and stops reaction, the pH to 6 of conditioned reaction product～8; Cooling is back, filtration is centrifugal, dry, promptly gets the spinosad microcapsule of this method preparation.In this preparation process, factors such as mixing speed, pH and reaction temperature all have certain influence to the particle diameter and the form of microcapsules.For example, the average grain diameter of microcapsules reduces along with the increase of mixing speed.When under acid catalysis, carrying out polycondensation reaction, joining day that should strict control acidulant is big or small with the pH value, if it is too fast to add sour speed, then gel occurs very soon and can't form microcapsules, can produce the autohemagglutination particle again too slowly.Therefore, progressively conditioned reaction pH value, and pH value should be controlled at the scope of above-mentioned requirements.Simultaneously, in the process that adds acidic catalyst, need to reduce mixing speed, otherwise originally the coating of formation is prone to smashed by high intensity turbulent, thereby influences the envelop rate of microcapsules.In addition, the temperature in reaction later stage should be higher than the temperature of initial reaction stage, but can not surpass the boiling point of capsule-core material and performed polymer.The above factor of controlling well simultaneously be make particle diameter little, be evenly distributed, the key point of ganoid microcapsules.
Among the above-mentioned preparation method, said organic solvent is selected from any one or more in benzinum, ethyl acetate, carrene, chloroform, benzene, toluene, chlorobenzene or the xylol.
Said emulsifier is selected from sorbitan trioleate, sodium lignin sulfonate, lauryl sodium sulfate, neopelex, dodecyl sodium sulfonate calcium, styrene-maleic anhydride copolymer, NP-10, polyvinyl alcohol, polymeric carboxylic salt, fatty acyl amido in methoxy benzenesulfonic acid sodium, gelatin, sodium carboxymethylcellulose, the naphthalene sulfonate any one or more.
Said dispersant is selected from any one or more in polyvinyl alcohol, phenylethylene-maleic anhydride copolymerization sodium salt, wooden sodium sulfonate, the Sodium Polyacrylate.
The acidic ph modifier that in above-mentioned preparation method, uses is selected from hydrochloric acid, hydrochloric acid-potassium chloride buffer solution, citric acid or phosphoric acid.The alkaline pH conditioning agent that uses is selected from triethanolamine, sodium hydroxide or ammoniacal liquor.
More than photomicroscope monitoring microencapsulation process is used in reaction, and differentiates the prepared microcapsule product.
Method of the present invention is utilized microencapsulation technology, active substance is coated on polymer-based material makes and its slow release improved drug utilization efficient, control and prolong drug deenergized period etc.The spinosad microcapsule preparation of this method preparation has following advantage:
(1) yield reaches more than 85%, and coating efficiency is high, and the slowly-releasing cycle is long.
(2) encapsulation process is simple, and is easy to operate, and stable reaction be easy to control, and equipment investment is few, and auxiliary additive is few, and production cost is low, and the market competitiveness is big, is suitable for suitability for industrialized production.
(3) control through microencapsulation makes the pleocidin rate of release controlled, can prolong its control phase to insect, improves effective rate of utilization, consolidates control efficiency.
(4) agricultural chemicals of preparation is not subject to rainwater destruction or is produced signs of degradation by irradiate light, can also effectively control phreatic pollution, reduces the influence to environment.
Do further detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.
Description of drawings
Fig. 1 is the microscope picture of spinosad microcapsule.
Embodiment
Embodiment 1
Accurately take by weighing 24.0g urea and add in the there-necked flask, measure 40mL 37% formalin, mixing speed is 1000r/min; Be stirred to till the whole dissolvings of urea, add triethanolamine and regulate pH to 8.0, be warmed up to 70 ℃ gradually; Keep above mixing speed and temperature-resistant, stop behind the reaction 1h, generate the transparency liquid of toughness; Then, add about 2 times to the distilled water diluting of formalin volume, obtain the stable urea-formaldehyde resin performed polymer aqueous solution.
Under the room temperature 1.0g pleocidin is dissolved in the 10mL chloroform fully; Add the 15mL benzinum again, fully behind the stirring and evenly mixing, add the quality percentage composition and be 0.7% lauryl sodium sulfate aqueous solution 70mL as emulsifier; 1000r/min stirs 10min, and capsule-core is fully disperseed and emulsification.Then, add above-mentioned urea-formaldehyde resin prepolymer solution 75mL, 1000～2000r/min; After continuing to stir 15min, reduce rotating speed, pump into HCl-KCl buffer solution with the constant flow pump constant speed to 700r/min; Conditioned reaction system pH to 2.0 in 1h behind the polycondensation reaction 1h, adds the quality percentage composition and is 0.4% polyvinyl alcohol 50mL as dispersant; After being warming up to 45 ℃ of curing cyst wall 2.5h, cancellation is heated, and stops reaction; With the pH to 7 of NaOH solution conditioned reaction product, cooling is back, filtration is centrifugal, dry, promptly gets the spinosad microcapsule of this method preparation.
The envelop rate of this spinosad microcapsule reaches more than 85%.Adopt microscopic examination prepared microcapsule product, as shown in Figure 1.
Embodiment 2
Accurately take by weighing 40.0g urea and add in the there-necked flask, measure 100mL 37% formalin, mixing speed is 1000r/min; Be stirred to till the whole dissolvings of urea, add triethanolamine and regulate pH to 8.0, be warmed up to 70 ℃ gradually; Keep above mixing speed and temperature-resistant, stop behind the reaction 1h, generate the transparency liquid of toughness; Then, add about 2 times to the distilled water diluting of formalin volume, obtain the stable urea-formaldehyde resin performed polymer aqueous solution.
Under the room temperature 1.5g pleocidin is dissolved in the 25mL chloroform fully; Add the 35mL benzinum again, fully behind the stirring and evenly mixing, add the quality percentage composition and be 0.7% styrene-maleic anhydride copolymer 120mL as emulsifier; 1000r/min stirs 10min, and capsule-core is fully disperseed and emulsification.Then, add above-mentioned urea-formaldehyde resin prepolymer solution 240mL, 1000～2000r/min; After continuing to stir 15min, reduce rotating speed, pump into 10% citric acid solution with the constant flow pump constant speed to 700r/min; Conditioned reaction system pH to 2.0 in 1h behind the polycondensation reaction 1h, adds the quality percentage composition and is 0.4% polyvinyl alcohol 75mL as dispersant; After being warming up to 45 ℃ of curing cyst wall 2.5h, cancellation is heated, and stops reaction; With the pH to 7 of NaOH solution conditioned reaction product, cooling is back, filtration is centrifugal, dry, promptly gets the spinosad microcapsule of this method preparation.
The envelop rate of this spinosad microcapsule reaches more than 85%.Adopt microscopic examination prepared microcapsule product.
Embodiment 3
Accurately take by weighing 36.0g urea and add in the there-necked flask, measure 60mL 37% formalin, mixing speed is 1000r/min; Be stirred to till the whole dissolvings of urea, add NaOH solution and regulate pH to 8.5, be warmed up to 80 ℃ gradually; Keep above mixing speed and temperature-resistant, stop behind the reaction 1h, generate the transparency liquid of toughness; Then, add about 2 times to the distilled water diluting of formalin volume, obtain the stable urea-formaldehyde resin performed polymer aqueous solution.
Under the room temperature 1.0g pleocidin is dissolved in the 30mL benzinum fully, fully behind the stirring and evenly mixing, adds the quality percentage composition and be 0.1% sodium dodecyl benzene sulfonate aqueous solution 120mL as emulsifier, 1000r/min stirs 10min, and capsule-core is fully disperseed and emulsification.Then, add above-mentioned urea-formaldehyde resin prepolymer solution 150mL, 1000～2000r/min; After continuing to stir 15min, reduce rotating speed, pump into HCl-KCl buffer solution with the constant flow pump constant speed to 700r/min; Conditioned reaction system pH to 2.5 in 20min behind the polycondensation reaction 1.5h, adds the quality percentage composition and is 0.4% polyvinyl alcohol 60mL as dispersant; After being warming up to 70 ℃ of curing cyst wall 3h, cancellation is heated, and stops reaction; With the pH to 8 of ammoniacal liquor conditioned reaction product, cooling is back, filtration is centrifugal, dry, promptly gets the spinosad microcapsule of this method preparation.
The envelop rate of this spinosad microcapsule reaches more than 85%.Adopt microscopic examination prepared microcapsule product.
Embodiment 4
Accurately take by weighing 40.0g urea and add in the there-necked flask, measure 100mL 37% formalin, mixing speed is 1000r/min; Be stirred to till the whole dissolvings of urea, add triethanolamine and regulate pH to 8.0, be warmed up to 60 ℃ gradually; Keep above mixing speed and temperature-resistant, stop behind the reaction 1h, generate the transparency liquid of toughness; Then, add about 3 times to the distilled water diluting of formalin volume, obtain the stable urea-formaldehyde resin performed polymer aqueous solution.
Under the room temperature 1.5g pleocidin is dissolved in 60mL ethyl acetate fully, fully behind the stirring and evenly mixing, adds the quality percentage composition and be 1% sorbitan trioleate 120mL as emulsifier, 1000r/min stirs 10min, and capsule-core is fully disperseed and emulsification.Then, add above-mentioned urea-formaldehyde resin prepolymer solution 240mL, 1000～2000r/min; After continuing to stir 15min, reduce rotating speed, pump into 10% citric acid solution with the constant flow pump constant speed to 500r/min; Conditioned reaction system pH to 2.0 in 1h behind the polycondensation reaction 1h, adds the quality percentage composition and is 0.4% Sodium Polyacrylate 75mL as dispersant; After being warming up to 45 ℃ of curing cyst wall 2h, cancellation is heated, and stops reaction; With the pH to 7 of NaOH solution conditioned reaction product, cooling is back, filtration is centrifugal, dry, promptly gets the spinosad microcapsule of this method preparation.
The envelop rate of this spinosad microcapsule reaches more than 85%.Adopt microscopic examination prepared microcapsule product.
Obviously, the above embodiment of the present invention only be for clearly the present invention is described and is done for example, and be not to be qualification to embodiment of the present invention.For the those of ordinary skill in affiliated field, on the basis of above-mentioned explanation, can also make other multi-form variation or change.Here can't give exhaustive to all embodiments.Everyly belong to the row that conspicuous variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
Claims (4)
1. a method for preparing biological pesticide spinosad microcapsule preparation is characterized in that this method comprises the steps:
The preparation of a, urea-formaldehyde prepolymer: take by weighing urea and be dissolved in 30%～40% formalin, the mol ratio of urea and formaldehyde is 1: 1～2.5, is stirred well to urea and dissolves fully; Regulate pH to 7.0～9.0, be warming up to 60 ℃～80 ℃, insulation reaction 0.5～3.5h; Generate the transparency liquid of toughness; Add distilled water diluting then, the volume ratio of formalin and distilled water is 1: 1～3, obtains stable urea-formaldehyde prepolymer aqueous solution;
The preparation of b, pleocidin mixture solution: pleocidin is dissolved in the organic solvent; The solid-to-liquid ratio of pleocidin and organic solvent is: weight: volume=1g: 20～50mL, and stir pleocidin is fully dissolved, add the quality percentage composition again and be 0.5%～2% emulsifier solution; Emulsifier solution is 2～4: 1 with the volume of organic solvent ratio; 1000～2000r/min stirs 10～50min then, gets final product after the clarification of phase solution forms stable O/W (oil/water) emulsion when mixing;
The preparation of c, spinosad microcapsule: under the room temperature said urea-formaldehyde prepolymer aqueous solution is joined in the said pleocidin mixture solution, said urea-formaldehyde prepolymer aqueous solution is 1～8 with the volume of organic solvent ratio that said dissolving pleocidin uses: 1,1000～2000r/min; Continue to stir 10～50min, performed polymer is dissolved in the dispersion medium of emulsion, reduce mixing speed to 500～900r/min then; Slowly the pH value of regulator solution makes pH value of solution reduce to 1.5～5.0 in 20～90min, behind the polycondensation reaction 1-3h; Adding quality percentage composition is 0.1%～1% dispersant solution, and dispersant solution is 1～2.5: 1 with the volume of organic solvent ratio, and is warming up to 40 ℃～70 ℃; Continue insulation reaction 2～5h; Cancellation is heated, and stops reaction, the pH to 6 of conditioned reaction product～8; Cooling is back, filtration is centrifugal, dry, promptly gets the spinosad microcapsule of this method preparation;
Wherein, said organic solvent is selected from any one or more in benzinum, ethyl acetate, carrene, chloroform, benzene, toluene, chlorobenzene or the xylol; Said emulsifier is selected from sorbitan trioleate, sodium lignin sulfonate, lauryl sodium sulfate, neopelex, dodecyl sodium sulfonate calcium, styrene-maleic anhydride copolymer, polymeric carboxylic salt, fatty acyl amido in methoxy benzenesulfonic acid sodium, the naphthalene sulfonate any one or more.
2. the method for preparing biological pesticide spinosad microcapsule preparation according to claim 1 is characterized in that said dispersant is selected from any one or more in polyvinyl alcohol, phenylethylene-maleic anhydride copolymerization sodium salt, wooden sodium sulfonate, the Sodium Polyacrylate.
3. the method for preparing biological pesticide spinosad microcapsule preparation according to claim 1 is characterized in that acidic ph modifier is selected from hydrochloric acid, hydrochloric acid-potassium chloride buffer solution, citric acid or phosphoric acid.
4. the method for preparing biological pesticide spinosad microcapsule preparation according to claim 1 is characterized in that the alkaline pH conditioning agent is selected from triethanolamine, sodium hydroxide or ammoniacal liquor.
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| CN102027904A (en) * | 2011-01-06 | 2011-04-27 | 北京燕化永乐农药有限公司 | Spinosad microcapsule suspending agent |
| CN102210315B (en) * | 2011-04-29 | 2013-06-19 | 中国农业大学 | Carbosulfan microcapsule suspending agent and preparation method thereof |
| CN102349509B (en) * | 2011-07-01 | 2013-07-31 | 华南农业大学 | Method for preparing lignin urea-formaldehyde pesticide microcapsule |
| CN104686561B (en) * | 2015-02-11 | 2017-04-05 | 武汉轻工大学 | Microcapsule formulation containing allyl group isosulfocyanate and preparation method and application |
| CN105230613A (en) * | 2015-11-06 | 2016-01-13 | 河北师范大学 | Preparation method of wheat chemical male gametocide microcapsule preparation |
| CN106366747B (en) * | 2016-08-29 | 2019-12-03 | 江苏金陵特种涂料有限公司 | A kind of photic preparation method for repairing microcapsules |
| CN107258777A (en) * | 2017-06-21 | 2017-10-20 | 北京明德立达农业科技有限公司 | A kind of seed treatment microcapsules suspension suspending agent of pyraclostrobin-containing and fluorine azoles bacterium aniline and preparation method thereof |
| CN110204260B (en) * | 2019-05-24 | 2021-01-01 | 武汉大学 | Ant-resistant concrete and preparation method thereof |
| CN111567530A (en) * | 2020-07-06 | 2020-08-25 | 济南中科绿色生物工程有限公司 | Spinosad insecticide and application thereof |
| CN116508760B (en) * | 2023-02-23 | 2024-03-29 | 河北兴柏农业科技股份有限公司 | Spinosad microcapsule powder and preparation method thereof |
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