CN105145551B - A kind of moisture dissipates blade face affinity type nano pesticide sustained release agent and preparation method thereof - Google Patents
A kind of moisture dissipates blade face affinity type nano pesticide sustained release agent and preparation method thereof Download PDFInfo
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- CN105145551B CN105145551B CN201510578066.3A CN201510578066A CN105145551B CN 105145551 B CN105145551 B CN 105145551B CN 201510578066 A CN201510578066 A CN 201510578066A CN 105145551 B CN105145551 B CN 105145551B
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Abstract
Blade face affinity type nano pesticide sustained release agent and preparation method thereof is dissipated the invention discloses a kind of moisture.The preparation method of the pesticide slow-releasing agent comprises the following steps：The particle for loading agricultural chemicals is dispersed in degraded agent solution, centrifuged after vibration, solid is collected, you can obtain the slow-releasing pesticide preparation.The present invention makes the electrical charge rejection effect between load medicine particle surface group, increase particle using superficial degradation processing mode, solves particle buildup settlement issues in suspension formulation；The hydrophilic radical on the surface of load powder by degradation treatment, also there is the effect of surfactant, it is possible to decrease moisture dissipates the surface tension of sustained release agent agent, strengthens its enrichment in corps leaf surface, loss of the medicine in sprinkling process is reduced, target deposition, enrichment and dosage transfer efficiency is improved.In addition, the present invention can control to carry the surface topography of medicine ion by adjusting degradation time, the release of active ingredient in pesticide slow-releasing agent is further controlled, the effective rate of utilization of agricultural chemicals is improved.
Description
Technical field
Blade face affinity type nano pesticide sustained release agent and preparation method thereof is dissipated the present invention relates to a kind of moisture, belongs to pesticide technology
Field.
Background technology
Agricultural chemicals is mankind's preventing and treating agricultural disease, worm, grass, the plague of rats and the important means of vector insect.But, agricultural chemicals conventional dosage forms
Deposit and be lost in the problems such as serious, consumption of organic solvent is big in use, brought to human health and the environment depended on for existence
It is serious to threaten.During use, medicine is easily assembled on crop blade face to be slid, and causes more than 90% medicament to dissipate in soil, sky
Among gas and water body environment or residue in agricultural product.In addition, a large amount of organic solvents can also enter environment in medicament, this is not only easy
Cause environmental pollution, seriously endanger health and triggered serious food security with ecological environment problem in Pesticide use.Cause
This, develop some efficiently, low toxicity, low-residual, environment amenable pesticides new formulation it is significant.
Moisture dissipates pesticide slow-release agent formulation, is to solve low and environmental problem the important means of agricultural chemicals utilization rate.Agricultural chemicals moisture
Powder preparation have the advantages that reduction machine solvent load, use and store and transport safe ready, production in do not produce " three wastes ", complied with agriculture
Medicine low toxicity, environment-friendly main trend.As pesticide slow-releasing agent, carry and broken in powder by bag pesticide active ingredient by particle
Split, dissolve, hydrolyzing or slowly being discharged by the diffusion of cinclides, the medicine longevity of residure can be extended, reducing spraying times with applying
Dose, improves the utilization rate of agricultural chemicals, improves pressure of the agricultural chemicals to environment, and the pattern for changing particle by degradation treatment may be used also
With Drug controlled release.Carrying powder can avoid medicine from being contacted with the direct of external environment, so as to prevent many environmental factors
Such as the destruction of light, heat, air, rainwater, soil, microorganism and other chemical substances to agricultural chemicals, reduce agricultural chemicals decompose, oxidation,
Degraded and the speed being lost in, so as to enhance the stability of agricultural chemicals in itself.Further, since the coating function of particle can drop significantly
Low contact toxicity, toxicity on inhalation and phytotoxicity to people and animals.This water-based suspension agent improves the effective rate of utilization of agricultural chemicals, life
Thing activity and prevention effect, reduce Pesticide use amount, reduce residues of pesticides and environmental pollution.
But, suspension is between colloidal dispersion system and coarse dispersion system, and particle free surface energy is big, holds very much
Easily assemble and deposit clumps mutually during storage and use.In addition, suspension Mechanical instability system, carries medicine
Free settling can occur under gravity for grain, cause system layering, precipitation occur.Suspension stability is related to original before and after spray
The uniformity of medicine distribution, it is closely related with insecticidal effect.Accordingly, it would be desirable to solve moisture dissipate sustained release agent anti-agglomeration with it is suspending stabilized
Sex chromosome mosaicism.
The content of the invention
Blade face affinity type nano pesticide sustained release agent and preparation method thereof, the agriculture are dissipated it is an object of the invention to provide a kind of moisture
The preparation of medicine sustained release agent uses degradation process method, on the one hand can be strengthened interparticle by making load medicine particle surface group
Repulsive interaction, can increase dispersiveness, the suspension of suspension after the sustained release agent is dispersed in water；On the other hand, medicine is carried
Particle is after processing, and the particle of surface group can reduce the surface tension of suspending agent, is conducive to improving target during sprinkling
Deposition, enrichment and dosage transfer efficiency.
A kind of preparation method for pesticide slow-releasing agent that the present invention is provided, comprises the following steps：The particle point of agricultural chemicals will be loaded
It is dispersed in degraded agent solution, is centrifuged after vibration, collects solid, you can obtain the slow-releasing pesticide preparation.
In above-mentioned preparation method, the particle of every 5~400 milligrams of the load agricultural chemicals is dispersed in 1 milliliter described
Degrade agent solution in, concretely every 4~200 milligrams, 4~150 milligrams, 4~100 milligrams, 4~80 milligrams, 4~50 milligrams, 4
~20 milligrams, 20~200 milligrams, 20~150 milligrams, 20~100 milligrams, 20~80 milligrams, 20~50 milligrams, 50~200 millis
Gram, 50~150 milligrams, 50~100 milligrams, 50~80 milligrams, 80~200 milligrams, 80~150 milligrams, 80~100 milligrams, 100
~200 milligrams, 100~150 milligrams, 150~200 milligrams, 4 milligrams, 20 milligrams, 50 milligrams, 80 milligrams, 100 milligrams, 150 millis
Gram or the particle of 200 milligrams of the medicine be dispersed in 1 milliliter of the degraded agent solution.
In above-mentioned preparation method, the particle can be microcapsules or microballoon；The carrier material of the particle can be containing ester
The biodegradable high polymer material of key；The biodegradable high polymer material containing ester bond can be biological synthesizing polyester
Or chemical synthesis polyester, concretely it is following 1) or 2)：
1) biosynthesis polyester：Appointing in polyhydroxyalkanoate, cellulose, polyaminoacid, starch, chitin and collagen
It is a kind of；
2) chemical synthesis polyester：Poly butylene succinate, PGA (PGA), PLA (PLA), it is poly- (lactide-
Glycolide) copolymer (PLGA), poly- (lactide-caprolactone) copolymer (PLC), poly- (glycolide-caprolactone) copolymer
(PGC), poly- (glycolide-lactide-caprolactone) copolymer (PGLC), poly- (glycolide-polyglycol ether) copolymer (PEG-b-
PGA), PLE copolymer (PEG-b-PLA), poly- (own lactide-polyglycol ether) copolymer (PEG-
B-PCL), poly- (lactide coglycolide-polyglycol ether) copolymer (PEG-b-PLGA), poly- (lactide-caprolactone-poly- second two
Alcohol ether) copolymer (PEG-b-PLC), poly- (glycolide-caprolactone-polyglycol ether) copolymer (PEG-b-PGC), molecular weight can
For 5,000~500,000, concretely 5,000~80,000,10,000~100,000,80,000~150,000,5,000,
10,000th, 50,000,80,000,100,000 or 150,000；Wherein polyglycol ether segment molecule amount can be 200~20,000,
Concretely 2400.
In above-mentioned preparation method, the mass-volume concentration of the degraded agent solution can be 1~250 mg/ml, specifically
Can for 1~150 mg/ml, 1~100 mg/ml, 1~80 mg/ml, 1~50 mg/ml, 1~20 milligram/
Milliliter, 20~150 mg/mls, 20~100 mg/mls, 20~80 mg/mls, 20~50 mg/mls, 50~
150 mg/mls, 50~100 mg/mls, 50~80 mg/mls, 80~180 mg/mls, 80~100 milligrams/milli
Liter, 100~150 mg/mls, 1 mg/ml, 20 mg/mls, 50 mg/mls, 80 mg/mls, 100 milligrams/
Milliliter or 150 mg/mls；Solvent can be that volume ratio is 1：The body of the water of (1~100) and the mixed liquor of ethanol, water and ethanol
Product is than concretely 1：(1~100), 1：(1~50), 1：(1~20), 1：(1~10), 1：(10~100), 1：(10~50),
1：(10~20), 1：(20~100), 1：(20~50), 1：(50~100), 1：1、1：10、1：20、1：50 or 1：100.
In above-mentioned preparation method, the degradation agent can be acidic materials or alkaline matter；The acidic materials specifically may be used
For hydrochloric acid, sulfuric acid or niter cake；The alkaline matter concretely sodium hydroxide, potassium hydroxide, barium hydroxide, hydroxide
Calcium, sodium carbonate or sodium acid carbonate.
In above-mentioned preparation method, the speed of the vibration can be 50~300r/min, concretely 50~250r/min,
50~200r/min, 50~150r/min, 50~100r/min, 100~250r/min, 100~200r/min, 100~150r/
Min, 150~250r/min, 150~200r/min, 200~250r/min, 250r/min, 200r/min, 150r/min,
100r/min、50r/min；Time can be 1~200min, concretely 2~120min, 2~60min, 5~75min, 10~
80min, 15~90min, 30~100min, 40~105min, 45~120min, 2min, 5min, 10min, 15min, 30min,
40min, 45min, 60min, 75min, 80min, 90min, 100min, 105min or 120min；
The rotating speed of the centrifugation can be 1000~10000r/min, concretely 2000~10000r/min, 2000~
8000r/min, 2000~6000r/min, 2000~5000r/min, 2000~3000r/min, 3000~10000r/min,
3000~8000r/min, 3000~6000r/min, 3000~5000r/min, 5000~10000r/min, 5000~8000r/
Min, 5000~6000r/min, 6000~10000r/min, 6000~8000r/min, 8000~10000r/min, 2000r/
Min, 3000r/min, 5000r/min, 6000r/min, 8000r/min or 10000r/min；Time can be 2~15min, specifically
Can for 3~8min, 5~10min, 6~12min, 8~15min, 3min, 5min, 6min, 8min, 10min, 12min or
15min。
In above-mentioned preparation method, methods described is after solid is collected, in addition to solid is washed and dried
Step；The number of times of the washing can be 3~6 times, 3~5 times, 4~6 times, 3 times, 4 times, 5 times or 6 times；The drying is dry for freezing
It is dry.
Invention further provides a kind of pesticide slow-releasing agent prepared by above-mentioned preparation method.
Agricultural chemicals in above-mentioned pesticide slow-releasing agent can be insecticide, include but is not limited to：Rynaxypyr, AVM,
Chlorine fluorine worm chrysanthemum ester, emamectin benzoate, phoxim, imidacloprid etc..
The present invention has the advantages that：
1) present invention makes the electric charge row between load medicine particle surface group, increase particle using superficial degradation processing mode
Reprimand is acted on, and solves particle buildup settlement issues in suspension formulation.
2) hydrophilic radical on the surface of load powder in the present invention Jing Guo degradation treatment, the also work with surfactant
With, it is possible to decrease moisture dissipates the surface tension of sustained release agent agent, strengthens its enrichment in corps leaf surface, reduces medicine in sprinkling process
Loss, improve target deposition, enrichment and dosage transfer efficiency.
3) microballoon pattern can be controlled by adjusting the time (duration of oscillation) of degradation treatment in the present invention, medicine can be controlled
The release of thing active ingredient；Medicine is decomposed by material or slowly discharged by the diffusion of cinclides, can be extended minimum
In the sustained release time limit under valid density, effective rate of utilization, the bioactivity of agricultural chemicals are improved, reduce Pesticide use amount, reduce agriculture
Medicine is remained and environmental pollution；High agricultural chemicals low toxicity can also be made, reduce to people, animal and beneficial microorganism acute poisoning, carry
High security.
4) in the slow-releasing pesticide preparation for preparing of the present invention, it is microcapsules and microballoon to carry powder, particulate material be containing
The degradable high polymer material of ester bond, with nontoxic, environmentally degradable and absorption, the good feature of biocompatibility.
5) slow-releasing pesticide preparation for preparing of the present invention is stored with solid powder, and it is convenient to preserve transportation safety, is added water point
Plant leaf surface and the body surface of insect can be sprayed onto after dissipating, it is to avoid the use of organic solvent.
Brief description of the drawings
Fig. 1 is the photo of the ESEM of obtained microcapsule-type water-based suspension agent in embodiment 1.
Fig. 2 is the photo of the ESEM of obtained microcapsule-type water-based suspension agent in embodiment 2.
Fig. 3 is the photo of the ESEM of obtained microcapsule-type water-based suspension agent in embodiment 3.
Fig. 4 is the photo of the ESEM of obtained microcapsule-type water-based suspension agent in embodiment 4.
Fig. 5 is the photo of the ESEM of obtained microcapsule-type water-based suspension agent in embodiment 5.
Fig. 6 is the photo of the ESEM of obtained microcapsule-type water-based suspension agent in embodiment 6.
Fig. 7 is the photo of the ESEM of obtained microcapsule-type water-based suspension agent in embodiment 7.
Fig. 8 is the photo of the ESEM of obtained microcapsule-type water-based suspension agent in embodiment 8.
Fig. 9 is that (left figure is processing for the photo of the ESEM after microspheric water-based suspension agent before treatment in embodiment 11
The pattern of preceding microballoon, right figure is the microballoon pattern after processing).
Figure 10 is accumulative the releasing of obtained microcapsule-type water-based suspension agent in untreated microcapsules, embodiment 2, embodiment 4
Put curve.
The potential and oxygen element quality hundred on Figure 11 microcapsule-type water-based suspension agent surfaces made under different duration of oscillations
Divide the column diagram of ratio.
Figure 12 (is followed successively by untreated micro- glue from top to bottom for the GPC images of material in alkali process liquid under different duration of oscillations
Capsule, example 2, example 3, example 4).
Figure 13 is the turbidity versus time curve of obtained microcapsule-type water-based suspension agent under different duration of oscillations.
Figure 14 is the blade face decoction hold-up of obtained microcapsule-type water-based suspension agent under different duration of oscillations.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent used etc., unless otherwise specified, are commercially obtained in following embodiments.
What the particle of the load agricultural chemicals in following embodiments was prepared via a method which respectively obtains：
(1) the PLA microcapsules of Rynaxypyr：PLA is dissolved in dichloromethane and is used as oil phase (100mg/ml), chlorine
The water slurry of worm benzamide is used as interior aqueous phase (10wt%).First, interior aqueous phase is mixed into (v/v, 1/3) with oil phase, with super
Just emulsification obtains primary emulsion to sound wave cell crushing instrument ultrasound.Then, it is 1.0% primary emulsion to be poured into quantitative mass fraction
In the PVA aqueous solution (v/v, 1/5), in the holding vessel that fast film emulsifier unit is poured into after mechanical agitation pre-emulsification, with 0.08MPa nitrogen
Atmospheric pressure repeatedly presses through pre-emulsion micropore and is 7.0 microns of film, until obtaining the emulsion emulsion of uniform particle diameter.Finally, will be multiple
Emulsion is stirred overnight, and solvent is volatilized completely.By the microballoon after solidification by being collected by centrifugation, with water washing is distilled 3 times, liquid nitrogen is cold
After jelly, obtain carrying medicine hollow microsphere using freeze dryer freeze-drying 24h.
(2) the PLGA microballoons of AVM：Industrial PLA and AVM are dissolved in dichloromethane as oil phase (poly- breast
Sour 200mg/ml, AVM 100mg/ml), mass fraction is that the 0.1%PVA aqueous solution is used as outer aqueous phase.First, by aqueous phase with
The pre- stirring of oil phase mixing (v/v, 1/5) machinery.Then, mixed liquor is poured into the holding vessel of fast film emulsifier unit,
Pre-emulsion is crossed 7.0 microns of film repeatedly under 0.1MPa nitrogen pressure, until obtaining the emulsion of uniform particle diameter.
(3) spherex of AVM：Starch and AVM are dissolved in dichloromethane as oil phase, (starch 50mg/
Ml, avilamycin 100mg/ml) mass fraction be the 0.1%PVA aqueous solution be used as outer aqueous phase.First, aqueous phase is mixed with oil phase
The pre- stirring of (v/v, 1/5) machinery.Then, mixed liquor is poured into the holding vessel of fast film emulsifier unit, in 0.5MPa nitrogen pressures
Pre-emulsion repeatedly excessively by 2.0 microns of film under power, until obtaining the emulsion of uniform particle diameter.
(4) the poly butylene succinate microballoon of chlorine fluorine worm chrysanthemum ester：Poly butylene succinate and chlorine fluorine worm chrysanthemum ester is molten
In dichloromethane as oil phase (poly butylene succinate 50mg/ml, chlorine fluorine worm chrysanthemum ester 100mg/ml), mass fraction is
The 0.1%PVA aqueous solution is used as outer aqueous phase.First, aqueous phase and oil phase (v/v, 1/5) mixing machinery are stirred in advance.Then, it will mix
Liquid is poured into the holding vessel of fast film emulsifier unit, and pre-emulsion is iterated through 7.0 microns under 0.08MPa nitrogen pressures
Film, until obtaining the emulsion of uniform particle diameter.
(5) the PLGC microballoons of emamectin benzoate：Emamectin benzoate and PLGC are dissolved in dichloromethane as oil phase (PLGC50mg/ml, first
Tie up salt 50mg/ml), mass fraction is that the 0.1%PVA aqueous solution is used as outer aqueous phase.First, aqueous phase and oil phase (v/v, 1/5) are mixed
Close the pre- stirring of machinery.Then, mixed liquor is poured into the holding vessel of fast film emulsifier unit, the handle under 0.08MPa nitrogen pressures
Pre-emulsion iterates through 9.0 microns of film, until obtaining the emulsion of uniform particle diameter.
(6) the PEG-b-PLGA microcapsules of phoxim：PEG-b-PLGA is dissolved in dichloromethane and is used as oil phase
(100mg/ml), the water slurry of phoxim is used as interior aqueous phase (5wt%).First, interior aqueous phase is mixed into (v/v, 1/ with oil phase
3), with ultrasonic cell disruption instrument ultrasound, just emulsification obtains primary emulsion.Then, primary emulsion is poured into quantitative mass fraction
To be poured into the 1.0%PVA aqueous solution after (v/v, 1/8), mechanical agitation pre-emulsification in the holding vessel of fast film emulsifier unit,
Pre-emulsion pressed through repeatedly under 0.08MPa nitrogen pressures 9.0 microns of film, until obtaining the emulsion emulsion of uniform particle diameter.Finally,
Double emulsion is stirred overnight, solvent is volatilized completely.By the microballoon after solidification by being collected by centrifugation, with distillation water washing 3 times, liquid
After chilled nitrogen, obtain carrying medicine hollow microsphere using freeze dryer freeze-drying 24h.
(7) the polyhydroxyalkanoate microballoon of imidacloprid：Industrial PLA and AVM are dissolved in dichloromethane as
Oil phase (polyhydroxyalkanoate 50mg/ml, imidacloprid 50mg/ml), mass fraction is that the 0.1%PVA aqueous solution is used as outer aqueous phase.
First, aqueous phase is mixed into the pre- stirring of (v/v, 1/3) machinery with oil phase.Then, mixed liquor is poured into the storage of fast film emulsifier unit
Deposit in tank, pre-emulsion pressed through repeatedly with 0.08MPa nitrogen pressure 7.0 microns of pore membrane, until obtaining answering for uniform particle diameter
Emulsion.
Embodiment 1, prepare microcapsule-type water-based suspension agent
Microcapsule-type water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sodium hydroxide to be dissolved in into volume ratio：50 ethanol and the in the mixed solvent of water, it is 80 millis to be made into concentration
The sodium hydroxide solution of grams per milliliter；
(2) PLA (molecular weight the is 100,000) microcapsules for loading kernel load Rynaxypyr are distributed to step
(1) in obtained sodium hydroxide solution, the suspension that mass concentration is 4 mg/mls is obtained；
(3) suspension made from step (2) is shaken up into 15min in lower 100r/min vibrations.Last suspension 3000r/min
Centrifugation 5min collects product.Products therefrom is with water washing 3 times, freeze-drying.
The stereoscan photograph of micro-capsule manufactured in the present embodiment is as shown in Figure 1.
Embodiment 2, prepare microcapsule-type water-based suspension agent
Microcapsule-type water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sodium hydroxide to be dissolved in into volume ratio：50 ethanol and the in the mixed solvent of water, it is 80 millis to be made into concentration
The sodium hydroxide solution of grams per milliliter；
(2) PLA (molecular weight the is 100,000) microcapsules for loading kernel load Rynaxypyr are dispersed in step
(1) in sodium hydroxide solution made from, the suspension that mass concentration is 4 mg/mls is obtained；
(3) suspension B made from step (2) is shaken up into 30min in lower 100r/min vibrations.Last suspension 3000r/
Min centrifugations 5min collects product.Products therefrom is with water washing 3 times, freeze-drying.
The stereoscan photograph of micro-capsule manufactured in the present embodiment is as shown in Figure 2.
Embodiment 3, prepare microcapsule-type water-based suspension agent
Microcapsule-type water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sodium hydroxide to be dissolved in into volume ratio：50 ethanol and the in the mixed solvent of water, it is 80 millis to be made into concentration
The sodium hydroxide solution of grams per milliliter；
(2) PLA (molecular weight the is 100,000) microcapsules for loading kernel load Rynaxypyr are disperseed into sodium hydroxide
In solution, the suspension that mass concentration is 4 mg/mls is obtained；
(3) suspension made from step (2) is shaken up into 45min in lower 100r/min vibrations.Last suspension 3000r/min
Centrifugation 5min collects product.Products therefrom is with water washing 3 times, freeze-drying.
The stereoscan photograph of micro-capsule manufactured in the present embodiment is as shown in Figure 3.
Embodiment 4, prepare microcapsule-type water-based suspension agent
Microcapsule-type water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sodium hydroxide to be dissolved in into volume ratio：50 ethanol and the in the mixed solvent of water, it is 80 millis to be made into concentration
The sodium hydroxide solution of grams per milliliter；
(2) PLA (molecular weight the is 100,000) microcapsules for loading kernel load Rynaxypyr are dispersed in step
(1) in sodium hydroxide solution made from, the suspension that mass concentration is 4 mg/mls is obtained；
(3) suspension made from step (2) is shaken up into 60min in lower 100r/min vibrations.Last suspension 3000r/min
Centrifugation 5min collects product.Products therefrom is with water washing 3 times, freeze-drying.
The stereoscan photograph of micro-capsule manufactured in the present embodiment is as shown in Figure 4.
Embodiment 5, prepare microcapsule-type water-based suspension agent
Microcapsule-type water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sodium hydroxide to be dissolved in into volume ratio：50 ethanol and the in the mixed solvent of water, it is 80 millis to be made into concentration
The sodium hydroxide solution of grams per milliliter；
(2) PLA (molecular weight the is 100,000) microcapsules for loading kernel load Rynaxypyr are dispersed in step
(1) in sodium hydroxide solution made from, the suspension that mass concentration is 4 mg/mls is obtained；
(3) suspension made from step (2) is shaken up into 75min in lower 100r/min vibrations.Last suspension 3000r/min
Centrifugation 5min collects product.Products therefrom is with water washing 3 times, freeze-drying.
The stereoscan photograph of micro-capsule manufactured in the present embodiment is as shown in Figure 5.
Embodiment 6, prepare microcapsule-type water-based suspension agent
Microcapsule-type water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sodium hydroxide to be dissolved in into volume ratio：50 ethanol and the in the mixed solvent of water, it is 80 millis to be made into concentration
The sodium hydroxide solution of grams per milliliter；
(2) PLA (molecular weight the is 100,000) microcapsules for loading kernel load Rynaxypyr are dispersed in step
(1) in sodium hydroxide solution made from, the suspension that mass concentration is 4 mg/mls is obtained；
(3) suspension made from step (2) is shaken up into 90min in lower 100r/min vibrations.Last suspension 3000r/min
Centrifugation 5min collects product.Products therefrom is with water washing 3 times, freeze-drying.
The stereoscan photograph of micro-capsule manufactured in the present embodiment is as shown in Figure 6.
Embodiment 7, prepare microcapsule-type water-based suspension agent
Microcapsule-type water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sodium hydroxide to be dissolved in into volume ratio：50 ethanol and the in the mixed solvent of water, it is 80 millis to be made into concentration
The sodium hydroxide solution of grams per milliliter；
(2) PLA (molecular weight the is 100,000) microcapsules for loading kernel load Rynaxypyr are dispersed in step
(1) in sodium hydroxide solution made from, the suspension that mass concentration is 4 mg/mls is obtained；
(3) suspension made from step (2) is shaken up into 105min in lower 100r/min vibrations.Last suspension 3000r/
Min centrifugations 5min collects product.Products therefrom is with water washing 3 times, freeze-drying.
The stereoscan photograph of micro-capsule manufactured in the present embodiment is as shown in Figure 7.
Embodiment 8, prepare microcapsule-type water-based suspension agent
Microcapsule-type water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sodium hydroxide to be dissolved in into volume ratio：50 ethanol and the in the mixed solvent of water, it is 80 millis to be made into concentration
The sodium hydroxide solution of grams per milliliter；
(2) PLA (molecular weight is 100,000) microcapsules dispersion steps (1) of kernel load Rynaxypyr will be loaded
In obtained sodium hydroxide solution, the suspension that mass concentration is 4 mg/mls is obtained；
(3) suspension made from step (2) is shaken up into 120min in lower 100r/min vibrations.Last suspension 3000r/
Min centrifugations 5min collects product.Products therefrom is with water washing 3 times, freeze-drying.
The stereoscan photograph of micro-capsule manufactured in the present embodiment is as shown in Figure 8.
Embodiment 9, prepare microspheric water-based suspension agent
Microspheric water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sodium carbonate to be dissolved in into volume ratio：10 ethanol and the in the mixed solvent of water, it is 150 millis to be made into concentration
The sodium carbonate liquor of grams per milliliter；
(2) PLGA (molecular weight the is 80,000) microballoon for loading kernel load AVM is dispersed in into step (1) to be made
Sodium carbonate liquor in, obtain mass concentration be 100 mg/mls suspension；
(3) suspension made from step (2) is shaken up into 40min in lower 200r/min vibrations.Last suspension 10000r/
Min centrifugations 6min collects product.Products therefrom is with water washing 4 times, freeze-drying.
Embodiment 10, prepare microspheric water-based suspension agent
Microspheric water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 hydrochloric acid to be added dropwise in volume ratio：1 ethanol and the in the mixed solvent of water, it is 20 milligrams/milli to be made into concentration
The hydrochloric acid solution risen；
(2) spherex for loading kernel load AVM is dispersed in hydrochloric acid solution made from step (1), obtained
Mass concentration is the suspension of 150 mg/mls；
(3) suspension made from step (2) is shaken up into 5min in lower 50r/min vibrations.Last suspension 2000r/min speed
Degree centrifugation 15min collects product.Products therefrom is with water washing 3 times, freeze-drying.
Embodiment 11, prepare microspheric water-based suspension agent
Microspheric water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sodium acid carbonate to be dissolved in into volume ratio：20 ethanol and the in the mixed solvent of water, it is 50 millis to be made into concentration
Grams per milliliter sodium bicarbonate solution；
(2) poly butylene succinate (molecular weight is 50,000) microballoon of the efficient chlorine fluorine worm chrysanthemum ester of kernel load will be loaded
In sodium bicarbonate solution made from dispersion steps (1), the suspension that mass concentration is 80 mg/mls is obtained；
(3) suspension made from step (2) is shaken up into 80min in lower 150r/min vibrations.Last suspension 8000r/min
Centrifugation 3min collects product.Products therefrom is with water washing 6 times, freeze-drying.
Microcapsules made from the present embodiment before treatment after stereoscan photograph, as shown in figure 9, wherein left figure for processing
It is the scanning of the poly butylene succinate microballoon of the efficient chlorine fluorine worm chrysanthemum ester of undispersed load kernel load in step (2) before
The photo of Electronic Speculum, right figure is the photo of the ESEM of the microballoon obtained after above-mentioned processing.
Embodiment 12, prepare microspheric water-based suspension agent
Microspheric water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 calcium hydroxide to be dissolved in into volume ratio：50 ethanol and the in the mixed solvent of water, it is 1 milli to be made into concentration
The aqua calcis of grams per milliliter；
(2) PLGC (molecular weight the is 150,000) microballoon for loading kernel load emamectin benzoate is dispersed in made from step (1)
In aqua calcis, the suspension that mass concentration is 50 mg/mls is obtained；
(3) suspension made from step (2) is shaken up into 100min in lower 100r/min vibrations.Last suspension 5000r/
Min centrifugations 8min collects product.Products therefrom is with water washing 5 times, freeze-drying.
Embodiment 13, prepare microcapsule-type water-based suspension agent
Microcapsule-type water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 sulfuric acid to be added dropwise in being dissolved in volume ratio：100 water and the in the mixed solvent of ethanol, being made into concentration is
The sulfuric acid solution of 100 mg/mls；
(2) by load kernel load phoxim PEG-b-PLGA (molecular weight is 10,000, wherein polyglycol ether section
Molecular weight is that 2400) microcapsules are dispersed in sulfuric acid solution made from step (1), and it is 200 mg/mls to obtain mass concentration
Suspension；
(3) suspension made from step (2) is shaken up into 2min in lower 250r/min vibrations.Last suspension 3000r/min
Centrifugation 10min collects product.Products therefrom is with water washing 5 times, freeze-drying.
Embodiment 14, prepare microspheric water-based suspension agent
Microspheric water-based suspension agent is prepared in accordance with the following steps：
(1) it is 1 to be added on niter cake and be dissolved in volume ratio：50 water and the in the mixed solvent of ethanol, being made into concentration is
The sodium bisulfate of 150 mg/mls；
(2) the polyhydroxyalkanoate microballoon for loading kernel load imidacloprid is dispersed in hydrogen sulfate made from step (1)
In sodium solution, the suspension that mass concentration is 20 mg/mls is obtained；
(3) suspension made from step (2) is shaken up into 10min in lower 150r/min vibrations.Last suspension 6000r/min
Centrifugation 12min collects product.Products therefrom is with water washing 4 times, freeze-drying.
Embodiment 15, different degradation times carry the influence of medicine particle surface structure to agricultural chemicals
Duration of oscillation (i.e. degradation time) in embodiment 1- embodiments 8 in step (2) be respectively 0.25h, 0.5h,
0.75h, 1h, 1.25h, 1.5h, 1.75h and 2h, remaining is consistent.Different degradation times are investigated separately below to microcapsules
The influence of surface topography and structure.
(1) influence of the different degradation times to surface of microcapsule pattern and structure
The photo of the ESEM of the microcapsules prepared in embodiment 1- embodiments 8 as Figure 1-Figure 8, by Fig. 1-
Fig. 8 can be seen that by carrying out simple degradation treatment, surface of microcapsule polymer ester linkage breaking, microcapsules table to microcapsules
The pattern in face is also roughening.Processing time is longer, and surface of microcapsule micropore is more.In addition, the microballoon in embodiment 11 is in processing
The photo of front and rear ESEM by contrasting as shown in figure 9, found, by carrying out simple degradation treatment, microballoon to microballoon
The pattern on surface is also roughening.
The surface topography of microcapsules or microballoon directly affects the slow release effect of agricultural chemicals, and the present invention is by adjusting degradation treatment
Time, the rate of release of active ingredient in a regulation microcapsules can be entered, respectively according to the preparation condition in embodiment 1-8 to micro- glue
Capsule is handled, and degradation time only is respectively set into 0h, 0.5h and 1h, and its Cumulative release profile is as shown in Figure 10, therefore, this
In inventive method, by adjusting degradation time, the release of active ingredient can control.
(2) under different degradation times surface of microcapsule potential and element variation
The surface potential (Z potentials) of microcapsules (microballoon) is the quantity of electric charge for representing microcapsules (microballoon) surface, surface charge
Bigger, the repulsive force between microcapsules (microballoon) is bigger, and microcapsules (microballoon) are more stable in aqueous, therefore Z potentials are
Characterize the important indicator whether microcapsules (microballoon) dispersion liquid is stablized.
Prepare microcapsules according to the method in embodiment 1-8, only by duration of oscillation be respectively set to 0h, 0.5h, 1.0h,
1.5h and 2h, potential and elementary analysis are carried out to obtained surface of microcapsule respectively.
Laser particle analyzer (Nano is used after obtained microcapsules to be diluted to suitable concentration, ultrasound with deionized water
ZS90；Malvern potential test) is carried out, surface of microcapsule potential is (left side) as shown in figure 11 under the different disposal time.Will be obtained
Microcapsules are dried to constant weight, are measured using Hitachi Electronic Speculum S-4300, oxygen element in microcapsules under the different disposal time
Weight/mass percentage composition is as shown in figure 11 (right side).By Figure 11 to find out, due to the degraded of polymer, the surface of microcapsules is generated greatly
The carboxyl and hydroxyl of amount.
By to the microsphere surface potential of processing and elementary analysis, finding with the increase of processing time, microsphere surface
There is first increasing the trend reduced afterwards in potential, when handling 1.0h, and the surface potential of microballoon is maximum, i.e., surface carboxyl groups are most, and
The elementary analysis rule on surface is also such.Because as processing time increases, the degraded of surface polymer, molecular weight is big
Big reduction, is finally dissolved in water.So as to being the carboxyl reduction on surface, and the potential on surface increases on the contrary.After GPC detection process
Solution, as shown in figure 12 in the PLA microcapsules of respectively untreated Rynaxypyr, embodiment 2 handle after solution,
Solution after being handled in solution, embodiment 4 after being handled in embodiment 3, the microcapsules it can be seen from the figure after treatment
Solution in engender the materials of some small-molecular-weights, it turned out that, this is water miscible small molecule PLA.
The stability and blade face decoction hold-up of the obtained suspension for carrying powder under embodiment 16, different degradation times
(1) stability
Its dispersiveness can be strengthened by carrying the interionic repulsive interaction of medicine particle surface carboxyl, reduce the reunion of microcapsules
And sedimentation.The stability of different microcapsule suspensions have studied by the measure of turbidity.
Prepare microcapsules according to the method in embodiment 1-8, only by duration of oscillation be respectively set to 0h, 0.5h, 1.0h,
1.5h and 2h, and be dispersed in respectively in water, the suspension that concentration is 2mg/ml is made, using Hash transmissometer 2100 to it
Turbidity is measured, and experimental result is as shown in figure 13.
As a result alkali process 1h microcapsules are found, it turbidity mutation time occurs the latest, and turbidity is minimum, explanation processing
The stability of 1h microcapsules preferably, is reunited most weak between particle, and the surface of microcapsule carboxyl that this is primarily due to handle 1h is most.
(2) blade face decoction hold-up
Prepare microcapsule-type water-based suspension agent according to the method in embodiment 1-8, only by duration of oscillation be respectively set to 0h,
0.5h, 1.0h, 1.5h and 2h, and be respectively dispersed in water obtained microcapsule-type water-based suspension agent, it is 2mg/ that concentration, which is made,
Ml suspension.Weigh a diameter of 7mm fresh cucumber leaf quality (m1, mg) after, by it in above-mentioned microcapsule suspensions
10s is soaked, it is rapid to pull out, it is suspended vertically, claim its weight (m when not dripped to blade face again2, mg), it is repeated 3 times, according to formula meter
Calculate hold-up (R, the mg/cm of decoction on unit area blade2)
R=(m2- m1)/S
S is the gross area (cm of cucumber leaves reverse side in formula2)
Experimental result is as shown in figure 14.
As seen from the figure, the liquid level hold-up of the suspension of the load medicine ion by degradation treatment is significantly improved, this master
If because carrying medicine particle surface carboxyl equivalent to surfactant, the surface tension of water-based suspension agent can be reduced, be conducive to
Powder is carried in crop blade face deposition, in addition, with the extension of drug-loading microcapsule processing time, decoction hold-up on blade surface
Also there is the trend of first increases and then decreases, this first increases mainly due to its surface carboxyl groups and reduced afterwards, handle after 1h, on the contrary wetability
It is deteriorated.
Therefore, pesticide slow-releasing agent (water-based suspension agent) of the present invention, will compared with the pesticide slow-releasing agent without degradation treatment
After it is dispersed in water, dispersiveness, stability and the slow release of gained aqueous dispersion preparation middle peasant's pharmaceutically active ingredient can be improved, improved
Target deposition, enrichment and dosage transfer efficiency.The sustained release time limit that the pesticide slow-releasing agent can extend under minimum effective concentration,
Effective rate of utilization, the bioactivity of agricultural chemicals are improved, Pesticide use amount is reduced, residues of pesticides and environmental pollution is reduced.
Claims (3)
1. a kind of preparation method of pesticide slow-releasing agent, comprises the following steps：The particle for loading agricultural chemicals is dispersed in degraded agent solution
In, centrifuged after vibration, collect solid, you can obtain the slow-releasing pesticide preparation；
The degradation agent is acidic materials or alkaline matter；
The acidic materials are hydrochloric acid, sulfuric acid or niter cake；
The alkaline matter is sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate or sodium acid carbonate；
The mass-volume concentration of the degraded agent solution is 1 ~ 250 mg/ml, and solvent is that volume ratio is 1：（1~100）Water
With the mixed liquor of ethanol；
The particle is microcapsules or microballoon；
The carrier material of the particle is the biodegradable high polymer material containing ester bond；
The biodegradable high polymer material containing ester bond is following 1）Or 2）：
1）Any of polyhydroxyalkanoate, cellulose, polyaminoacid, starch, chitin and collagen；
2）It is poly butylene succinate, PGA, PLA, poly-（Lactide coglycolide）It is copolymer, poly-（Lactide-oneself in
Ester）It is copolymer, poly-（Glycolide-caprolactone）It is copolymer, poly-（Glycolide-lactide-caprolactone）It is copolymer, poly-（Glycolide-poly-
Glycol ether）It is copolymer, poly-（Lactide-polyglycol ether）It is copolymer, poly-（Own lactide-polyglycol ether）It is copolymer, poly-（Third
Lactide-co-glycolides-polyglycol ether）It is copolymer, poly-（Lactide-caprolactone-polyglycol ether）It is copolymer, poly-（Glycolide-oneself
Lactone-polyglycol ether）Copolymer, molecular weight is 5,000 ~ 500,000, and wherein polyglycol ether segment molecule amount is 200 ~ 20,
000；
The particle of every 5 ~ 400 milligrams of the load agricultural chemicals is dispersed in 1 milliliter of degraded agent solution；
The speed of the vibration is 50 ~ 300r/min, and the time is 1 ~ 200min；The rotating speed of the centrifugation is 1000 ~ 10000r/
Min, the time is 2 ~ 15min.
2. preparation method according to claim 1, it is characterised in that：Methods described collect solid after, in addition to pair
The step that solid is washed and dried；The number of times of the washing is 3 ~ 6 times；The drying is freeze-drying.
3. the pesticide slow-releasing agent that the preparation method described in claim 1 or 2 is prepared.
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| CN106561644A (en) * | 2016-11-09 | 2017-04-19 | 中国科学院化学研究所 | Capsule type compound pesticide formulation and preparation method and application thereof |
| CN106614565B (en) * | 2017-02-14 | 2020-07-31 | 仲恺农业工程学院 | Fat-soluble nano pesticide microcapsule and preparation method thereof |
| CN107853299B (en) * | 2017-12-03 | 2020-09-22 | 中国农业科学院农业环境与可持续发展研究所 | Preparation method of leaf surface affinity type pesticide nano drug-loading system |
| CN108684688A (en) * | 2018-06-14 | 2018-10-23 | 国家纳米科学中心 | A kind of nano pesticide composition and preparation method thereof |
| CN110972753A (en) * | 2020-01-10 | 2020-04-10 | 湖南文理学院 | Agricultural light conversion spray liquid and preparation method thereof |
| CN115812700A (en) * | 2021-12-31 | 2023-03-21 | 中山大学 | Nano pesticide and preparation method thereof |
| CN114600879A (en) * | 2022-03-09 | 2022-06-10 | 山东省食品发酵工业研究设计院 | Water-based nano pesticide and production method thereof |
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| CN101743960A (en) * | 2010-02-01 | 2010-06-23 | 吴学民 | Thiacloprid microcapsule powder agent, suspending agent and preparation method and application thereof |
| CN103432602A (en) * | 2013-08-27 | 2013-12-11 | 中国科学院化学研究所 | Micro-capsule ultrasonic contrast agent and preparation method thereof |
| CN104430310A (en) * | 2014-11-25 | 2015-03-25 | 北京农学院 | Controlled-release pesticide suspending agent and preparation method thereof |
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| CN101743960A (en) * | 2010-02-01 | 2010-06-23 | 吴学民 | Thiacloprid microcapsule powder agent, suspending agent and preparation method and application thereof |
| CN103432602A (en) * | 2013-08-27 | 2013-12-11 | 中国科学院化学研究所 | Micro-capsule ultrasonic contrast agent and preparation method thereof |
| CN104430310A (en) * | 2014-11-25 | 2015-03-25 | 北京农学院 | Controlled-release pesticide suspending agent and preparation method thereof |
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