CN105409944A - Preparation method for pyrethrin microcapsules - Google Patents
Preparation method for pyrethrin microcapsules Download PDFInfo
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- CN105409944A CN105409944A CN201511013309.5A CN201511013309A CN105409944A CN 105409944 A CN105409944 A CN 105409944A CN 201511013309 A CN201511013309 A CN 201511013309A CN 105409944 A CN105409944 A CN 105409944A
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- pyrethrins
- microcapsules
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Abstract
The invention relates to a preparation method for pyrethrin microcapsules. The preparation method comprises the following steps: firstly, carrier preparation is carried out, namely, a polymerization reaction with a mol ratio of succinic acid, butylene glycol and lactic acid being 1:1:0.2-0.3 is carried out, and a carrier PBS-co-PLA is obtained; secondly, oil phase preparation is carried out, namely, PBS-co-PLA, pyrethrin and dichloromethane are weighed with a mass ratio of PBS-co-PLA, pyrethrin and dichloromethane being 3.5-4.5:1:10, the PBS-co-PLA carrier is dissolved in dichloromethane, after the PBS-co-PLA is dissolved in dichloromethane fully, the pyrethrin active compound is added and dissolved and an oil phase is obtained; thirdly, water phase preparation is carried out, deionized water is measured and taken with a mass ratio of the oil phase to the water phase being 1:5-7, an emulsifier dispersant is added in water and dissolved and a water phase is obtained; fourthly, microcapsule preparation is carried out, namely, the oil phase is added in the water phase, an oil and water mixed emulsion is obtained, an antifoaming agent is added, microcapsule suspension is prepared after curing, water washing is carried out, the supernatant is removed, and a finished product is obtained after drying. The method is simple in technology and is environmentally friendly. The obtained pyrethrin microcapsules have a good form, the encapsulation efficiency is 78%, the drug loading capacity is 50%, the effective release period is 30 days, the drug release amount is 94%, and the pyrethrin microcapsule is an ideal pesticide sustained release agent.
Description
Technical field
The invention belongs to preparation technique of pesticide field, be specifically related to a kind of preparation method of pyrethrins microcapsules.
Background technology
Pyrethrins is the broad spectrum pesticide that a class can prevent and treat various pests, its insecticidal toxicity than older generation insecticide as organochlorine, organic phosphor, carbamates improve 10 ~ 100 times.Pyrethroid has strong action of contace poison to insect, and some kind has stomach toxicity or fumigation action concurrently, but does not all have systemic action.Its mechanism of action upsets the normal physiological of insect nerve, make it by excited, spasm is dead to benumbing.Pyrethroid is because consumption is little, working concentration is low, therefore safer to people and animals, very little to the pollution of environment.Its shortcoming is mainly high to fish toxicity, also has injury to some beneficial insect, reuses for a long time and insect also can be caused to develop immunity to drugs.
Microcapsules (Microcapsules, MC) be a kind ofly will to be wrapped up as the activated material of core tool (for former medicine in agricultural chemicals) by chemistry, physics or physicochemical method as carrier using the macromolecule of natural or Prof. Du Yucang or some suitable material, form a kind of microencapsulation with semi permeability cyst membrane.After the machining of pesticide micro capsule, also need them with certain concentration dispersion suspension (generally based on water) in the continuous phase of flowing, be called micro-capsule suspension (CapsuleSuspensions, CS), then dispenser is carried out to crop.Pesticide micro capsule forms primarily of two parts, i.e. carrier material and the former medicine of core, and carrier is the key affecting core activity.The particle diameter of usual microcapsules is generally between 1-100 μm, and from the appearance, pesticide micro capsule, the spitting image of aqueous suspension agent and aqueous emulsion, is all be dispersed in the heterogeneous system among water or other continuous phase.
The advantage of Microcapsules of Pesticides mainly contains: 1. because sustained release agent decreases the decomposition to agricultural chemicals of light in environment, air, water and microorganism, and change release performance, thus the lasting period is extended, and dosage reduces, dispenser widens interval time, saving of labor economizes medicine.2., because the Co ntrolled release measure of sustained release agent makes that high-toxic pesticide is low to be poisoned, reduce former medicine to the toxicity of people, animal, fish etc. and excitant, alleviate the pollution to environment and the poisoning to crops, thus expand the range of application of agricultural chemicals.3. by control release technic process, improve the physical property of medicament, improve the stability of former medicine, improve uvioresistant linchpin and penetrate ability, and liquid pesticidal curable type, storage, transport, use and post processing are all very easy.4. reduce the loss caused because of former medicine volatilization, the penetrating odor of the medicine that demasks.5. improve the compounding capacity with the agricultural chemicals that usually to mismatch, due to can by used in combination for the microcapsule formulations of Multiple Pesticides, interaction between agricultural chemicals need not be worried and the drug effect that causes weakens, thus the generation of the pest resistance to insecticide relatively alleviated.
In the world, started to be applied to formulations of pesticide processing as far back as 20 century 70 microencapsulation technologies, but at present, the product quantity of microencapsulation is quite limited.1976, the Pennwalt company of the U.S. is proposed first Microcapsules of Pesticides: parathion-methyl microcapsules (Penncap ~ M), move towards practical with the initial Typical Representative of Microcapsules of Pesticides, it makes the fugitive parathion-methyl of high poison significantly reduce toxicity, extends residual effect.After this large amount of basic research has agriculturally been carried out in the research and development of microcapsules, and achieve certain progress, more than 200 agro-chemical companies is about had to study in the development and application field of microcapsule formulations at present, Microcapsules of Pesticides is developed so far existing more than 40 years history, but compared with medical microcapsules field, development is relatively slow, and current commercial pesticide micro capsule kind is also little.
The method of pesticide micro capsule mainly contains interfacial polymerization, coacervation phase separation method, situ aggregation method, solvent evaporation method etc., and these methods not only complex process, cost is higher, also wants in a large number with an organic solvent, contaminated environment.
Summary of the invention
For the problems referred to above, the present invention aims to provide simple, the with low cost and preparation method of eco-friendly pyrethrins microcapsules of a kind of technique.
A preparation method for pyrethrins microcapsules, comprises the following steps:
(1) carrier preparation: according to succinic acid: butanediol: lactic acid=1:1:0.2-0.3 mol ratio carries out polymerisation, obtain the copolymerization carrier PBS-co-PLA of poly butylene succinate and PLA;
(2) oil phase preparation: PBS-co-PLA in mass ratio: pyrethrins: carrene=3.5-4.5:1:10 takes each component, is dissolved in carrene by PBS-co-PLA carrier, and until completely dissolved, add the former medicine of pyrethrins, abundant stirring and dissolving, obtains oil phase;
(3) aqueous phase preparation: oil phase in mass ratio: aqueous phase=1:5-7 measures deionized water, adds emulsif iotaers dispersing agents, dissolves to obtain aqueous phase completely;
(4) microcapsules preparation: after oil phase is joined aqueous phase, clipper is used to shear 3-8min, obtained oil mixing with water emulsion, add the defoamer of cumulative volume 0.1-2%, it is complete to carrene volatilization that constant temperature stirs emulsion, and carrier material is separated out, solidify to form microcapsule suspensions, gained suspension is washed, removes supernatant, dry and obtain pyrethrins microcapsules finished product.
In step (1), polymerisation adopts four different interior oxygen base titaniums and phosphoric acid as catalyzer, and catalyst amount is the 0.1-0.2% of reactant gross mass.
In step (1), polymeric reaction temperature is 230-250 DEG C, and reaction pressure is 50-80Pa, and the reaction time is 3-4h.
In step (2), adopt ultrasonic cleaning machine accelerate dissolution.
In step (3), emulsifying dispersant and addition are: 2wt% Tween 80, class of 3wt% department 80,2wt%PVA-1788 or 3wt%PVA-1788.
In step (4), clipper rotating speed is 7000-10000rpm.
In step (4), defoamer is isoamyl alcohol.
In step (4), constant temperature whipping temp is 25-30 DEG C, and the time is 7-9h.
In step (4), washing times is 1-3 time.
In step (4), drying condition is 40-50 DEG C, 0.5-2 days.
The inventive method preparation technology is simple, and the organic solvent of use is few, environmental friendliness.The pyrethrins Microcapsules Size prepared is between 4.5-5.5 μm, form is better, surface relative smooth, dry successor can keep good form, envelop rate reaches more than 78%, and drugloading rate reaches more than 50%, and effective release period is more than 30 days, release amount can reach more than 94%, is desirable pesticide slow-releasing agent.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further details.
Embodiment 1
(1) carrier preparation: be that the different interior oxygen base titanium of catalyzer four and the phosphoric acid of the succinic acid of 1:1:0.2, butanediol, lactic acid and 0.1wt% puts into the two neck flasks that electronic reinforcement agitator, condensing reflux pipe are housed by mol ratio; after under the protection of nitrogen, oil bath is heated to 240 DEG C; dehydration 1h; then vacuumize; controlled pressure is to low vacuum in 50Pa; carry out degreasing reaction; reaction is stopped after 3h; under the protection of nitrogen; the high-molecular copolymer PBS-co-PLA of white solid is just namely obtained, by products therefrom vacuum drying at 60 DEG C after cooling.
(2) oil phase preparation: accurately take 3.5mgPBS-co-PLA and be dissolved in l0mL carrene, until completely dissolved, the more former medicine of the pyrethrins adding 1mg, fully stir and use ultrasonic cleaning machine accelerate dissolution, obtaining oil phase.
(3) aqueous phase preparation: measure 98mL deionized water, add 2wt%PVA-1788, by magnetic stirrer 40min until dissolve to obtain aqueous phase completely.
(4) microcapsules preparation: after oil phase is joined aqueous phase, uses clipper with the rotating speed cutting 5min of 8000rpm, and obtained oil mixing with water emulsion, instills 100 μ L defoamer isoamyl alcohol.By emulsion constant temperature (25 DEG C) low speed stirs 9h on magnetic stirring apparatus, treat that carrene volatilizees gradually, carrier material is separated out, and finally solidify to form microcapsule suspensions.By gained suspension washing high speed centrifugation 2 times, remove supernatant, electrically heated drying cabinet (set temperature is 40 DEG C) inner drying 2 days, both pyrethrins microcapsules finished product.
Embodiment 2
(1) carrier preparation: be that the different interior oxygen base titanium of catalyzer four and the phosphoric acid of the succinic acid of 1:1:0.3, butanediol, lactic acid and 0.12wt% puts into the two neck flasks that electronic reinforcement agitator, condensing reflux pipe are housed by mol ratio; after under the protection of nitrogen, oil bath is heated to 240 DEG C; dehydration 1h; then vacuumize; controlled pressure is to low vacuum in 80Pa; carry out degreasing reaction; reaction is stopped after 4h; under the protection of nitrogen; the high-molecular copolymer PBS-co-PLA of white solid is just namely obtained, by products therefrom vacuum drying at 60 DEG C after cooling.
(2) oil phase preparation: accurately take 4.5mgPBS-co-PLA and be dissolved in l0mL carrene, until completely dissolved, the more former medicine of the pyrethrins adding 1mg, fully stir and use ultrasonic cleaning machine accelerate dissolution, obtaining oil phase.
(3) aqueous phase preparation: measure 98mL deionized water, add class of 3wt% department 80, by magnetic stirrer 40min until dissolve to obtain aqueous phase completely.
(4) microcapsules preparation: after oil phase is joined aqueous phase, uses clipper with the rotating speed cutting 5min of 9000rpm, and obtained oil mixing with water emulsion, instills 200 μ L defoamer isoamyl alcohol.By emulsion constant temperature (30 DEG C) low speed stirs 7h on magnetic stirring apparatus, treat that carrene volatilizees gradually, carrier material is separated out, and finally solidify to form microcapsule suspensions.By gained suspension washing high speed centrifugation 3 times, remove supernatant, electrically heated drying cabinet (set temperature is 50 DEG C) inner drying 1 day, both pyrethrins microcapsules finished product.
Embodiment 3
(1) carrier preparation: be that the different interior oxygen base titanium of catalyzer four and the phosphoric acid of the succinic acid of 1:1:0.25, butanediol, lactic acid and 0.115wt% puts into the two neck flasks that electronic reinforcement agitator, condensing reflux pipe are housed by mol ratio; after under the protection of nitrogen, oil bath is heated to 240 DEG C; dehydration 1h; then vacuumize; controlled pressure is to low vacuum in 67Pa; carry out degreasing reaction; reaction is stopped after 3.5h; under the protection of nitrogen; the high-molecular copolymer PBS-co-PLA of white solid is just namely obtained, by products therefrom vacuum drying at 60 DEG C after cooling.
(2) oil phase preparation: accurately take 4mgPBS-co-PLA and be dissolved in l0mL carrene, until completely dissolved, the more former medicine of the pyrethrins adding 1mg, fully stir and use ultrasonic cleaning machine accelerate dissolution, obtaining oil phase.
(3) aqueous phase preparation: measure 98mL deionized water, add 3wt%PVA-1788, by magnetic stirrer 40min until dissolve to obtain aqueous phase completely.
(4) microcapsules preparation: after oil phase is joined aqueous phase, uses clipper with the rotating speed cutting 5min of 7000rpm, and obtained oil mixing with water emulsion, instills 150 μ L defoamer isoamyl alcohol.By emulsion constant temperature (28 DEG C) low speed stirs 8h on magnetic stirring apparatus, treat that carrene volatilizees gradually, carrier material is separated out, and finally solidify to form microcapsule suspensions.By gained suspension washing high speed centrifugation 3 times, remove supernatant, electrically heated drying cabinet (set temperature is 45 DEG C) inner drying 1 day, both pyrethrins microcapsules finished product.
The pyrethrins microcapsules finished product obtained to embodiment 1-3 carries out observation by light microscope, and its form is better, and evenly and be all spherical, surperficial relative smooth, dry successor can keep good form to encystation, and each data parameters is as shown in table 1.
The pyrethrins properties of microcapsules parameter that each embodiment of table 1 is obtained
| Particle diameter | Envelop rate | Drugloading rate | Effective release period | Release amount | |
| Embodiment 1 | 4.5-5.5μm | 78.23% | 50.71% | 31 days | 94.26% |
| Embodiment 2 | 4.5-5.5μm | 78.15% | 51.81% | 33 days | 95.22% |
| Embodiment 3 | 4.5-5.5μm | 79.05% | 53.63% | 33 days | 94.65% |
Claims (10)
1. a preparation method for pyrethrins microcapsules, is characterized in that, comprises the following steps:
(1) carrier preparation: according to succinic acid: butanediol: lactic acid=1:1:0.2-0.3 mol ratio carries out polymerisation, obtain the copolymerization carrier PBS-co-PLA of poly butylene succinate and PLA;
(2) oil phase preparation: PBS-co-PLA in mass ratio: pyrethrins: carrene=3.5-4.5:1:10 takes each component, is dissolved in carrene by PBS-co-PLA carrier, and until completely dissolved, add the former medicine of pyrethrins, abundant stirring and dissolving, obtains oil phase;
(3) aqueous phase preparation: oil phase in mass ratio: aqueous phase=1:5-7 measures deionized water, adds emulsif iotaers dispersing agents, dissolves to obtain aqueous phase completely;
(4) microcapsules preparation: after oil phase is joined aqueous phase, clipper is used to shear 3-8min, obtained oil mixing with water emulsion, add the defoamer of cumulative volume 0.1-2%, it is complete to carrene volatilization that constant temperature stirs emulsion, and carrier material is separated out, solidify to form microcapsule suspensions, gained suspension is washed, removes supernatant, dry and obtain pyrethrins microcapsules finished product.
2. the preparation method of pyrethrins microcapsules according to claim 1, is characterized in that, in step (1), polymerisation adopts four different interior oxygen base titaniums and phosphoric acid as catalyzer, and catalyst amount is the 0.1-0.2% of reactant gross mass.
3. the preparation method of pyrethrins microcapsules according to claim 1, is characterized in that, in step (1), polymeric reaction temperature is 230-250 DEG C, and reaction pressure is 50-80Pa, and the reaction time is 3-4h.
4. the preparation method of pyrethrins microcapsules according to claim 1, is characterized in that, in step (2), adopts ultrasonic cleaning machine accelerate dissolution.
5. the preparation method of pyrethrins microcapsules according to claim 1, is characterized in that, in step (3), emulsifying dispersant and addition are: 2wt% Tween 80, class of 3wt% department 80,2wt%PVA-1788 or 3wt%PVA-1788.
6. the preparation method of pyrethrins microcapsules according to claim 1, is characterized in that, in step (4), clipper rotating speed is 7000-10000rpm.
7. the preparation method of pyrethrins microcapsules according to claim 1, is characterized in that, in step (4), defoamer is isoamyl alcohol.
8. the preparation method of pyrethrins microcapsules according to claim 1, is characterized in that, in step (4), constant temperature whipping temp is 25-30 DEG C, and the time is 7-9h.
9. the preparation method of pyrethrins microcapsules according to claim 1, is characterized in that, in step (4), washing times is 1-3 time.
10. the preparation method of pyrethrins microcapsules according to claim 1, is characterized in that, in step (4), drying condition is 40-50 DEG C, 0.5-2 days.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201511013309.5A CN105409944A (en) | 2015-12-31 | 2015-12-31 | Preparation method for pyrethrin microcapsules |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106149095A (en) * | 2016-08-14 | 2016-11-23 | 张天奇 | A kind of fabric lining containing hot energy storage material |
| CN106942291A (en) * | 2017-03-24 | 2017-07-14 | 孙志廷 | It is a kind of to be coated with chitosan Polylactic Acid Extended Release microcapsules of matrine and preparation method thereof |
| CN114072226A (en) * | 2019-05-17 | 2022-02-18 | 农业科技集团有限公司 | Method and process for obtaining high-stability natural pyrethrin microbial capsules |
-
2015
- 2015-12-31 CN CN201511013309.5A patent/CN105409944A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106149095A (en) * | 2016-08-14 | 2016-11-23 | 张天奇 | A kind of fabric lining containing hot energy storage material |
| CN106942291A (en) * | 2017-03-24 | 2017-07-14 | 孙志廷 | It is a kind of to be coated with chitosan Polylactic Acid Extended Release microcapsules of matrine and preparation method thereof |
| CN114072226A (en) * | 2019-05-17 | 2022-02-18 | 农业科技集团有限公司 | Method and process for obtaining high-stability natural pyrethrin microbial capsules |
| EP3970847A4 (en) * | 2019-05-17 | 2023-02-08 | Grupo Agrotecnologia, S.L. | Method and procedure for obtaining micro biocapsules of natural pyrethrins with high stability |
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Application publication date: 20160323 |