CN109258663B - Methylamino abamectin benzoate PPC microsphere and preparation method thereof - Google Patents
Methylamino abamectin benzoate PPC microsphere and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A—HUMAN NECESSITIES
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- 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
- A01N25/08—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 containing solids as carriers or diluents
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- 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
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Abstract
The invention belongs to the field of pesticide processing, and particularly relates to emamectin benzoate PPC microspheres and a preparation method thereof. The methylamino abamectin benzoate PPC microsphere comprises a core material and a wall material, wherein the core material is methylamino abamectin benzoate, and the wall material is a degradable material PPC. The microsphere is prepared by adopting an improved solvent volatilization method, and the preparation method comprises the following steps: preparing a drug-containing oil phase solution, preparing an emulsifier aqueous solution, preparing a primary emulsion and preparing microspheres. The prepared microspheres solve the problem that the PPC microspheres are easy to agglomerate; the problem of low encapsulation efficiency of the microspheres is solved by changing the organic solvent component in the oil phase, the performance of the wall material is improved, the particle size of the microspheres is reduced, and the drug-loading rate is increased.
Description
Technical Field
The invention belongs to the field of pesticide processing, and particularly relates to emamectin benzoate PPC microspheres and a preparation method thereof.
Background
Emamectin benzoate (emamectin benzoate for short) is a novel high-efficiency semi-synthetic antibiotic pesticide synthesized from a fermentation product, namely, abamectin B1, and has the characteristics of super-high efficiency, low toxicity, low residue, no public hazard and other biological pesticides. But is affected by factors such as over-high or over-low acidity, illumination and the like, and the emamectin benzoate is easy to degrade. The photolysis-prone emamectin benzoate is prepared into microspheres or microcapsules, so that the sustained-release effect of the emamectin benzoate can be achieved, and the purposes of safety and environmental protection are achieved.
In the past, the topic group has adopted a solvent volatilization method, and a biodegradable material polylactic acid (PLA), PLA and PPC blended film is used as a wall material to prepare the pesticide microsphere suspending agent. PLA is a biodegradable material, but the cost is higher, and the biodegradation time is longer. The polypropylene carbonate (PPC) is prepared from propylene oxide and CO2The amorphous biodegradable polymer obtained by copolymerization has low costAnd is considered to be a "green material". The blending of PPC and PLA can reduce the cost and improve the environment-friendly performance of the wall material. However, PPC is a hydrophilic non-crystalline polymer, and has carboxyl on a molecular chain, so that the PPC has good toughness, insufficient brittleness and high solution viscosity, and the emamectin benzoate prepared by singly using PPC is easy to agglomerate by using a common microsphere preparation method, and the encapsulation rate of the emamectin benzoate is low. Therefore, the subject group adopts an improved solvent volatilization method to prepare the emamectin benzoate microsphere with the PPC as the wall material, thereby achieving the purposes of simple operation, cost reduction and environmental protection.
Disclosure of Invention
The invention aims to provide an emamectin benzoate microsphere prepared by adopting polypropylene carbonate (PPC) as a wall material, and solves the problem that the PPC microsphere is easy to agglomerate by changing the components of an internal and external aqueous emulsion in water in a solvent volatilization method; the problem of low encapsulation efficiency of the microspheres is solved by changing the organic solvent component in the oil phase, the performance of the wall material is improved, the particle size of the microspheres is reduced, and the drug-loading rate is increased.
In order to achieve the purpose, the invention adopts the following technical scheme:
the methylamino abamectin benzoate PPC microsphere comprises a core material and a wall material, wherein the core material is methylamino abamectin benzoate, and the wall material is a degradable material PPC. The preparation method comprises the following steps:
(1) preparing a drug-containing oil phase solution: uniformly mixing a core material and a wall material according to a mass ratio of 1:3-1:1, adding a volatile organic solvent dichloromethane, sealing, dissolving in an ice-water bath, adding one of acetone, methanol or ethanol, and uniformly mixing to obtain a drug-containing oil phase solution;
(2) preparation of an aqueous emulsifier solution: dissolving emulsifier in water at a ratio of 10-15g/L, adding TWEEN80 and SPAN80, and mixing;
(3) preparation of primary emulsion: stirring the emulsifier aqueous solution prepared in the step (2) by using a high-speed homogenizer, and quickly injecting the drug-containing oil phase solution prepared in the step (1) into the emulsifier aqueous solution under the condition of uniform dispersion of the emulsion to prepare O/W primary emulsion;
(4) preparing microspheres: and (3) uniformly mixing the primary emulsion prepared in the step (3) and the external water phase according to the volume ratio of 1:2-1:6, stirring at the temperature of 26-28 ℃ and at the rotation speed of 1000rpm under the condition of keeping out of the sun until no organic solvent smell exists, filtering, washing with water for three times, centrifuging, and drying in a vacuum drying box at the temperature of 35-38 ℃ to obtain the emamectin benzoate PPC microspheres.
The mass concentration of the wall material PPC in the step (1) is 30-80 mg/mL.
The mass ratio of the dichloromethane to the acetone, the methanol or the ethanol in the step (1) is 1:1-2: 1.
The emulsifier in the step (2) is gelatin or a mixed emulsifier of OP10 and PVA1788 in a mass ratio of 1:1: -1: 3.
The final concentration of the TWEEN80 in the step (2) is 0.5-1.5g/L, and the final concentration of SPAN80 is 0.25-0.5 g/L.
The milk homogenizing and dispersing conditions in the step (3) are as follows: the temperature is 25-35 ℃, the dispersion speed is 7000 and 10000rpm, and the emulsification time is 0.5-5 min.
The external water phase in the step (4) is TWEEN80 aqueous solution with the final concentration of 0.5-1.5 g/L.
The invention has the advantages that:
(1) the polypropylene carbonate (PPC) is prepared from CO2Alternating copolymer synthesized by copolymerization with propylene oxide, and CO in degradation product2The PPC is microencapsulated by the emamectin benzoate to prepare a microsphere sustained release preparation, so that the production cost can be reduced, and the environmental compatibility can be improved.
(2) The subject group has applied for patent by microencapsulating emamectin benzoate with PLA or PLA/PPC blended material to prepare microsphere sustained release preparation. However, PPC is a hydrophilic non-crystalline polymer, and has carboxyl on the molecular chain, so that the toughness is good, the brittleness is insufficient, the solution viscosity is high, and the microspheres prepared by the single PPC and the emamectin benzoate salt by the solvent volatilization method are easy to agglomerate no matter whether pure water is used as an external water phase or not, and cannot be powdered. According to the invention, after the addition effects of different emulsifiers are tried on the basis of the original method, tween80\ span80 is added into the internal and external water phases, and the corresponding proportion is adjusted, so that the problem of agglomeration of the PPC microspheres is solved well, freeze-drying is not needed, and the method of vacuum drying after filtration can be directly adopted to strip the microsphere powder.
Drawings
FIG. 1 is a 5000-fold microimage of an electronic scanning electron microscope of the modified emamectin benzoate PPC microspheres.
FIG. 2 is a scanning electron microscope image at 5000 times microscopic imaging showing the adhesion of the microspheres of the non-modified pre-emamectin benzoate PPC of comparative example 1.
FIG. 3 is a 5000-fold microimage of an electron scanning electron microscope showing that the unmodified emamectin benzoate PPC microspheres of comparative example 2 contain more fragments.
Detailed Description
Example 1
(1) Preparing a drug-containing oil phase solution: 0.2g of emamectin benzoate is taken as a core material; 0.6g of PPC is taken as a wall material; mixing a core material and a wall material according to the mass ratio of 1:3, then adding 4mL of a volatile organic solvent dichloromethane, sealing, dissolving in an ice water bath, and then adding 4mL of acetone to obtain a drug-containing oil phase solution, wherein the mass concentration of the wall material is 75 mg/mL;
(2) preparation of an aqueous emulsifier solution: the emulsifier is OP10 and PVA1788 mixed emulsifier (mass ratio is 1: 3), the emulsifier water solution mass concentration is 10g/L, and TWEEN80 with final concentration of 0.5g/L and SPAN80 with final concentration of 0.25g/L are added and mixed evenly;
(3) preparation of primary emulsion: stirring the emulsifier aqueous solution prepared in the step (2) by using a high-speed homogenizer, and quickly injecting the drug-containing oil phase solution prepared in the step (1) into 200mL of emulsifier aqueous solution under the condition of uniform dispersion of emulsion to prepare O/W primary emulsion; the milk homogenization dispersion conditions were: the temperature is 27 ℃, the dispersion speed is 7000rpm, and the emulsification time is 0.5 min;
(4) preparing microspheres: mixing the primary emulsion prepared in the step (3) with 800mL of external water phase, wherein the external water phase is a TWEEN80 aqueous solution with the final concentration of 0.5g/L, the reaction temperature is 27 ℃, and the primary emulsion is stirred at the rotating speed of 800rpm under the condition of keeping out of the sun until no organic solvent smell exists; filtering, washing with water, centrifuging, and drying at 35 deg.C in vacuum drying oven to obtain emamectin benzoate PPC microsphere.
The obtained microspheres are powdery, have smooth surfaces, uniform particle size distribution, average particle size of 5.58 mu m and encapsulation rate of 85.5 percent.
Example 2
(1) Preparing a drug-containing oil phase solution: 0.3g of emamectin benzoate is taken as a core material; 0.3g of PPC is taken as a wall material; mixing a core material and a wall material according to the mass ratio of 1:1, then adding 5mL of volatile organic solvent dichloromethane, sealing, dissolving in ice water bath, and then adding 2.5mL of acetone to obtain a drug-containing oil phase solution, wherein the mass concentration of the wall material is 40 mg/mL;
(2) preparation of an aqueous emulsifier solution: the emulsifier is gelatin, the mass concentration of the emulsifier aqueous solution is 15g/L, and TWEEN80 with the final concentration of 1.5g/L and SPAN80 with the final concentration of 0.5g/L are added and mixed evenly;
(3) preparation of primary emulsion: stirring the emulsifier aqueous solution prepared in the step (2) by using a high-speed homogenizer, and quickly injecting the drug-containing oil phase solution prepared in the step (1) into 150mL of emulsifier aqueous solution under the condition of uniform dispersion of the emulsion to prepare O/W primary emulsion; the milk homogenization dispersion conditions were: the temperature is 28 ℃, the dispersion speed is 8000rpm, and the emulsification time is 1 min;
(4) preparing microspheres: mixing the primary emulsion prepared in the step (3) with 750mL of external water phase, wherein the external water phase is 1g/L TWEEN80 aqueous solution, the reaction temperature is 27 ℃, and the primary emulsion is stirred at the rotating speed of 800rpm under the condition of keeping out of the sun until no organic solvent smell exists; filtering, washing with water, centrifuging, and drying at 35 deg.C in vacuum drying oven to obtain emamectin benzoate PPC microsphere.
The obtained microspheres are powdery, have smooth surfaces, uniform particle size distribution, average particle size of 5.75 mu m and encapsulation efficiency of 81.6 percent.
Example 3
(1) Preparing a drug-containing oil phase solution: 0.2g of emamectin benzoate is taken as a core material; 0.4g of PPC is taken as a wall material; mixing a core material and a wall material according to the mass ratio of 1:2, then adding 5mL of volatile organic solvent dichloromethane, sealing, dissolving in ice water bath, and then adding 3mL of acetone to obtain a drug-containing oil phase solution, wherein the mass concentration of the wall material is 50 mg/mL;
(2) preparation of an aqueous emulsifier solution: the emulsifier is gelatin, the mass concentration of the emulsifier aqueous solution is 12.5g/L, and TWEEN80 with the final concentration of 0.5g/L and SPAN80 with the final concentration of 0.5g/L are added and mixed evenly;
(3) preparation of primary emulsion: stirring the emulsifier aqueous solution prepared in the step (2) by using a high-speed homogenizer, and quickly injecting the drug-containing oil phase solution prepared in the step (1) into 200mL of emulsifier aqueous solution under the condition of uniform dispersion of emulsion to prepare O/W primary emulsion; the milk homogenization dispersion conditions were: the temperature is 27 ℃, the dispersion speed is 8000rpm, and the emulsification time is 1.5 min;
(4) preparing microspheres: mixing the primary emulsion prepared in the step (3) with 800mL of external water phase, wherein the external water phase is a TWEEN80 aqueous solution with the final concentration of 0.5g/L, the reaction temperature is 27 ℃, and the primary emulsion is stirred at the rotating speed of 800rpm under the condition of keeping out of the sun until no organic solvent smell exists; filtering, washing with water, centrifuging, and drying at 35 deg.C in vacuum drying oven to obtain emamectin benzoate PPC microsphere.
The obtained microspheres are powdery, have smooth surfaces, uniform particle size distribution, average particle size of 5.76 mu m and encapsulation efficiency of 90.1 percent.
The obtained emamectin benzoate PPC microspheres are subjected to microscopic photography by a scanning electron microscope (5000 times), the result is shown in figure 1, and the obtained microspheres have good balling property, are dispersed, have no fragments and are uniform in particle size distribution.
Comparative example 1
(1) Preparing a drug-containing oil phase solution: 0.3g of emamectin benzoate is taken as a core material; 0.3g of PPC is taken as a wall material; mixing a core material and a wall material according to the mass ratio of 1:1, then adding 5mL of volatile organic solvent dichloromethane, sealing, dissolving in ice water bath, and then adding 2.5mL of acetone to obtain a drug-containing oil phase solution, wherein the mass concentration of the wall material is 40 mg/mL;
(2) preparation of an aqueous emulsifier solution: the emulsifier is gelatin, and the mass concentration of the emulsifier aqueous solution is 15 g/L;
(3) preparation of the emulsion: stirring the emulsifier aqueous solution prepared in the step (2) by using a high-speed homogenizer, and quickly injecting the drug-containing oil phase solution prepared in the step (1) into 150mL of emulsifier aqueous solution under the condition of uniform dispersion of the emulsion to prepare O/W emulsion; the milk homogenization dispersion conditions were: the temperature is 28 ℃, the dispersion speed is 8000rpm, and the emulsification time is 1 min;
(4) preparing microspheres: and (4) stirring the emulsion prepared in the step (3) at the rotating speed of 800rpm under the condition of keeping out of the light until no organic solvent smell exists. Filtering, washing with water, centrifuging, and drying at 35 deg.C in vacuum drying oven to obtain emamectin benzoate PPC microsphere.
The results of microscopic photography of the prepared emamectin benzoate PPC microspheres by using a scanning electron microscope (5000 times) are shown in figure 2, and compared with the operation conditions of the examples, the microspheres prepared in the comparative example 1 have no external water phase and no TWEEN80 and SPAN80 are added in the primary emulsion, have smaller spheres but are all adhered into one piece and cannot be separated.
Comparative example 2
(1) Preparing a drug-containing oil phase solution: 0.3g of emamectin benzoate is taken as a core material; 0.3g of PPC is taken as a wall material; mixing a core material and a wall material according to the mass ratio of 1:1, then adding 5mL of volatile organic solvent dichloromethane, sealing, dissolving in ice water bath, and then adding 2.5mL of acetone to obtain a drug-containing oil phase solution, wherein the mass concentration of the wall material is 40 mg/mL;
(2) preparation of an aqueous emulsifier solution: the emulsifier is gelatin, the mass concentration of the emulsifier aqueous solution is 15g/L, and TWEEN80 with the final concentration of 1.5g/L and SPAN80 with the final concentration of 0.5g/L are added and mixed evenly;
(3) preparation of the emulsion: stirring the emulsifier aqueous solution prepared in the step (2) by using a high-speed homogenizer, and quickly injecting the drug-containing oil phase solution prepared in the step (1) into 150mL of emulsifier aqueous solution under the condition of uniform dispersion of the emulsion to prepare O/W emulsion; the milk homogenization dispersion conditions were: the temperature is 28 ℃, the dispersion speed is 8000rpm, and the emulsification time is 1 min;
(4) preparing microspheres: and (4) stirring the emulsion prepared in the step (3) at the rotating speed of 800rpm under the condition of keeping out of the light until no organic solvent smell exists. Filtering, washing with water, centrifuging, and drying at 35 deg.C in vacuum drying oven to obtain emamectin benzoate PPC microsphere.
The obtained emamectin benzoate PPC microspheres are subjected to microscopic imaging by using a scanning electron microscope (5000 times), the result is shown in figure 3, compared with the operation conditions of the embodiment, the comparative example 2 has no external water phase, the prepared microspheres are spherical and can be separated, but more fragments exist on the surfaces of the microspheres, and the encapsulation efficiency is not high.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (1)
1. A preparation method of emamectin benzoate PPC microspheres is characterized by comprising the following steps:
(1) preparing a drug-containing oil phase solution: uniformly mixing a core material and a wall material according to a mass ratio of 1:3-1:1, adding a volatile organic solvent dichloromethane, sealing, dissolving in an ice-water bath, adding one of acetone, methanol or ethanol, and uniformly mixing to obtain a drug-containing oil phase solution; the core material is emamectin benzoate, and the wall material is a degradable material PPC;
(2) preparation of an aqueous emulsifier solution: dissolving emulsifier in water at a ratio of 10-15g/L, adding TWEEN80 and SPAN80, and mixing;
(3) preparation of primary emulsion: stirring the emulsifier aqueous solution prepared in the step (2) by using a high-speed homogenizer, and quickly injecting the drug-containing oil phase solution prepared in the step (1) into the emulsifier aqueous solution under the condition of uniform dispersion of the emulsion to prepare O/W primary emulsion; the volume of the emulsifier aqueous solution is 200 mL;
(4) preparing microspheres: uniformly mixing the primary emulsion prepared in the step (3) and an external water phase according to the volume ratio of 1:2-1:6, stirring at the temperature of 26-28 ℃ and the rotation speed of 1000rpm under the condition of keeping out of the sun until no organic solvent smell exists, filtering, washing with water for three times, centrifuging, and drying in a vacuum drying box at the temperature of 35-38 ℃ to obtain emamectin benzoate PPC microspheres; the volume of the external water phase is 800 mL;
the mass concentration of the wall material PPC in the step (1) is 30-80 mg/mL;
the mass ratio of the dichloromethane to the acetone, the methanol or the ethanol in the step (1) is 1:1-2:1;
the emulsifier in the step (2) is gelatin or a mixed emulsifier of OP10 and PVA1788 in a mass ratio of 1:1-1: 3;
the final concentration of the TWEEN80 in the step (2) is 0.5-1.5g/L, and the final concentration of SPAN80 is 0.25-0.5g/L;
the milk homogenizing and dispersing conditions in the step (3) are as follows: the temperature is 25-35 ℃, the dispersion speed is 7000 and 10000rpm, and the emulsification time is 0.5-5 min;
the external water phase in the step (4) is TWEEN80 aqueous solution with the final concentration of 0.5-1.5 g/L.
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| CN105419296A (en) * | 2016-01-18 | 2016-03-23 | 中国科学院长春应用化学研究所 | Liquid mulching film and preparation method thereof |
| CN106673852A (en) * | 2017-01-05 | 2017-05-17 | 中国农业大学 | Microelement suspended pesticidal fertilizer containing pesticidal microcapsules |
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| CN105419296A (en) * | 2016-01-18 | 2016-03-23 | 中国科学院长春应用化学研究所 | Liquid mulching film and preparation method thereof |
| CN106673852A (en) * | 2017-01-05 | 2017-05-17 | 中国农业大学 | Microelement suspended pesticidal fertilizer containing pesticidal microcapsules |
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| 可降解聚碳酸亚丙酯-毒死蜱微胶囊的制备及缓释性能评价;孟锐等;《农药学学报》;20120920;摘要、表1-3、图3、第567、569、572页 * |
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