CN114287421B - Ultraviolet-resistant biological pesticide composite microcapsule and preparation method thereof - Google Patents
Ultraviolet-resistant biological pesticide composite microcapsule and preparation method thereof Download PDFInfo
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Abstract
The invention provides an anti-ultraviolet biological pesticide composite microcapsule and a preparation method thereof, belonging to the technical field of pesticide microcapsules. The invention provides an anti-ultraviolet biological pesticide composite microcapsule, which comprises a microcapsule capsule wall material and biological pesticide wrapped in the microcapsule capsule wall material; the microcapsule material is polyurethane, and the microcapsule material contains lignin-inorganic semiconductor nano-composite. According to the invention, the lignin-inorganic semiconductor nano-composite is introduced into the microcapsule capsule wall material as an ultraviolet shielding agent, and under the illumination condition, photo-generated electrons are transferred to lignin molecules under the traction action of lignin unsaturated bonds, so that the separation of photo-generated electron-hole pairs in a semiconductor can be promoted, and the ultraviolet resistance of the microcapsule capsule wall material can be remarkably improved; meanwhile, lignin has the characteristic of antioxidation, and can eliminate photodegradation of biological pesticides by the photocatalytic activity of semiconductors.
Description
Technical Field
The invention relates to the technical field of pesticide microcapsules, in particular to an ultraviolet-resistant biological pesticide composite microcapsule and a preparation method thereof.
Background
In recent years, development of green agriculture has become a main melody of agricultural production. The biopesticide has advantages in the fields of organic agriculture, pollution-free agriculture and green agriculture diseases and insect pests control. Biopesticides refer to agents that kill or inhibit agricultural pests using living organisms (fungi, bacteria, insect viruses, transgenic organisms, natural enemies, etc.) or their metabolites (pheromones, auxins, naphthylacetic acid, 2,4-D, etc.). Compared with chemical pesticides, the biological pesticide has the advantages of strong selectivity, no harm to human and livestock and small influence on environment.
The pesticide microencapsulation technology can be used for coating active substances of solid and liquid pesticides in a degradable capsule film to prepare the microcapsule. The biological pesticide is prepared into microcapsules, so that the pesticide can be endowed with good slow release performance, and the duration of the pesticide can be prolonged by 2-3 times; after the biological pesticide is prepared into the microcapsule, the use amount of the original pesticide can be reduced to 1/2-1/3 of the original use amount, and the application amount of the pesticide is obviously reduced.
However, biopesticides often have the property of ultraviolet light degradation. After the biopesticide is applied to the outdoor field, ultraviolet rays in sunlight induce photodegradation thereof, which reduces the field control effect of the biopesticide.
Disclosure of Invention
In view of the above, the invention aims to provide an ultraviolet-resistant composite biopesticide microcapsule and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an anti-ultraviolet biological pesticide composite microcapsule, which comprises a microcapsule capsule wall material and biological pesticide wrapped in the microcapsule capsule wall material;
the microcapsule material is polyurethane, and the microcapsule material contains lignin-inorganic semiconductor nano-composite.
Preferably, the lignin-inorganic semiconductor composite material is lignin-TiO 2 Nanocomposite, lignin-ZnO nanocomposite, lignin-SiO 2 Nanocomposite and lignin-CeO 2 One or more of the nanocomposites.
Preferably, the lignin-inorganic semiconductor nano-composite is contained in the microcapsule capsule wall material in an amount of 30-50 wt%.
Preferably, the lignin-TiO 2 The preparation method of the nano-composite comprises the following steps:
mixing quaternized alkali lignin, inorganic acid, butyl titanate and water, and performing hydrothermal reaction to obtain lignin-TiO 2 A nanocomposite;
the lignin-SiO 2 The preparation method of the nano-composite comprises the following steps:
mixing quaternized alkali lignin, inorganic acid, tetraethoxysilane and water, and performing hydrothermal reaction to obtain lignin-TiO 2 A nanocomposite;
the preparation method of the lignin-ZnO nano-composite comprises the following steps:
mixing quaternized alkali lignin, inorganic alkali, soluble zinc salt and water, performing hydrothermal reaction, and adjusting the pH value to 6-8 to obtain lignin-ZnO nano-composite;
the lignin-CeO 2 The preparation method of the nano-composite comprises the following steps:
mixing quaternized alkali lignin, inorganic alkali, soluble cerium salt and water, performing hydrothermal reaction, and regulating pH value to 7.8 to obtain lignin-CeO 2 A nanocomposite.
Preferably, the biological pesticide is one or more of gibberellin, emamectin benzoate, matrine, liuyangmycin, abamectin, methoxy abamectin, validamycin, polyoxin, ningnanmycin, zhongshengmycin and agricultural resistance 12.
Preferably, the particle size of the lignin-inorganic semiconductor composite material is 150-300 nm, and the particle size of the ultraviolet-resistant biopesticide composite microcapsule is 500-800 nm.
The invention provides a preparation method of the ultraviolet-resistant biological pesticide composite microcapsule, which comprises the following steps:
mixing biological pesticide, isocyanate compound and organic solvent to obtain oil phase;
mixing lignin-inorganic semiconductor nano-composite, auxiliary emulsifier and water to obtain a water phase;
mixing the oil phase and the water phase, and emulsifying to obtain O/W type Pickering emulsion;
mixing the O/W type Pickering emulsion with a chain extender, and performing interfacial polymerization reaction to obtain the ultraviolet-resistant biopesticide composite microcapsule.
Preferably, the isocyanate compound is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate and lysine diisocyanate;
the chain extender is a polyol and/or a polyamine.
Preferably, the mass ratio of the isocyanate compound to the biological pesticide is 2-15:5-25;
the mass ratio of the isocyanate compound to the lignin-inorganic semiconductor nano-composite is 2-15:1-5;
the mass ratio of the isocyanate compound to the chain extender is 2-15:1-5.
Preferably, the temperature of the interfacial polymerization reaction is 50-80 ℃ and the time is 2-5 h.
The invention provides an anti-ultraviolet biological pesticide composite microcapsule, which comprises a microcapsule capsule wall material and biological pesticide wrapped in the microcapsule capsule wall material; the microcapsule material is polyurethane, and the microcapsule material contains lignin-inorganic semiconductor nano-composite. According to the invention, the lignin-inorganic semiconductor nano-composite is introduced into the microcapsule capsule wall material as an ultraviolet shielding agent, and under the illumination condition, photo-generated electrons are transferred to lignin molecules under the traction action of lignin unsaturated bonds, so that the separation of photo-generated electron-hole pairs in a semiconductor can be promoted, and the ultraviolet resistance of the microcapsule capsule wall material can be remarkably improved; meanwhile, lignin has the characteristic of antioxidation, and can eliminate photodegradation of biological pesticides by the photocatalytic activity of semiconductors. In the invention, polyurethane has the advantages of excellent mechanical property, thermal stability, good biocompatibility and the like, and the lignin-inorganic semiconductor nano-composite is used as a Pickering emulsifier to be added into a biological pesticide microcapsule suspension system, so that the ultraviolet photolysis resistance of the original drug is further improved.
Drawings
FIG. 1 is a microstructure image of the composite ultraviolet-resistant biopesticide microcapsule in example 1 of the present invention;
FIG. 2 shows the UV-protective effect of the composite microcapsule of the UV-protective biopesticide obtained in example 1 of the present invention;
FIG. 3 shows the UV-protective effect of the composite microcapsule of the UV-protective biopesticide obtained in example 2 of the present invention;
FIG. 4 shows the UV-protective effect of the composite microcapsule of the UV-protective biopesticide obtained in example 3 of the present invention;
FIG. 5 shows the UV-protective effect of the composite microcapsule of the UV-protective biopesticide obtained in example 4 of the present invention.
Detailed Description
The invention provides an anti-ultraviolet biological pesticide composite microcapsule, which comprises a microcapsule capsule wall material and biological pesticide wrapped in the microcapsule capsule wall material;
the microcapsule material is polyurethane, and the microcapsule material contains lignin-inorganic semiconductor nano-composite.
In the present invention, the lignin-inorganic semiconductor composite material is preferably lignin-TiO 2 Nanocomposite, lignin-ZnO nanocomposite, lignin-SiO 2 Nanocomposite and lignin-CeO 2 One or more of the nanocomposites; in the present invention, the particle diameter of the lignin-inorganic semiconductor composite material is preferably 150 to 300nm, more preferably 200 to 250nm.
The lignin-inorganic semiconductor nanocomposite is preferably contained in an amount of 30 to 50wt%, more preferably 35 to 45 wt%, and still more preferably 40wt% in the microcapsule shell.
In the present invention, the lignin-TiO 2 The method of preparing the nanocomposite preferably comprises the steps of:
mixing quaternized alkali lignin, inorganic acid, butyl titanate and water, and performing hydrothermal reaction to obtain lignin-TiO 2 A nanocomposite.
The invention has no special requirements on the source of the Quaternized Alkali Lignin (QAL), and the quaternized alkali lignin which is conventionally and commercially available in the field can be used or prepared by self. When the quaternized alkali lignin is prepared by itself, the preparation method preferably comprises:
mixing alkali lignin with 3-chloro-2-hydroxypropyl ammonium chloride, and performing substitution reaction to obtain quaternized alkali lignin.
In the present invention, the mass ratio of the Alkali Lignin (AL) to the 3-chloro-2-hydroxypropyl ammonium chloride is preferably 1 to 10:1, more preferably 3 to 6:1.
In the present invention, the mixing is preferably stirring, and the temperature of the substitution reaction is preferably 70 to 90 ℃, more preferably 80 to 85 ℃; the time is preferably 4 hours.
After the substitution reaction, the present invention preferably performs a post-treatment on the resulting substitution reaction solution. In the present invention, the post-treatment preferably includes:
and (3) dialyzing and freeze-drying the obtained substitution reaction liquid to obtain quaternized alkali lignin solid.
In the present invention, the dialysis preferably has a molecular weight cut-off of 1000 to 5000, more preferably 2000 to 3000. The method of the present invention is not particularly limited, and the method of lyophilization known to those skilled in the art may be used.
The invention mixes quaternized alkali lignin, inorganic acid, butyl titanate and water to carry out hydrothermal reaction. In the present invention, the inorganic acid is preferably hydrochloric acid and/or sulfuric acid, and the concentration of the inorganic acid is preferably 20 to 50wt%, more preferably 30 to 40wt%. In the present invention, the quaternized alkali lignin is preferably mixed with water to obtain an aqueous solution having a concentration of 20 to 60wt%, and the pH of the aqueous solution is adjusted to 1 to 5, more preferably 2 to 3, using an inorganic acid.
In the invention, the mass ratio of the quaternized alkali lignin to the butyl titanate is preferably 1:3-3:1.
In the present invention, the temperature of the hydrothermal reaction is preferably 100℃and the time is preferably 6 hours.
After the hydrothermal reaction, the method preferably carries out solid-liquid separation, solid washing and drying on the obtained hydrothermal reaction liquid to obtain lignin-TiO 2 Nanocomposite solids.
In the present invention, the lignin-SiO 2 The method of preparing the nanocomposite preferably comprises the steps of:
mixing quaternized alkali lignin, inorganic acid, tetraethoxysilane and water, and performing hydrothermal reaction to obtain lignin-TiO 2 A nanocomposite.
In the present invention, the source of the quaternized alkali lignin is the same as above, and will not be described herein.
In the present invention, the lignin-SiO 2 Specific preparation process of nano-composite and lignin-TiO 2 The nanocomposite is similar, except that the raw material butyl titanate is replaced with ethyl orthosilicate, and will not be described again.
In the present invention, the preparation method of the lignin-ZnO nanocomposite preferably includes the steps of:
mixing quaternized alkali lignin, inorganic alkali, soluble zinc salt and water, performing hydrothermal reaction, and adjusting the pH value to 6-8, more preferably 7.8, so as to obtain the lignin-ZnO nano-composite.
In the present invention, the source of the quaternized alkali lignin is the same as above, and will not be described herein. In the present invention, the inorganic base is preferably NaOH. In the present invention, the quaternized alkali lignin is preferably mixed with water to obtain an aqueous solution having a concentration of 20 to 60wt%, and the pH of the aqueous solution is adjusted to 8 to 12, more preferably 9 to 10, with an inorganic base.
In the present invention, the soluble zinc salt is preferably one or more of zinc acetate, zinc chloride, zinc nitrate and zinc sulfate. In the invention, the mass ratio of the quaternized alkali lignin to the soluble zinc salt is preferably 1:3-3:1.
In the present invention, the temperature of the hydrothermal reaction is preferably 85℃and the time is preferably 4 hours.
After the hydrothermal reaction, the invention preferably carries out solid-liquid separation, solid washing and drying on the obtained hydrothermal reaction liquid to obtain the lignin-ZnO nanocomposite.
In the present invention, the lignin-CeO 2 The method of preparing the nanocomposite preferably comprises the steps of:
mixing quaternized alkali lignin, inorganic alkali, soluble cerium salt and water, performing hydrothermal reaction, and regulating pH value to 7.8 to obtain lignin-CeO 2 A nanocomposite.
In the present invention, the source of the quaternized alkali lignin is the same as above, and will not be described herein. In the present invention, the inorganic base is preferably NaOH. In the present invention, the quaternized alkali lignin is preferably mixed with water to obtain an aqueous solution having a concentration of 20 to 60wt%, and the pH of the aqueous solution is adjusted to 8 to 12, more preferably 9 to 10, with an inorganic base.
In the present invention, the soluble cerium salt is preferably one or more of cerium sulfate, cerium nitrate and cerium chloride. In the invention, the mass ratio of the quaternized alkali lignin to the soluble cerium salt is preferably 1:3-3:1.
In the present invention, the temperature of the hydrothermal reaction is preferably 65℃and the time is preferably 4 hours.
After the hydrothermal reaction, the method preferably carries out solid-liquid separation, solid washing and drying on the obtained hydrothermal reaction liquid to obtain lignin-CeO 2 A nanocomposite.
In the invention, the biological pesticide is preferably one or more of gibberellin, emamectin benzoate, matrine, liuyang mycin, abamectin, methoxy abamectin, validamycin, polyoxin, ningnanmycin, zhongshengmycin and agricultural resistance 12. In the present invention, the mass content of the biopesticide in the uv-protective biopesticide composite microcapsule is preferably 2 to 20%, more preferably 5 to 15%, and even more preferably 10%.
In the present invention, the particle size of the ultraviolet-resistant biopesticide composite microcapsule is preferably 500 to 800nm, more preferably 600 to 700nm.
The invention provides a preparation method of the ultraviolet-resistant biological pesticide composite microcapsule, which comprises the following steps:
mixing biological pesticide, isocyanate compound and organic solvent to obtain oil phase;
mixing lignin-inorganic semiconductor nano-composite, auxiliary emulsifier and water to obtain a water phase;
mixing the oil phase and the water phase, and emulsifying to obtain O/W type Pickering emulsion;
mixing the O/W type Pickering emulsion with a chain extender, and performing interfacial polymerization reaction to obtain the ultraviolet-resistant biopesticide composite microcapsule.
The invention mixes biological pesticide, isocyanate compound and organic solvent to obtain oil phase. In the invention, the isocyanate compound is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate and lysine diisocyanate.
In the present invention, the organic solvent is preferably one or more of N-butyl acetate, isobutyl acetate, sec-butyl acetate, N-dimethyloctanoamide, N-dimethyldecanoamide, no. 200 solvent oil and No. 150 solvent oil.
In the invention, the mass ratio of the isocyanate compound to the biopesticide is preferably 2-15:5-25, more preferably 5-10:10-15.
In the present invention, the mass ratio of the isocyanate compound to the organic solvent is preferably 2 to 15:5 to 20, more preferably 5 to 10:10 to 15.
The mixing means is not particularly limited in the present invention, and mixing means well known to those skilled in the art may be used.
The invention mixes lignin-inorganic semiconductor nano-composite, auxiliary emulsifier and water to obtain water phase. In the present invention, the co-emulsifier is preferably one or more of PVA, tween-80, EL-40, EL-60, AEO-6, AEO-9 and triton X-100, more preferably PVA.
In the present invention, the mass ratio of the isocyanate compound to the lignin-inorganic semiconductor nanocomposite is preferably 2 to 15:1 to 5, more preferably 5 to 10:2 to 4.
In the present invention, the mixing means is preferably stirring mixing.
The oil phase and the water phase are mixed and emulsified to obtain the O/W type Pickering emulsion. In the present invention, the emulsification is preferably performed under stirring at a rate of preferably 300 to 1000rpm, more preferably 500 to 800rpm.
The O/W type Pickering emulsion and the chain extender are mixed for interfacial polymerization reaction to obtain the ultraviolet-resistant biological pesticide composite microcapsule. In the present invention, the chain extender is preferably a polyol and/or a polyamine. In the present invention, the polyol is preferably one or more of polyether polyol, ethylene glycol, hexylene glycol, glycerol and pentaerythritol. In the present invention, the polyether polyol is preferably one or more of polyoxyethylene glycol having a molecular weight of 200 to 4000, polyoxypropylene glycol having a molecular weight of 200 to 4000, and polytetrahydrofuran glycol having a molecular weight of 250 to 2000.
In the present invention, the polyamine is preferably one or more of ethylenediamine, hexamethylenediamine, isophoronediamine, 1, 2-propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
In the present invention, the mass ratio of the isocyanate compound to the chain extender is preferably 2 to 15:1 to 5, more preferably 5 to 10:2 to 4. In the present invention, the interfacial polymerization is preferably carried out under stirring at a rate of preferably 300 to 1000rpm, more preferably 500 to 800rpm.
In the present invention, the temperature of the interfacial polymerization reaction is preferably 50 to 80 ℃, more preferably 60 to 70 ℃; the time is preferably 2 to 5 hours, more preferably 3 to 4 hours.
After the interfacial polymerization reaction, the invention preferably adds an antifreezing agent and a dispersing agent into the obtained interfacial polymerization reaction liquid to obtain the ultraviolet-resistant biological pesticide composite microcapsule water suspension. The invention has no special requirements on the specific types of the antifreezing agent and the dispersing agent, and the antifreezing agent and the dispersing agent which are well known to the person skilled in the art can be used.
In the ultraviolet-resistant biopesticide composite microcapsule water suspending agent, the mass percentage of the antifreezing agent is preferably 1-3%, and the mass percentage of the dispersing agent is preferably 1-3%.
The ultraviolet-resistant biopesticide composite microcapsules and the preparation method thereof provided by the invention are described in detail below with reference to examples, but they are not to be construed as limiting the scope of the invention.
Example 1
(1) Preparation of quaternized alkali lignin
100g of an alkali lignin solution having a concentration of 25wt% was added to the reactor flask. 3g of 3-chloro-2-hydroxypropyl ammonium chloride were added dropwise at 85 ℃. And (3) after the dripping is completed, continuing to react for 4 hours, dialyzing and purifying the reaction liquid, and freeze-drying to obtain the quaternized alkali lignin.
(2) Preparation of lignin-ZnO nanocomposite
After dissolving quaternized alkali lignin powder, 1g NaOH with 100g water, the mixture was mixed with 5g Zn (Ac) 2 The solution was mixed and stirred and incubated at 85℃for 4h. Cooling to room temperature, regulating the pH value of the solution to 7.8, centrifuging, washing and drying to obtain the quaternized alkali lignin-ZnO nano-composite.
(3) Preparation of biopesticide microcapsule by Pickering emulsion interfacial polymerization
First, 6g of emamectin benzoate, 15g of isobutyl acetate and 8g of diphenylmethane-4, 4' -diisocyanate were mixed and stirred at room temperature until completely dissolved to form an oil phase.
Next, 2g of lignin-ZnO nanocomposite was dispersed in 60g of water, and 1g of co-emulsifier PVA was added as an aqueous phase. Mixing the water phase with the oil phase, stirring and dispersing to form the O/W Pickering emulsion.
The Pickering emulsion prepared above was transferred to a three-necked flask equipped with a mechanical stirrer and thermometer at 60℃and stirred well at 500 rpm. Adding 10g of ethylenediamine with the concentration of 20wt% into the solution to perform interfacial polymerization reaction for 2 hours to form the ultraviolet-resistant emamectin benzoate microcapsule, and adding 1.5g of antifreezing agent and 1.5g of dispersing agent into the system to obtain the 5.7wt% ultraviolet-resistant emamectin benzoate microcapsule water suspending agent.
The microstructure pictures of the obtained ultraviolet-proof emamectin benzoate microcapsules are shown in fig. 1, and the pictures (a) and (b) in fig. 1 are pictures with different magnification factors respectively. As can be seen from FIG. 1, the ultraviolet-proof emamectin benzoate microcapsule provided by the invention has a regular spherical shape, and the particle size of the ultraviolet-proof emamectin benzoate microcapsule is 500-800 nm.
The common emamectin benzoate microcapsule is prepared, and the difference with the preparation of the ultraviolet-resistant emamectin benzoate microcapsule is that lignin-inorganic semiconductor nano-composite with ultraviolet shielding is not added to be used as a Pickering emulsifier, and the emulsifier is PVA.
The methanol dispersion liquid of the ultraviolet-proof emamectin benzoate microcapsule suspending agent, the methanol solution of the original emamectin benzoate and the methanol dispersion liquid of the common emamectin benzoate microcapsule are prepared at the same concentration, the solutions are respectively irradiated under ultraviolet lamps (36W and 254 nm), the samples are taken at intervals, the concentration is calculated by high performance liquid chromatography, the graph of the residual content of the original emamectin benzoate microcapsule and the time relation chart is shown as figure 2, and the common emamectin benzoate microcapsule and the ultraviolet-proof emamectin benzoate microcapsule have certain protection effect on the degradation of the emamectin benzoate, but the degradation rate of the emamectin benzoate in the ultraviolet-proof emamectin benzoate microcapsule is obviously lower than that of the original emamectin benzoate microcapsule and the common emamectin benzoate microcapsule, so that the ultraviolet-proof emamectin benzoate microcapsule has good ultraviolet-proof effect.
Example 2
(1) Preparation of quaternized alkali lignin
100g of an alkali lignin solution having a concentration of 25wt% was added to the reactor flask. At 85℃5g of 3-chloro-2-hydroxypropyl ammonium chloride are added dropwise. And (3) after the dripping is completed, continuing to react for 4 hours, dialyzing and purifying the reaction liquid, and freeze-drying to obtain the quaternized alkali lignin.
(2) Quaternized alkali lignin-TiO 2 Preparation of nanocomposites
The quaternized alkali lignin was formulated into a 5% aqueous solution with stirring, and the pH of the solution was adjusted to 1. Adding 5g of butyl titanate into the solution, reacting for 6 hours at 100 ℃, collecting precipitate after the reaction is finished, washing and drying to obtain QAL-TiO 2 。
(3) Preparation of biopesticide microcapsule by Pickering emulsion interfacial polymerization
Firstly, 3g of validamycin, 10g of n-butyl acetate and 9g of isophorone diisocyanate are stirred and mixed at room temperature until the components are completely dissolved to form an oil phase;
secondly, dispersing 2g of quaternized alkali lignin-TiO 2 nano-composite into 60g of water, and adding 1g of co-emulsifier PVA as a water phase;
finally, mixing the water phase with the oil phase, stirring and dispersing to form the O/W type Pickering emulsion.
The Pickering emulsion prepared above was transferred to a three-necked flask equipped with a mechanical stirrer and thermometer at 50℃and stirred well at 400 rpm. 10g of triethylene tetramine with the concentration of 30wt% is added into the solution to carry out interfacial polymerization reaction to form the ultraviolet-proof validamycin microcapsule, and 1g of antifreezing agent and 1g of dispersing agent are added into the system to obtain the 3wt% ultraviolet-proof validamycin microcapsule water suspension.
The general validamycin microcapsule is prepared by referring to the method of the embodiment 1, the methanol dispersion liquid of the validamycin microcapsule suspending agent, the methanol solution of the validamycin raw drug and the methanol dispersion liquid of the general validamycin microcapsule with the same concentration are prepared, the solutions are respectively irradiated under ultraviolet lamps (36W and 254 nm), samples are taken at intervals, the concentration is calculated by using high performance liquid chromatography, the relation between the residual content of the raw drug and the time is shown as figure 3, and the general validamycin microcapsule and the ultraviolet validamycin microcapsule have a certain protection effect on the degradation of the validamycin, but the degradation rate of the validamycin in the ultraviolet validamycin microcapsule is obviously lower than that of the raw drug and the general validamycin microcapsule, which indicates that the ultraviolet validamycin microcapsule has good ultraviolet resistance effect.
Example 3
(1) Preparation of quaternized alkali lignin
100g of an Alkali Lignin (AL) solution having a concentration of 25wt% was added to the reactor flask. At 85℃10g of 3-chloro-2-hydroxypropyl ammonium chloride are added dropwise. After the dripping is completed, the reaction is continued for 4 hours, and the reaction liquid is dialyzed and purified and freeze-dried to obtain QAL. The reaction route is as follows:
(2) Quaternized lignin-SiO 2 Nanocomposite preparation
6g of quaternized lignin-SiO are stirred 2 The nanocomposite is formulated as an aqueous suspension of a concentration. Adding 10g of tetraethoxysilane into the solution, reacting for 6 hours at 100 ℃, collecting precipitate after the reaction is finished, washing and drying to obtain quaternized lignin-SiO 2 A nanocomposite.
(3) Preparation of biopesticide microcapsule by Pickering emulsion interfacial polymerization
First, 5g of avermectin, 12g of sec-butyl acetate and 8g of isophorone diisocyanate were mixed and stirred at room temperature until completely dissolved to form an oil phase.
Next, 1g of quaternized lignin-SiO 2 The nanocomposite was dispersed in 70g of water, and 1g of co-emulsifier PVA was added as an aqueous phase. Mixing the water phase with the oil phase, stirring and dispersing to form the O/W Pickering emulsion.
The Pickering emulsion prepared above was transferred to a three-necked flask equipped with a mechanical stirrer and thermometer at 65℃and stirred uniformly at a certain speed. 15g of glycerol with the concentration of 50wt% is added into the solution to carry out interfacial polymerization reaction for 3 hours to form the ultraviolet-resistant avermectin microcapsule, and 1g of antifreezing agent and 1g of dispersing agent are added into the system to obtain the 5wt% ultraviolet-resistant avermectin microcapsule water suspending agent.
The method of reference example 1 is used for preparing the common avermectin microcapsule, the suspending agent methanol dispersion liquid of the ultraviolet-proof avermectin microcapsule, the original drug methanol solution of the avermectin and the methanol dispersion liquid of the common avermectin microcapsule are prepared at the same concentration, the solutions are respectively irradiated under ultraviolet lamps (36W and 254 nm), samples are taken at intervals, the concentration is calculated by high performance liquid chromatography, the relation chart of the residual content of the original drug and the time is shown as figure 4, and as can be seen from figure 4, the common avermectin microcapsule and the ultraviolet-proof avermectin microcapsule have a certain protection effect on the degradation of the avermectin, but the degradation rate of the avermectin in the ultraviolet-proof avermectin microcapsule is obviously lower than that of the original drug and the common avermectin microcapsule, so that the ultraviolet-proof avermectin microcapsule has good ultraviolet-proof effect.
Example 4
(1) Preparation of quaternized alkali lignin
100g of an alkali lignin solution having a concentration of 25wt% was added to the reactor flask. At 85℃4g of 3-chloro-2-hydroxypropyl ammonium chloride are added dropwise. And (3) after the dripping is completed, continuing to react for 4 hours, dialyzing and purifying the reaction liquid, and freeze-drying to obtain the quaternized alkali lignin.
(2) Lignin-CeO 2 Preparation of nanocomposites
Dissolving quaternized alkali lignin powder and 10g NaOH with 100g water, mixing with CeCl 3 The solution was mixed and stirred and incubated at 85℃for 4h. Cooling to room temperature, regulating the pH of the solution to 7.8, centrifuging, washing and drying to obtain quaternized alkali lignin-CeO 2 A nanocomposite.
(3) Preparation of biopesticide microcapsule by Pickering emulsion interfacial polymerization
First, 2g of gibberellin, 8g of isobutyl acetate and 8g of diphenylmethane-4, 4' -diisocyanate were mixed and stirred at room temperature until completely dissolved to form an oil phase.
Next, 2g lignin-CeO was added 2 The nanocomposite was dispersed in 65g of water, and 1g of PVA was added as an aqueous phase. Mixing the water phase with the oil phase, stirring and dispersing to form the O/W Pickering emulsion.
The Pickering emulsion prepared above was transferred to a three-necked flask equipped with a mechanical stirrer and thermometer at 60℃and stirred well at 500 rpm. 15g of tetraethylenepentamine with the concentration of 10wt% is added into the solution to carry out interfacial polymerization reaction for 2 hours to form the ultraviolet-proof gibberellin microcapsule, and 1.5g of antifreezing agent and 1.5g of dispersing agent are added into the system to obtain the ultraviolet-proof gibberellin microcapsule water suspending agent with the concentration of 2 wt%.
The method of reference example 1 is used for preparing ordinary gibberellin microcapsule, the same concentration of the suspension agent methanol dispersion liquid of the anti-ultraviolet gibberellin microcapsule, the gibberellin raw medicine methanol solution and the ordinary gibberellin microcapsule methanol dispersion liquid are prepared, the solutions are respectively irradiated under ultraviolet lamps (36W and 254 nm), samples are taken at intervals, the concentration is calculated by high performance liquid chromatography, the relation between the residual content of raw medicine and time is shown as a graph in figure 5, and as can be seen from the graph in figure 5, the ordinary gibberellin microcapsule and the anti-ultraviolet gibberellin microcapsule have a certain protection effect on the degradation of gibberellin, but the degradation rate of the gibberellin in the anti-ultraviolet gibberellin microcapsule is obviously lower than that of the raw medicine and the ordinary gibberellin microcapsule, so that the anti-ultraviolet effect of the anti-ultraviolet gibberellin microcapsule is good.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (1)
1. An anti-ultraviolet biological pesticide composite microcapsule comprises a microcapsule capsule wall material and biological pesticide wrapped in the microcapsule capsule wall material;
the microcapsule material is polyurethane, and the microcapsule material contains lignin-inorganic semiconductor nano-composite;
the lignin-inorganic semiconductor composite material is a lignin-ZnO nano composite; the biological pesticide is emamectin benzoate;
the preparation method of the ultraviolet-resistant biological pesticide composite microcapsule comprises the following steps:
(1) Preparation of quaternized alkali lignin:
adding 100g of alkali lignin solution with the concentration of 25wt% into a reactor flask, dropwise adding 3g of 3-chloro-2-hydroxypropyl ammonium chloride at the temperature of 85 ℃, continuing to react for 4 hours after the dropwise adding is completed, dialyzing and purifying the reaction solution, and freeze-drying to obtain quaternized alkali lignin;
(2) Preparation of lignin-ZnO nanocomposite:
after dissolving quaternized alkali lignin powder, 1g NaOH with 100g water, the mixture was mixed with 5g Zn (Ac) 2 Mixing and stirring the solution, preserving the temperature at 85 ℃ for 4 hours, cooling to room temperature, regulating the pH of the solution to 7.8, centrifuging, washing and drying to obtain the quaternized alkali lignin-ZnO nano-composite;
(3) Preparing a biological pesticide microcapsule by Pickering emulsion interfacial polymerization:
first, 6g of emamectin benzoate, 15g of isobutyl acetate and 8g of diphenylmethane-4, 4' -diisocyanate are mixed and stirred at room temperature until complete dissolution forms an oil phase;
secondly, dispersing 2g of lignin-ZnO nano-composite into 60g of water, adding 1g of co-emulsifier PVA as a water phase, mixing the water phase with the oil phase, and stirring and dispersing to form O/W type Pickering emulsion;
transferring the Pickering emulsion prepared above into a three-necked flask with a mechanical stirrer and a thermometer at 60 ℃, uniformly stirring at 500rpm, adding 10g of ethylenediamine with concentration of 20wt% into the solution, and performing interfacial polymerization for 2h to form an ultraviolet-resistant emamectin benzoate microcapsule; the ultraviolet-proof emamectin benzoate microcapsule has a regular spherical shape, and the particle size of the ultraviolet-proof emamectin benzoate microcapsule is 500-800 nm.
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