CN113040160A - Pesticide microcapsule suspending agent and preparation method thereof - Google Patents
Pesticide microcapsule suspending agent and preparation method thereof Download PDFInfo
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- CN113040160A CN113040160A CN202110317628.4A CN202110317628A CN113040160A CN 113040160 A CN113040160 A CN 113040160A CN 202110317628 A CN202110317628 A CN 202110317628A CN 113040160 A CN113040160 A CN 113040160A
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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
- 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
- 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
- A01N25/02—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 liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/18—Nitro compounds
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
Abstract
The invention relates to the technical field of pesticide preparations, and provides a pesticide microcapsule suspending agent and a preparation method thereof. In the invention, the polyisocyanate prepolymer is used as a component of an oil phase, is emulsified with a water phase and then is subjected to crosslinking curing, so that side reactions can be prevented, and the problems of poor stability and low encapsulation efficiency of the pesticide microcapsule suspending agent prepared by directly using polyisocyanate and polyol to react at an oil-water interface to form a microcapsule shell and then performing crosslinking curing can be solved. Experimental results show that the pesticide microcapsule suspending agent provided by the invention is excellent in stability, and the pesticide encapsulation rate can reach 95%.
Description
Technical Field
The invention relates to the technical field of pesticide preparations, in particular to a pesticide microcapsule suspending agent and a preparation method thereof.
Background
At present, the traditional pesticide formulations mainly comprise missible oil, wettable powder, aqueous emulsion, aqueous suspension and the like, but the formulations still have a plurality of defects in the processing and using processes, such as low pesticide utilization rate, easy generation of phytotoxicity, environmental pollution, short shelf life, degradation and loss of effective components and the like. The pesticide microcapsule has the effects of protecting sensitive components, prolonging the lasting period, reducing the toxicity of the pesticide, improving the stability of the pesticide to environmental factors such as light, heat, pH and the like, improving the effective utilization rate of the pesticide, reducing the using amount of the pesticide, and has great advantages compared with the traditional pesticide dosage form.
The preparation method of the pesticide microcapsule suspending agent at the present stage mainly comprises two methods: the interfacial polymerization method is characterized in that a capsule wall film forming reaction occurs on an immiscible oil-water two-phase interface, and the reaction can be carried out at normal temperature. The other is an in-situ polymerization method, which comprises the steps of mixing the original drug, the solvent, the emulsifier and water, shearing the mixture into an oil-in-water emulsion by using a homogenizer, adding the water-soluble film-forming agent into the emulsion-like pesticide, heating, adding the catalyst, then coating the mixture to form a film, and adding a proper amount of auxiliary agent after the reaction is finished to prepare the microcapsule suspending agent. In both preparation methods: the in-situ polymerization method has the advantages of complex process flow, long polymerization period, large equipment investment and relatively harsh operating conditions. The interfacial polymerization method has the advantages of simple process, mild operation conditions, small equipment investment, short production period and easy mastering of production technology, so the interfacial polymerization method is usually adopted to prepare the pesticide microcapsule suspending agent at the present stage. For preparing the pesticide microcapsule preparation by the polymerization method, the stability and the encapsulation efficiency of the emulsion are key factors for improving the utilization rate of the pesticide and the slow release effect of the pesticide.
The microcapsule taking polyurethane as the wall material has the characteristics of good biocompatibility, easy adjustment of mechanical property and structure and the like, and is widely applied to the industrial production of pesticide microcapsules. The traditional method for preparing the pesticide microcapsule suspending agent by taking polyurethane as a wall material is to directly use polyisocyanate and polyol to react at an oil-water interface to form a microcapsule shell, and then carry out crosslinking and solidification, the reaction process is simple, but because the reaction for forming the microcapsule shell at the oil-water interface has higher control requirements on temperature and reaction time, emulsion breaking can be realized at an excessively high temperature, the reaction is incomplete due to excessively low temperature, the reaction time must be prolonged, and the polyisocyanate is in a water-containing system, and part of the polyisocyanate is easy to react with water to cause the loss of raw materials and the generation of byproducts, so that the prepared pesticide microcapsule suspending agent has poor stability and low encapsulation rate. Therefore, it is highly desirable to provide a pesticide microcapsule suspension with good stability and high encapsulation efficiency and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a pesticide microcapsule suspending agent with good stability and high encapsulation efficiency and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a pesticide microcapsule suspending agent which is prepared from the following raw materials in parts by weight:
preferably, the preparation method of the polyisocyanate prepolymer comprises the following steps: polyether polyol, polyisocyanate and dibutyltin dilaurate are mixed for polymerization reaction to obtain the polyisocyanate prepolymer.
Preferably, the mass ratio of the polyether polyol, the polyisocyanate and the dibutyltin dilaurate is 1 (1.5-6) to (0.001-0.01).
Preferably, the temperature of the polymerization reaction is 70-85 ℃, and the time of the polymerization reaction is 2-5 h.
Preferably, the polyisocyanate includes one or two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, and lysine diisocyanate.
Preferably, the polyether polyol comprises one or two of polyoxyethylene glycol with the molecular weight of 200-4000, polyoxypropylene glycol with the molecular weight of 200-4000 and polytetrahydrofuran glycol with the molecular weight of 250-2000.
Preferably, the pesticide raw pesticide comprises one or more of emamectin benzoate, pyraclostrobin, pendimethalin, abamectin, chlorpyrifos, thiamethoxam and butachlor.
Preferably, the emulsifier comprises one or more of tween series, polyvinyl alcohol, OP series, NP series, EL series and AEO series.
Preferably, the curing agent comprises one or more of ethylenediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
The invention also provides a preparation method of the pesticide microcapsule suspending agent in the technical scheme, which comprises the following steps:
(1) mixing the pesticide raw material, an organic solvent and a polyisocyanate prepolymer to obtain an oil phase;
(2) dissolving an emulsifier in deionized water to obtain a water phase;
(3) mixing the oil phase obtained in the step (1) and the water phase obtained in the step (2) and emulsifying to obtain emulsion;
(4) and (4) mixing a chain extender and a curing agent with the emulsion obtained in the step (3) to perform a crosslinking reaction to obtain the pesticide microcapsule suspending agent.
The invention provides a pesticide microcapsule suspending agent which is prepared from the following raw materials in parts by weight: 15-35 parts of polyisocyanate prepolymer, 5-20 parts of pesticide raw material, 30-50 parts of organic solvent, 5-20 parts of emulsifier, 60-70 parts of deionized water, 1-10 parts of chain extender and 1-10 parts of curing agent. The invention takes polyisocyanate prepolymer, pesticide raw medicine and organic solvent as oil phase, emulsifier and deionized water as water phase, and when in use, the oil phase and the water phase are directly emulsified and then cross-linked and solidified to obtain the pesticide microcapsule suspending agent. In the invention, the polyisocyanate prepolymer is used as a component of an oil phase, is emulsified with a water phase and then is subjected to crosslinking curing, so that side reactions can be prevented, and the problems of poor stability and low encapsulation efficiency of the pesticide microcapsule suspending agent prepared by directly using polyisocyanate and polyol to react at an oil-water interface to form a microcapsule shell and then performing crosslinking curing can be solved. Experimental results show that the pesticide microcapsule suspending agent provided by the invention is excellent in stability, and the pesticide encapsulation rate can reach 95%.
Drawings
Fig. 1 is an SEM image of the pesticidal microcapsule suspension prepared in example 1 of the present invention.
Detailed Description
The invention provides a pesticide microcapsule suspending agent which is prepared from the following raw materials in parts by weight:
in the invention, the raw materials for preparing the pesticide microcapsule suspending agent comprise 15-35 parts by weight of polyisocyanate prepolymer, preferably 20-30 parts by weight, and more preferably 25-30 parts by weight. In the invention, the polyisocyanate prepolymer used as a raw material for preparing the pesticide microcapsule suspending agent can be directly crosslinked and cured to quickly form a microcapsule shell, so that side reactions can be prevented, and the stability and the encapsulation efficiency of the pesticide microcapsule suspending agent can be improved.
In the present invention, the preparation method of the polyisocyanate prepolymer preferably includes: polyether polyol, polyisocyanate and dibutyltin dilaurate are mixed for polymerization reaction to obtain the polyisocyanate prepolymer. In the invention, the prepolymer prepared by the method has the advantage of good stability.
In the invention, the polyether polyol preferably comprises one or two of polyoxyethylene glycol with the molecular weight of 200-4000, polyoxypropylene glycol with the molecular weight of 200-4000 and polytetrahydrofuran glycol with the molecular weight of 250-2000, and more preferably comprises one or two of polyoxyethylene glycol with the molecular weight of 400-1000, polyoxyethylene glycol with the molecular weight of 600-800 and polytetrahydrofuran glycol with the molecular weight of 1000-2000. The source of the polyether polyol in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used. In the present invention, the polyether polyol is used as a main raw material for preparing the polyurethane microcapsule.
In the present invention, the polyisocyanate preferably includes one or two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate, and lysine diisocyanate, and more preferably includes one or two of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and isopropyl acetate. The source of the polyisocyanate in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used. In the invention, the polyisocyanate is used as a raw material for polymerization reaction, and can be polymerized with polyether polyol to obtain a polyisocyanate prepolymer.
In the present invention, the dibutyltin dilaurate is used as a catalyst for polymerization. The source of dibutyltin dilaurate is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the ratio of the amounts of the polyether polyol, polyisocyanate and dibutyltin dilaurate is preferably 1 (1.5-6) to (0.001-0.01), more preferably 1: (2-4): (0.002-0.006). In the present invention, when the ratio of the amounts of the polyether polyol, the polyisocyanate and the dibutyltin dilaurate is in the above range, the polymerization reaction can be sufficiently performed.
The operation mode of mixing the polyether polyol, the polyisocyanate and the dibutyltin dilaurate is not particularly limited in the present invention, and the mixing mode known to those skilled in the art can be adopted. In the present invention, the polyether polyol, polyisocyanate and dibutyltin dilaurate in combination preferably comprises: firstly, removing water from polyether polyol, and then mixing the polyether polyol after water removal with polyisocyanate and dibutyltin dilaurate.
The operation of removing water from the polyether polyol is not particularly limited, and the water in the polyether polyol can be removed by adopting a water removing mode commonly used by a person skilled in the art. In the invention, the operation of removing water from the polyether polyol is preferably reduced pressure distillation, and the vacuum degree of the reduced pressure distillation is preferably 0.09 MPa; the temperature of the reduced pressure distillation is preferably 100-120 ℃, and more preferably 105-115 ℃; the time of the reduced pressure distillation is preferably 2-4 h, and more preferably 3-4 h. In the present invention, the removal of water from the polyether polyol can prevent the occurrence of side reactions during the polymerization reaction due to the presence of water, and when the parameter of the vacuum distillation is in the above range, the water in the polyether polyol can be sufficiently removed.
In the present invention, the mixing of the polyether polyol after water removal with the polyisocyanate and dibutyltin dilaurate is preferably performed under mechanical stirring. The mechanical stirring speed is not particularly limited, and the components can be uniformly mixed.
After polyether polyol, polyisocyanate and dibutyltin dilaurate are mixed, the mixed mixture is subjected to polymerization reaction to obtain a polyisocyanate prepolymer.
In the invention, the temperature of the polymerization reaction is preferably 70-85 ℃, and more preferably 75-80 ℃; the time of the polymerization reaction is preferably 2-5 h, and more preferably 3-4 h; the polymerization is preferably carried out under nitrogen. The flow rate of the nitrogen is not particularly limited and can be adjusted according to the requirement. In the present invention, the nitrogen gas can prevent the occurrence of side reactions. In the present invention, when the temperature and time of the polymerization reaction are within the above ranges, the polyether polyol and the polyisocyanate can be sufficiently reacted.
In the invention, the raw materials for preparing the pesticide microcapsule suspending agent comprise 5-20 parts by weight of pesticide raw materials, preferably 10-20 parts by weight, and more preferably 10-15 parts by weight. In the invention, the pesticide raw pesticide preferably comprises one or more of emamectin benzoate, pyraclostrobin, pendimethalin, abamectin, chlorpyrifos, thiamethoxam and butachlor. In the invention, the polyisocyanate prepolymer is used as one of the raw materials of the pesticide microcapsule suspending agent, so that the pesticide microcapsule suspending agent can be prevented from reacting during preparation, and the pesticide microcapsule suspending agent provided by the invention can be suitable for various types of pesticide raw materials.
In the invention, the raw materials for preparing the pesticide microcapsule suspending agent comprise 30-50 parts by weight of organic solvent, preferably 35-45 parts by weight, and more preferably 35-40 parts by weight. In the present invention, the organic solvent preferably includes one or more of dichloromethane, xylene, ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, acetone, azomethylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, and mineral spirits No. 150, and more preferably includes ethyl acetate, acetone, isopropyl acetate, or dichloromethane. In the invention, the organic solvent, the polyisocyanate prepolymer and the pesticide raw material fully form a stably dispersed oil phase.
In the invention, the raw materials for preparing the pesticide microcapsule suspending agent comprise 5-20 parts by weight of emulsifier, preferably 10-15 parts by weight. In the present invention, the emulsifier preferably includes one or more of Tween series, polyvinyl alcohol, OP series, NP series, EL series, and AEO series, and more preferably includes polyethylene, EL-60, or EL-40. In the invention, when the emulsifier is the above kind, the stability of the emulsion can be improved, and the pesticide microcapsule with uniform particle size can be obtained more favorably.
In the invention, the raw materials for preparing the pesticide microcapsule suspending agent comprise 60-70 parts by weight of deionized water. In the invention, the deionized water is used as a solvent and can form a water phase after being mixed with an emulsifier.
In the invention, the raw materials for preparing the pesticide microcapsule suspending agent comprise 1-10 parts by weight of chain extender, preferably 2-8 parts by weight, and more preferably 5-8 parts by weight. In the present invention, the chain extender preferably includes one or more of ethylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-propanediol, dipropylene glycol, 1, 6-hexanediol, glycerol, triethanolamine and pentaerythritol. In the invention, the chain extender can react with polyisocyanate to cause the molecular chain to be diffused and extended, thus forming the polyisocyanate prepolymer.
In the invention, the raw materials for preparing the pesticide microcapsule suspending agent comprise 1-10 parts by weight of curing agent, preferably 2-8 parts by weight, and more preferably 5-8 parts by weight. In the present invention, the curing agent preferably includes one or more of ethylenediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, more preferably diethylenetriamine, isophoronediamine, hexamethylenediamine or ethylenediamine. In the invention, the curing agent can promote a crosslinking reaction and improve the strength of the polyurethane pesticide microcapsule.
The invention takes polyisocyanate prepolymer, pesticide raw medicine and organic solvent as oil phase, and when in use, the oil phase and the water phase are directly emulsified and then cross-linked and solidified to obtain the pesticide microcapsule suspending agent. In the invention, the polyisocyanate prepolymer is used as a component of an oil phase, is emulsified with a water phase and then is subjected to crosslinking curing, so that side reactions can be prevented, and the problems of poor stability and low encapsulation efficiency of the pesticide microcapsule suspending agent prepared by directly using polyisocyanate and polyol to react at an oil-water interface to form a microcapsule shell and then performing crosslinking curing can be solved.
The invention also provides a preparation method of the pesticide microcapsule suspending agent in the technical scheme, which comprises the following steps:
(1) mixing the pesticide raw material, an organic solvent and a polyisocyanate prepolymer to obtain an oil phase;
(2) dissolving an emulsifier in deionized water to obtain a water phase;
(3) mixing the oil phase obtained in the step (1) and the water phase obtained in the step (2) and emulsifying to obtain emulsion;
(4) and (4) mixing a chain extender and a curing agent with the emulsion obtained in the step (3) to perform a crosslinking reaction to obtain the pesticide microcapsule suspending agent.
The invention mixes the pesticide original drug, the organic solvent and the polyisocyanate prepolymer to obtain the oil phase.
The operation method for mixing the pesticide raw material, the organic solvent and the polyisocyanate prepolymer is not particularly limited, and the components can be uniformly mixed. In the invention, the mixing of the pesticide raw material, the organic solvent and the polyisocyanate prepolymer preferably comprises the following steps: dissolving a pesticide raw material in an organic solvent to obtain a pesticide raw material solution, and mixing the pesticide raw material solution with the polyisocyanate prepolymer. In the invention, when the pesticide raw material, the organic solvent and the polyisocyanate prepolymer are mixed in the above manner, all the components can be fully and uniformly mixed.
The invention dissolves the emulsifier in the deionized water to obtain the water phase. The operation method for dissolving the emulsifier in the deionized water is not particularly limited, and the emulsifier can be dissolved in the deionized water.
After the oil phase and the water phase are respectively obtained, the oil phase and the water phase are mixed and emulsified to obtain the emulsion.
The operation mode of mixing the oil phase and the water phase is not particularly limited in the present invention, and a mixing mode known to those skilled in the art may be adopted. In the present invention, the mixing is preferably mechanical stirring. The speed and time of the mechanical stirring are not particularly limited, and the components can be uniformly mixed. In the present invention, the oil phase and the water phase are mixed to facilitate the subsequent emulsification.
In the invention, the emulsification is preferably high-speed shearing, and the speed of the high-speed shearing is preferably 8000-20000 rpm, more preferably 10000-15000 rpm; the high-speed shearing time is preferably 5-15 min, and more preferably 10-15 min. In the present invention, when the high-speed shearing parameter is in the above range, the mixed solution of the oil phase and the water phase can be sufficiently emulsified to obtain a uniform and stable emulsion.
After the emulsion is obtained, the chain extender and the curing agent are mixed with the emulsion to carry out crosslinking reaction, so as to obtain the pesticide microcapsule suspending agent.
In the present invention, the mixing of the chain extender and the curing agent with the emulsion is preferably performed under mechanical agitation. In the present invention, the mechanical agitation can promote the chain extender, the curing agent, and the emulsion to be uniformly mixed.
In the invention, the temperature of the crosslinking reaction is preferably 60-80 ℃, and more preferably 70-80 ℃; the time of the crosslinking reaction is preferably 2-4 h, and more preferably 3-4 h. In the present invention, the crosslinking reaction can be sufficiently performed when the temperature and time of the crosslinking reaction are within the above ranges.
In the invention, the stability of the emulsion is a key factor of interfacial polymerization, the traditional interfacial polymerization method directly uses polyisocyanate and polyol to react at an oil-water interface to form a microcapsule shell, and then carries out crosslinking and curing, the reaction process is simple, but because the control requirements of the first step reaction on the temperature and the reaction time are higher, the emulsion is broken by overhigh temperature, the reaction is incomplete due to overhigh temperature, the reaction time can be prolonged, and the polyisocyanate is in a water-containing system, so that the raw material loss and the generation of byproducts are caused by partial easy reaction with water, and the stability and the encapsulation rate of the polyurethane pesticide microcapsule are low. According to the preparation method provided by the invention, the polyurethane prepolymer is used as an oil phase, and can be directly crosslinked and cured after emulsification, so that the microcapsule shell can be quickly formed, and the stability and the encapsulation efficiency of the polyurethane pesticide microcapsule can be improved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Adding 2.5g of polyoxyethylene glycol (PEG-400) with molecular weight of 400 into a four-neck flask with a stirrer and a thermometer, and distilling under reduced pressure for 2h at 110 ℃ and a vacuum degree of 0.09MPa to remove water in the raw materials; heating the dewatered PEG-400, 5g of isophorone diisocyanate, 4g of ethyl acetate and 0.02g of dibutyltin dilaurate to 70 ℃ under the stirring condition, reacting for 3h at 300rpm in a nitrogen atmosphere, and cooling to room temperature to obtain a polyurethane prepolymer; (the ratio of the amounts of substances of polyether polyol, polyisocyanate and dibutyltin dilaurate was 1: 3.6: 0.005).
(2) Dissolving 5g of emamectin benzoate in 10g of ethyl acetate, adding the ethyl acetate into the polyurethane prepolymer obtained in the step (1), and uniformly stirring to obtain an oil phase;
(3) weighing 2g of polyvinyl alcohol, and dissolving in 50mL of deionized water to prepare a water phase;
(4) mixing the oil phase and the water phase, and shearing and emulsifying at a high speed of 10000rpm for 5min to obtain uniform and stable emulsion;
(5) 1g of 1, 4g of butanediol and 0.5g of diethylenetriamine are added into the emulsion, and the mixture is cured and reacted for 3 hours at 500rpm and 60 ℃ to obtain the polyurethane pesticide microcapsule suspending agent.
The pesticide microcapsule suspension prepared in this example 1 was observed with a scanning electron microscope to obtain an SEM image as shown in fig. 1. As can be seen from FIG. 1, the polyurethane pesticide microcapsule prepared by the embodiment has regular and spherical shape, the average particle size is 600nm, and the particle size distribution is uniform.
The method for measuring the encapsulation efficiency of the microcapsule comprises the following steps:
accurately weighed out 0.01g of the dry polyurethane pesticide microcapsules prepared in this example (to the nearest 0.001g) and placed in a 100mL volumetric flask, the volume of the sample was measured with methanol: water 1: the solution of 1 is added to 100mL, kept stand for 5min, centrifuged and then measured for absorbance by an ultraviolet spectrophotometry. Then, the volumetric flask was sonicated for 15min with a sonicator and centrifuged, and the absorbance was measured again. Calculating the mass of the active ingredients outside the microcapsule by a standard curve method, and calculating the encapsulation efficiency according to a formula (I):
the pesticide encapsulation efficiency of the pesticide microcapsule suspension prepared in this example was 95% as obtained by the above method.
Example 2
(1) Adding 3g of PEG-600 into a four-neck flask with a stirrer and a thermometer, and distilling under reduced pressure for 2h at 110 ℃ and a vacuum degree of 0.09MPa to remove water in the raw materials; heating the dewatered PEG-600, 3g of toluene diisocyanate, 3g of acetone and 0.02g of dibutyltin dilaurate to 70 ℃ under the stirring condition, reacting for 2h at 300rpm in a nitrogen atmosphere, and cooling to room temperature to obtain a polyurethane prepolymer; (ii) a (the ratio of the amounts of the substances of polyether polyol, polyisocyanate and dibutyltin dilaurate is 1: 3.45: 0.006);
(2) dissolving 9g of pyraclostrobin in 15g of acetone, adding the acetone into the synthesized prepolymer, and uniformly stirring to prepare an oil phase;
(3) weighing 6g of EL-40, and dissolving in 50mL of deionized water to prepare a water phase;
(4) mixing the oil phase and the water phase, and shearing and emulsifying at a high speed of 10000rpm for 5min to obtain uniform and stable emulsion;
(5) adding 1g of triethanolamine and 0.5g of isophorone diamine into the emulsion, and carrying out curing reaction at 600rpm and 80 ℃ for 6h to obtain the polyurethane pesticide microcapsule suspending agent.
The pyraclostrobin polyurethane microcapsule emulsion prepared by the embodiment is milk white, the average particle size of the polyurethane microcapsule is 400nm, and the pesticide encapsulation rate obtained by the method in the embodiment 1 is 92%.
Example 3
(1) Adding 8g of polytetrahydrofuran diol (PTMG-1000) with molecular weight of 1000 into a four-neck flask with a stirrer and a thermometer, and distilling under reduced pressure for 2h at 110 deg.C and vacuum degree of 0.09MPa to remove water in the raw materials; heating the dewatered PTMG-1000, 4g of hexamethylene diisocyanate, 5g of isopropyl acetate and 0.02g of dibutyltin dilaurate to 70 ℃ under the condition of stirring, reacting for 2h under the condition of stirring at 300rpm in a nitrogen atmosphere, and cooling to room temperature after the reaction is finished to obtain a polyurethane prepolymer (the mass ratio of polyether polyol to polyisocyanate to dibutyltin dilaurate is 1: 2.98: 0.004);
(2) dissolving 15g of pendimethalin in 20g of butyl acetate, adding the solution into the synthesized prepolymer, and uniformly stirring to obtain an oil phase;
(3) weighing 8gEL-60, and dissolving in 50mL deionized water to obtain a water phase;
(4) mixing the oil phase and the water phase, and shearing and emulsifying at a high speed of 10000rpm for 10min to obtain uniform and stable emulsion;
(5) and adding 1g of glycerol and 0.8g of hexamethylenediamine into the emulsion, and carrying out curing reaction at 600rpm and 70 ℃ for 3h to obtain the polyurethane pesticide microcapsule suspending agent.
The pendimethalin polyurethane microcapsule emulsion prepared in the embodiment is light yellow, the average particle size of the polyurethane microcapsule is 700nm, and the pesticide encapsulation efficiency obtained by the method in the embodiment 1 is 91%.
Example 4
(1) 2g of polyoxypropylene diol having a molecular weight of 800 (PPG-800) was charged into a four-necked flask equipped with a stirrer and a thermometer, and the mixture was distilled under reduced pressure at 110 ℃ under a vacuum of 0.09MPa for 2 hours to remove water from the starting materials. Weighing 2g of PEG800 in a four-neck flask, and distilling under reduced pressure for 1h at 110 ℃ and under the vacuum degree of 0.09MPa to remove water in the raw materials; heating the dewatered PPG-800, 2g of diphenylmethane diisocyanate, 5g of dichloromethane and 0.01g of dibutyltin dilaurate to 70 ℃ under the stirring condition, stirring and reacting at 300rpm for 3h under the nitrogen atmosphere, and cooling to room temperature after the reaction is finished to obtain a polyurethane prepolymer (the mass ratio of polyether polyol to polyisocyanate to dibutyltin dilaurate is 1: 3.2: 0.006);
(2) dissolving 7g of abamectin in 10g of dichloromethane, adding the dichloromethane into the synthesized prepolymer, and uniformly stirring to obtain an oil phase;
(3) weighing 1.5g of polyvinyl alcohol, and dissolving in 50mL of deionized water to prepare a water phase;
(4) mixing the oil phase and the water phase, and shearing and emulsifying at a high speed of 10000rpm for 10min to obtain uniform and stable emulsion;
(5) adding 1g of ethylene glycol and 1.5g of ethylenediamine into the emulsion, and carrying out curing reaction at 500rpm and 70 ℃ for 3h to obtain the polyurethane pesticide microcapsule suspending agent.
The avermectin polyurethane microcapsule emulsion prepared in the embodiment is milk white, the average particle size of the polyurethane microcapsule is 500nm, and the pesticide encapsulation rate obtained by the method in the embodiment 1 is 93%.
The embodiment shows that the pesticide microcapsule suspending agent provided by the invention is excellent in stability, and the polyurethane pesticide microcapsule prepared by the embodiment is regular in appearance, spherical, uniform in particle size distribution, excellent in stability and high in pesticide encapsulation efficiency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A pesticide microcapsule suspending agent is prepared from the following raw materials in parts by weight:
2. the pesticide microcapsule suspension as claimed in claim 1, wherein the preparation method of the polyisocyanate prepolymer comprises: polyether polyol, polyisocyanate and dibutyltin dilaurate are mixed for polymerization reaction to obtain the polyisocyanate prepolymer.
3. The pesticide microcapsule suspension as claimed in claim 2, wherein the mass ratio of the polyether polyol, the polyisocyanate and the dibutyltin dilaurate is 1 (1.5-6) to (0.001-0.01).
4. The pesticide microcapsule suspension according to claim 2, wherein the polymerization temperature is 70-85 ℃ and the polymerization time is 2-5 h.
5. A pesticidal microcapsule suspension according to claim 2, wherein the polyisocyanate comprises one or two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, tetramethylxylylene diisocyanate and lysine diisocyanate.
6. The pesticide microcapsule suspension according to claim 2, wherein the polyether polyol comprises one or two 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.
7. A pesticidal microcapsule suspension according to claim 1, wherein the bulk pesticide comprises one or more of emamectin benzoate, pyraclostrobin, pendimethalin, abamectin, chlorpyrifos, thiamethoxam and butachlor.
8. The pesticidal microcapsule suspension according to claim 1, wherein the emulsifier comprises one or more of tween series, polyvinyl alcohol, OP series, NP series, EL series and AEO series.
9. The pesticidal microcapsule suspension according to claim 1, wherein the curing agent comprises one or more of ethylenediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
10. A method for producing the pesticidal microcapsule suspension of any one of claims 1 to 9, comprising the steps of:
(1) mixing the pesticide raw material, an organic solvent and a polyisocyanate prepolymer to obtain an oil phase;
(2) dissolving an emulsifier in deionized water to obtain a water phase;
(3) mixing the oil phase obtained in the step (1) and the water phase obtained in the step (2) and emulsifying to obtain emulsion;
(4) and (4) mixing a chain extender and a curing agent with the emulsion obtained in the step (3) to perform a crosslinking reaction to obtain the pesticide microcapsule suspending agent.
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