CN113115786A - Glutathione-responsive polyurethane microcapsule suspension and preparation method and application thereof - Google Patents
Glutathione-responsive polyurethane microcapsule suspension and preparation method and application thereof Download PDFInfo
- Publication number
- CN113115786A CN113115786A CN202110430411.4A CN202110430411A CN113115786A CN 113115786 A CN113115786 A CN 113115786A CN 202110430411 A CN202110430411 A CN 202110430411A CN 113115786 A CN113115786 A CN 113115786A
- Authority
- CN
- China
- Prior art keywords
- glutathione
- polyurethane microcapsule
- microcapsule suspension
- wall material
- responsive polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides a glutathione responsive polyurethane microcapsule suspension and a preparation method and application thereof, belonging to the technical field of pesticides. The glutathione-responsive polyurethane microcapsule suspension provided by the invention takes pyraclostrobin as an effective component, and the disulfide bond is introduced into the capsule wall material, so that when the polyurethane microcapsule enters a plant body, the capsule wall material is damaged by glutathione existing in the plant body, and the pesticide can be accurately released. Therefore, the polyurethane microcapsule has glutathione responsiveness, and the responsiveness does not depend on the stimulation of environment (temperature, pH, humidity and the like), so that the pesticide utilization rate and the product safety are greatly improved. Meanwhile, the polyurethane microcapsule has excellent embedding effect, good stability of the polyurethane microcapsule suspension and long lasting period.
Description
Technical Field
The invention relates to the technical field of pesticides, in particular to a glutathione responsive polyurethane microcapsule suspension and a preparation method and application thereof.
Background
With social progress and development, the conventional pesticide formulations such as missible oil and powder gradually show the defects of high toxicity, high residue, poor environmental compatibility and the like, and are inconsistent with the requirement of people on pursuing green environmental protection. At present, the research and development of high-toxicity pesticide formulations are developed towards low toxicity and no toxicity, wherein the microcapsule suspending agent gradually becomes an important trend of the research and development of pesticide formulations due to the characteristics of slow release, low toxicity, high efficiency, safety to people, livestock and environment and the like.
The traditional pyraclostrobin pesticide formulation has the problems of easiness in photolysis, short duration, large residue, low utilization rate and the like in the application process, so that the problems existing in the pyraclostrobin can be effectively improved by microencapsulating the pyraclostrobin.
Compared with the traditional pesticide, the responsive release pesticide has the characteristic of being immediately and accurately released after responding to stimulation. At present, research on the responsive release pesticide microcapsules mainly focuses on environmental changes such as light, pH value and temperature, but many limitations exist in the field application aspect due to the fact that the environmental changes in the field cannot be controlled.
Disclosure of Invention
The invention aims to provide a glutathione-responsive polyurethane microcapsule suspension, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a glutathione responsive polyurethane microcapsule suspension, which comprises the following preparation raw materials in percentage by mass:
1-25% of pyraclostrobin, 3-15% of a capsule core solvent, 2-15% of an oily capsule wall material, 1-12% of a water-based capsule wall material, 2-10% of an emulsifier, 0.5-4% of a dispersant, 0.02-4% of an antifreezing agent, 0.01-0.1% of an antifoaming agent and the balance of water;
wherein the oil capsule wall material is polyisocyanate;
the water-based capsule wall material comprises a first monomer and a second monomer, wherein the first monomer is a disulfide compound, and the second monomer is an alcohol monomer and/or an amine monomer.
Preferably, the polyisocyanate includes at least one of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate.
Preferably, the disulfide compound includes at least one of 2-hydroxyethyl disulfide and 1,1 '-dihydroxy-3, 3' -dihexyl disulfide.
Preferably, the alcohol monomer includes at least one of ethylene glycol, glycerol and polyethylene glycol, and the amine monomer includes at least one of ethylenediamine, hexamethylenediamine, 1, 2-propanediamine, butanediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
Preferably, the molecular weight of the polyethylene glycol is 200-1600.
Preferably, the content of the disulfide compound in the water-based capsule wall material is 30-70 wt%.
Preferably, the capsule core solvent comprises at least one of solvent oil, alcohol solvent, ketone solvent, ester solvent, alkane solvent and substituted alkane solvent.
Preferably, the emulsifier includes at least one of a farm milk series emulsifier, a tween series emulsifier, an AEO series emulsifier, an OP series emulsifier, an NP series emulsifier, and an EL series emulsifier;
the dispersant comprises at least one of sodium lignosulfonate, sodium alkyl sulfate, sodium alkyl benzene sulfonate and polycarboxylate;
the antifreeze comprises at least one of ethylene glycol and sodium chloride;
the antifoaming agent comprises at least one of FAG-470 antifoaming agent, LD-205 antifoaming agent, GP-330 antifoaming agent and LD-02 antifoaming agent.
The invention provides a preparation method of a glutathione-responsive polyurethane microcapsule suspension, which comprises the following steps:
mixing pyraclostrobin, a capsule core solvent and an oily capsule wall material to obtain an oil phase;
mixing an emulsifier, water and part of a dispersant to obtain a water phase;
mixing the oil phase and the water phase for emulsification to obtain emulsion;
mixing the emulsion, the defoaming agent and the water-based capsule wall material, and carrying out polymerization reaction to obtain a polymerization reaction product system;
and mixing the polymerization reaction product system, the antifreezing agent and the dispersing agent to obtain the glutathione-responsive polyurethane microcapsule suspension.
The invention provides application of the glutathione-responsive polyurethane microcapsule suspension liquid in the technical scheme or the glutathione-responsive polyurethane microcapsule suspension liquid prepared by the preparation method in the technical scheme in preventing and treating wheat scab
The invention provides a glutathione responsive polyurethane microcapsule suspension, which comprises the following preparation raw materials in percentage by mass: 1-25% of pyraclostrobin, 3-15% of a capsule core solvent, 2-15% of an oily capsule wall material, 1-12% of a water-based capsule wall material, 2-10% of an emulsifier, 0.5-4% of a dispersant, 0.02-4% of an antifreezing agent, 0.01-0.1% of an antifoaming agent and the balance of water; wherein the oily capsule wall material is polyisocyanate, and the aqueous capsule wall material comprises a disulfide compound containing hydroxyl. The glutathione-responsive polyurethane microcapsule suspension provided by the invention takes pyraclostrobin as an effective component, and the disulfide bond is introduced into the capsule wall material, so that when the polyurethane microcapsule enters a plant body, the capsule wall material is damaged by glutathione existing in the plant body, and the pesticide can be accurately released. Therefore, the polyurethane microcapsule has glutathione responsiveness, and the responsiveness does not depend on the stimulation of environment (temperature, pH, humidity and the like), so that the pesticide utilization rate and the product safety are greatly improved. Meanwhile, the polyurethane microcapsule has excellent embedding effect, good stability of the polyurethane microcapsule suspension and long lasting period.
The invention provides a preparation method of a glutathione-responsive polyurethane microcapsule suspension, which comprises the following steps: mixing pyraclostrobin, a capsule core solvent and an oily capsule wall material to obtain an oil phase; mixing an emulsifier, water and part of a dispersant to obtain a water phase; mixing the oil phase and the water phase for emulsification to obtain emulsion; mixing the emulsion with a water-based capsule wall material, and carrying out polymerization reaction to obtain a polymerization reaction product system; and mixing the polymerization reaction product system, the antifreezing agent and the rest dispersing agent to obtain the glutathione-responsive polyurethane microcapsule suspension. The preparation method provided by the invention has the advantages of high yield of the polyurethane microcapsule, simple process flow, no need of harsh operating conditions and expensive production equipment, low cost and suitability for industrial production.
Drawings
FIG. 1 is an SEM image of a glutathione-responsive polyurethane microcapsule prepared in example 1;
FIG. 2 is an SEM image of the glutathione-responsive polyurethane microcapsule prepared in example 2;
FIG. 3 is an SEM image of glutathione-responsive polyurethane microcapsules prepared in example 3;
FIG. 4 is an SEM image of the glutathione-responsive polyurethane microcapsule prepared in example 4;
fig. 5 is a graph showing the release performance results of the glutathione-responsive polyurethane microcapsule prepared in example 1.
Detailed Description
The invention provides a glutathione responsive polyurethane microcapsule suspension, which comprises the following preparation raw materials in percentage by mass:
1-25% of pyraclostrobin, 3-15% of a capsule core solvent, 2-15% of an oily capsule wall material, 1-12% of a water-based capsule wall material, 2-10% of an emulsifier, 0.5-4% of a dispersant, 0.02-4% of an antifreezing agent, 0.01-0.1% of an antifoaming agent and the balance of water;
wherein the oil capsule wall material is polyisocyanate;
the water-based capsule wall material comprises a first monomer and a second monomer, wherein the first monomer is a disulfide compound, and the second monomer is an alcohol monomer and/or an amine monomer.
According to the mass percentage, the raw materials for preparing the glutathione-responsive polyurethane microcapsule suspension comprise 1-25% of pyraclostrobin, preferably 3-25%, and more preferably 9-15%.
According to the mass percentage, the preparation raw materials of the glutathione-responsive polyurethane microcapsule suspension comprise 3-15% of capsule core solvent, preferably 5-12%, and more preferably 7-9%. In the present invention, the capsule core solvent preferably includes at least one of mineral spirit, alcohol solvent, ketone solvent, ester solvent, alkane solvent and substituted alkane solvent; the solvent oil is preferably 200# solvent oil or 150# solvent oil, the alcohol solvent is preferably isopropanol or n-butanol, the ketone solvent is preferably acetone or cyclohexanone, the ester solvent is preferably ethyl acetate, methyl oleate, dibutyl phthalate or butyl acetate, the alkane solvent is preferably hexane, and the substituted alkane solvent is preferably dichloromethane.
According to the mass percentage, the preparation raw materials of the glutathione-responsive polyurethane microcapsule suspension comprise 2-15% of oily capsule wall materials, preferably 3-12%, and more preferably 6-9%. In the present invention, the oil wall material is a polyisocyanate, and the polyisocyanate preferably includes at least one of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate, and more preferably toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or lysine diisocyanate.
According to the mass percentage, the raw materials for preparing the glutathione-responsive polyurethane microcapsule suspension comprise 1-12% of water-based capsule wall material, preferably 3-11%, more preferably 4-10%, and further preferably 5-8%. In the present invention, the aqueous wall material comprises a first monomer and a second monomer. In the present invention, the first monomer is a disulfide compound, and the disulfide compound preferably includes at least one of 2-hydroxyethyl disulfide and 1,1 '-dihydroxy-3, 3' -dihexyl disulfide, and more preferably 2-hydroxyethyl disulfide or 1,1 '-dihydroxy-3, 3' -dihexyl disulfide. In the invention, the second monomer is an alcohol monomer and/or an amine monomer; the alcohol monomer preferably comprises at least one of ethylene glycol, glycerol and polyethylene glycol, and more preferably ethylene glycol, glycerol or polyethylene glycol; the molecular weight of the polyethylene glycol is preferably 200-1600, more preferably 200-800, and specifically can be 200, 400, 600 or 800; the amine monomer preferably includes at least one of ethylenediamine, hexamethylenediamine, 1, 2-propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and more preferably ethylenediamine, hexamethylenediamine, 1, 2-propylenediamine, butylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. In the invention, the content of the disulfide compound in the water-based capsule wall material is preferably 30-70 wt%, more preferably 36-67 wt%, and even more preferably 40-50 wt%. In the embodiment of the present invention, the aqueous capsule wall material may be a disulfide compound/alcohol monomer binary mixed system, specifically, a 2-hydroxyethyl disulfide/glycerol mixed system or a 2-hydroxyethyl disulfide/ethylene glycol mixed system; the water-based capsule wall material can also be a disulfide compound/amine monomer binary mixed system, and specifically can be a 1,1 '-dihydroxy-3, 3' -dihexyldisulfide/triethylene tetramine mixed system; the water-based capsule wall material can also be a disulfide compound/alcohol monomer/amine monomer ternary mixed system, and specifically can be a 2-hydroxyethyl disulfide/polyethylene glycol/triethylene tetramine ternary mixed system. In the embodiment of the present invention, the mass ratio of 2-hydroxyethyl disulfide to glycerin in the 2-hydroxyethyl disulfide/glycerin mixed system is preferably 1: 1, the mass ratio of the 2-hydroxyethyl disulfide to the ethylene glycol in the 2-hydroxyethyl disulfide/ethylene glycol mixed system is preferably 2: 3, the mass ratio of the 1,1 '-dihydroxy-3, 3' -dihexyl disulfide to the triethylene tetramine in the 1,1 '-dihydroxy-3, 3' -dihexyl disulfide/triethylene tetramine mixed system is preferably 2: 1, the mass ratio of the 2-hydroxyethyl disulfide to the polyethylene glycol to the triethylene tetramine in the 2-hydroxyethyl disulfide/polyethylene glycol/triethylene tetramine ternary mixed system is preferably 4: 6: 1.
according to the mass percentage, the raw materials for preparing the glutathione-responsive polyurethane microcapsule suspension comprise 2-10% of emulsifier, preferably 4-8%. In the present invention, the emulsifier preferably includes at least one of a farm milk-series emulsifier, a tween-series emulsifier, an AEO-series emulsifier, an OP-series emulsifier, an NP-series emulsifier, and an EL-series emulsifier, and more preferably a farm milk-series emulsifier, a tween-series emulsifier, an AEO-series emulsifier, an OP-series emulsifier, an NP-series emulsifier, or an EL-series emulsifier; the agricultural milk series emulsifier is preferably agricultural milk 500#, agricultural milk 600#, agricultural milk 700#, agricultural milk 1601# or agricultural milk 1602#, the tween series emulsifier is preferably tween 60 or tween 80, the AEO series emulsifier is preferably AEO-5, the OP series emulsifier is preferably OP-10, the NP series emulsifier is preferably NP-10, and the EL series emulsifier is preferably EL-20, EL-40 or EL-60.
According to the mass percentage, the raw materials for preparing the glutathione-responsive polyurethane microcapsule suspension comprise 0.5-4% of dispersing agent, preferably 1-2%. In the present invention, the dispersant preferably includes at least one of sodium lignosulfonate, sodium alkylsulfate, sodium alkylbenzenesulfonate and polycarboxylate, more preferably sodium lignosulfonate, sodium alkylsulfate, sodium alkylbenzenesulfonate or polycarboxylate; wherein, the alkyl sodium sulfate is preferably sodium dodecyl sulfate, the sodium alkyl benzene sulfonate is preferably sodium dodecyl benzene sulfonate, and the polycarboxylate is preferably sodium polycarboxylate.
According to the mass percentage, the raw materials for preparing the glutathione-responsive polyurethane microcapsule suspension comprise 0.02-4% of an antifreezing agent, and preferably 1-2%. In the present invention, the antifreeze preferably includes at least one of ethylene glycol and sodium chloride, more preferably ethylene glycol or sodium chloride.
According to the mass percentage, the raw materials for preparing the glutathione-responsive polyurethane microcapsule suspension comprise 0.01-0.1% of defoaming agent, and preferably 0.04-0.05%. In the present invention, the antifoaming agent preferably includes at least one of a FAG-470 antifoaming agent, a LD-205 antifoaming agent, a GP-330 antifoaming agent, and a LD-02 antifoaming agent, and more preferably a FAG-470 antifoaming agent, a LD-205 antifoaming agent, a GP-330 antifoaming agent, or a LD-02 antifoaming agent.
According to the mass percentage, the raw material for preparing the glutathione responsive polyurethane microcapsule suspension comprises the balance of water.
The invention provides a preparation method of a glutathione-responsive polyurethane microcapsule suspension, which comprises the following steps:
mixing pyraclostrobin, a capsule core solvent and an oily capsule wall material to obtain an oil phase;
mixing an emulsifier, water and part of a dispersant to obtain a water phase;
mixing the oil phase and the water phase for emulsification to obtain emulsion;
mixing the emulsion, the defoaming agent and the water-based capsule wall material, and carrying out polymerization reaction to obtain a polymerization reaction product system;
and mixing the polymerization reaction product system, the antifreezing agent and the rest dispersing agent to obtain the glutathione-responsive polyurethane microcapsule suspension.
The pyraclostrobin, the capsule core solvent and the oily capsule wall material are mixed to obtain the oil phase. In the invention, the pyraclostrobin, the capsule core solvent and the oily capsule wall material are preferably mixed in a manner that the pyraclostrobin is dissolved in the capsule core solvent, the oily capsule wall material is added into an obtained system, and then the mixture is uniformly mixed under a stirring condition to obtain an oil phase.
The invention mixes the emulsifier, water and partial dispersant to obtain water phase. In the present invention, the emulsifier, water and a part of the dispersant are preferably mixed by adding the emulsifier and the part of the dispersant to water, and then mixing them uniformly under stirring to obtain an aqueous phase.
After obtaining the water phase and the oil phase, the invention mixes the oil phase and the water phase for emulsification to obtain the emulsion. In the invention, the emulsification is preferably carried out under the shearing condition of 8000-12000 r/min, more preferably 10000 r/min; the emulsifying time is preferably 3-8 min, and more preferably 5 min. In an embodiment of the invention, the emulsification is in particular performed in a high shear emulsifier.
After the emulsion is obtained, the emulsion, the defoaming agent and the water-based capsule wall material are mixed for polymerization reaction to obtain a polymerization reaction product system. The emulsion is preferably mixed with the defoaming agent to obtain mixed feed liquid; and then mixing the mixed liquid with the water-based capsule wall material to carry out polymerization reaction. In the invention, the polymerization reaction preferably comprises a first-stage reaction and a second-stage reaction which are sequentially carried out, wherein the first-stage reaction is preferably carried out at the temperature of 20-40 ℃, more preferably at the temperature of 30-40 ℃ and for the time of 2-4 h, more preferably at the time of 2-3 h; the temperature of the second stage reaction is preferably 60-70 ℃, more preferably 60-65 ℃, and the time is preferably 1-3 hours, more preferably 1-2 hours. In the invention, the components in the aqueous capsule wall material are preferably not added simultaneously, and particularly, when the aqueous capsule wall material is a disulfide compound/alcohol monomer binary mixed system, the mixed material liquid and the alcohol monomer are preferably mixed for a first-stage reaction, and then the obtained first-stage reaction product system is mixed with the disulfide compound for a second-stage reaction; when the water-based capsule wall material is a disulfide compound/amine monomer binary mixed system, the invention preferably mixes the mixed feed liquid with the disulfide compound to carry out a first-stage reaction, and then mixes the obtained first-stage reaction product system with the amine monomer to carry out a second-stage reaction; when the water-based capsule wall material is a disulfide compound/alcohol monomer/amine monomer ternary mixed system, the mixed material liquid and the alcohol monomer are preferably mixed to carry out a first-stage reaction, and then the obtained first-stage reaction product system is mixed with the disulfide compound and the amine monomer to carry out a second-stage reaction. In the invention, when the emulsion is mixed with alcohol monomers or disulfide compounds, the alcohol monomers or disulfide compounds are preferably dripped into the mixed feed liquid, and the dripping speed is preferably and independently 6-10 drops/min; the invention slowly and dropwise adds the alcohol monomer or the disulfide compound into the mixed feed liquid, so as to prevent the too fast reaction, particle coalescence and uneven particles. In the invention, the polymerization reaction is preferably carried out under the condition of stirring, and the stirring speed is preferably 400-600 r/min, and more preferably 500 r/min. In the invention, in the polymerization reaction, the oily capsule wall material and the aqueous capsule wall material react to coat the pyraclostrobin surface to form the polyurethane capsule wall material; specifically, in the process of the first-stage reaction, the oil capsule wall material reacts with a part of the water-based capsule wall material to form polyurethane (isocyanate and hydroxyl are generated through reaction), in the process of the second-stage reaction, the oil capsule wall material further reacts with the water-based capsule wall material added in the system, a layer of polyurea ester (generated through reaction of isocyanate and amino) or polyurethane is further coated on the surface of the polyurethane to realize solidification, and finally, the polyurethane capsule wall material (specifically comprising a single polyurethane capsule wall or a polyurethane-polyurea ester hybrid capsule wall) containing disulfide bonds is formed on the surface of the pyraclostrobin, so that the obtained polyurethane microcapsule has glutathione responsiveness, and the responsiveness does not depend on the stimulation of environment (temperature, pH, humidity and the like), and the pesticide utilization rate and the product safety are greatly improved.
In the invention, after the polymerization reaction is finished, the obtained polymerization reaction product system, the antifreezing agent and the residual dispersant are directly mixed without any post-treatment, so that the glutathione-responsive polyurethane microcapsule suspension is obtained. In the invention, the polymerization reaction product system, the antifreeze and the residual dispersant are preferably mixed by adding the antifreeze and the residual dispersant into the polymerization reaction product system, and then stirring and mixing uniformly to obtain the glutathione-responsive polyurethane microcapsule suspension.
After the mixing is finished, in order to facilitate characterization or performance test, the glutathione-responsive polyurethane microcapsule suspension is preferably filtered, the obtained filter cake is washed by 10 wt% of ethanol water solution, and then is dried for 24 hours at the temperature of 25 ℃ to obtain the glutathione-responsive polyurethane microcapsule.
The invention provides application of the glutathione-responsive polyurethane microcapsule suspension in the technical scheme or the glutathione-responsive polyurethane microcapsule suspension prepared by the preparation method in the technical scheme in preventing and treating small head blight. In the invention, the specific use method of the glutathione-responsive polyurethane microcapsule suspension is preferably water spraying, and the application amount is preferably 80 mu L/m2。
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
The raw materials for preparing the glutathione-responsive polyurethane microcapsule suspension in the embodiment are shown in table 1, and the preparation method comprises the following steps:
dissolving pyraclostrobin in butyl acetate, adding isophorone diisocyanate, and stirring and mixing uniformly to obtain an oil phase;
adding tween 80 and sodium polycarboxylate into water, and uniformly stirring and mixing to obtain a water phase;
mixing the oil phase and the water phase, carrying out high-speed shearing emulsification for 5min under the condition of 10000r/min to obtain uniform emulsion, mixing the emulsion with a defoaming agent, dropwise adding glycerol into the obtained mixed liquid at the speed of 10 drops/min, and reacting for 3h at the temperature of 30 ℃ at 500 r/min; adding 2-hydroxyethyl disulfide into the obtained system, heating to 60 ℃, and carrying out heat preservation and curing for 2 h; and adding sodium polycarboxylate and glycol into the obtained system, and uniformly stirring and mixing to obtain the glutathione responsive polyurethane microcapsule suspension.
And filtering the glutathione-responsive polyurethane microcapsule suspension, washing the obtained filter cake with 10% ethanol water solution, and drying at 25 ℃ for 24h to obtain the glutathione-responsive polyurethane microcapsule.
Example 2
The raw materials for preparing the glutathione-responsive polyurethane microcapsule suspension in the embodiment are shown in table 1, and the preparation method comprises the following steps:
dissolving pyraclostrobin in No. 200 solvent oil, adding isophorone diisocyanate, and stirring and mixing uniformly to obtain an oil phase;
mixing EL-40, sodium dodecyl benzene sulfonate and water, and stirring and mixing uniformly to obtain a water phase;
mixing the oil phase and the water phase, carrying out high-speed shearing emulsification for 5min under the condition of 10000r/min to obtain uniform emulsion, mixing the emulsion with a defoaming agent, dropwise adding ethylene glycol into the obtained mixed feed liquid at the speed of 10 drops/min, and reacting for 3h at the temperature of 30 ℃ at 500 r/min; adding 2-hydroxyethyl disulfide into the obtained system, heating to 60 ℃, and carrying out heat preservation and curing for 2 h; and adding the rest sodium dodecyl benzene sulfonate and NaCl into the obtained system, and stirring and mixing uniformly to obtain the glutathione responsive polyurethane microcapsule suspension.
And filtering the glutathione-responsive polyurethane microcapsule suspension, washing the obtained filter cake with 10% ethanol water solution, and drying at 25 ℃ for 24h to obtain the glutathione-responsive polyurethane microcapsule.
Example 3
The raw materials for preparing the glutathione-responsive polyurethane microcapsule suspension in the embodiment are shown in table 1, and the preparation method comprises the following steps:
dissolving pyraclostrobin in ethyl acetate, adding hexamethylene diisocyanate, and uniformly stirring and mixing to obtain an oil phase;
mixing NP-10, sodium dodecyl sulfate and water, and stirring and mixing uniformly to obtain a water phase;
mixing the oil phase and the water phase, carrying out high-speed shearing emulsification for 5min under the condition of 10000r/min to obtain uniform emulsion, mixing the emulsion with a defoaming agent, dropwise adding 1,1 '-dihydroxy-3, 3' -dihexyl disulfide into the obtained mixed feed liquid at the speed of 10 drops/min, and reacting for 2h under the conditions of 500r/min and 40 ℃; adding triethylene tetramine into the obtained system, heating to 60 ℃, and carrying out heat preservation and curing for 1 h; and adding sodium dodecyl sulfate and ethylene glycol into the obtained system, and stirring and mixing uniformly to obtain the glutathione responsive polyurethane microcapsule suspension.
And filtering the glutathione-responsive polyurethane microcapsule suspension, washing the obtained filter cake with 10% ethanol water solution, and drying at 25 ℃ for 24h to obtain the glutathione-responsive polyurethane microcapsule.
Example 4
The raw materials for preparing the glutathione-responsive polyurethane microcapsule suspension in the embodiment are shown in table 1, and the preparation method comprises the following steps:
dissolving pyraclostrobin in ethyl acetate, adding isophorone diisocyanate, and stirring and mixing uniformly to obtain an oil phase;
mixing EL-40, sodium dodecyl benzene sulfonate and water, and stirring and mixing uniformly to obtain a water phase;
mixing the oil phase and the water phase, carrying out high-speed shearing emulsification for 5min under the condition of 10000r/min to obtain uniform emulsion, mixing the emulsion with a defoaming agent, dropwise adding polyethylene glycol (with the molecular weight of 400) into the obtained mixed liquid at the speed of 10 drops/min, and reacting for 3h under the conditions of 500r/min and 30 ℃; adding 2-hydroxyethyl disulfide and triethylene tetramine into the obtained system, heating to 60 ℃, and carrying out heat preservation for curing for 2 hours; and adding sodium dodecyl benzene sulfonate and NaCl into the obtained system, and stirring and mixing uniformly to obtain the glutathione responsive polyurethane microcapsule suspension.
And filtering the glutathione-responsive polyurethane microcapsule suspension, washing the obtained filter cake with 10% ethanol water solution, and drying at 25 ℃ for 24h to obtain the glutathione-responsive polyurethane microcapsule.
Table 1 types and mass percentages of raw materials prepared in examples 1 to 4
The glutathione-responsive polyurethane microcapsule suspension and the glutathione-responsive polyurethane microcapsule prepared in the embodiments 1 to 4 are characterized and tested, and the characteristics are as follows:
1. and (3) characterization: FIGS. 1 to 4 are SEM images of the glutathione-responsive polyurethane microcapsules prepared in examples 1 to 4, and it can be seen from FIGS. 1 to 4 that the glutathione-responsive polyurethane microcapsules are approximately spherical in shape and uniform in size.
2. Encapsulation efficiency and particle size: the results are shown in Table 2.
3. Dispersibility: putting 99.5mL of hard water into a conical measuring cylinder with a plug, taking 0.5mL of glutathione-responsive polyurethane microcapsule suspension by using an injector, dripping the glutathione-responsive polyurethane microcapsule suspension into the hard water from a position 5cm away from the measuring cylinder, and observing the dispersion condition; the dispersion condition grades comprise excellent, good and inferior, and the phenomena of each grade are as follows:
and (3) excellent: the water enters the device in a cloud form, and no visible particles sink;
good: automatically dispersing in water, and dispersing the particles after slight shaking;
poor: it can not be automatically dispersed in water, and can be dispersed in the form of granule or flocculent.
The dispersion results of the glutathione-responsive polyurethane microcapsule suspension prepared in each example are shown in table 2, and it can be seen from table 2 that the glutathione-responsive polyurethane microcapsule suspension provided by the invention has better dispersion.
3. Release performance: accurately weighing 1g of glutathione-responsive polyurethane microcapsule, placing the glutathione-responsive polyurethane microcapsule into a triangular flask, adding 100mL of deionized water and 100mL of methanol into the triangular flask as release media, adding 1mL of 4mM glutathione solution (the solvent is 50% methanol aqueous solution by volume fraction) into the triangular flask, then placing the triangular flask into a constant-temperature water bath oscillator, oscillating at room temperature and 120rpm, and suspending the glutathione-responsive polyurethane microcapsule in the system for release. A series of time points are selected for sampling, the sampling amount is 2mL each time, and an equal volume of release medium (namely 50% methanol water solution in volume fraction) is added into the triangular flask at the same time, so that the volume of the release medium in the triangular flask is ensured to be unchanged. Extracting the taken 2mL sample by using dichloromethane, then fixing the volume by using methanol, detecting the content of the pyraclostrobin in the sample by using an ultraviolet spectrophotometry, and specifically calculating the content of the pyraclostrobin in the sample by using a formula shown in formula 1.
Q in formula 1: accumulating the release amount; v: total volume of sample (mL); cn: concentration sampled at n (mg/L); vi: volume sampled at i (mL); m: the mass (mg) of pyraclostrobin in the glutathione responsive polyurethane microcapsule; n: number of replacements of the release medium.
Fig. 5 is a graph showing the release performance of the glutathione-responsive polyurethane microcapsule prepared in example 1, wherein a in fig. 5 is the absence of glutathione and b is the addition of glutathione. As can be seen from FIG. 5, when glutathione is not added, the cumulative release rate of pyraclostrobin is 82%; after glutathione was added, the cumulative release rate of pyraclostrobin was 92%.
Specific results of the release performance of the glutathione-responsive polyurethane microcapsules in each embodiment are shown in table 2, and it can be known from table 2 that the glutathione-responsive polyurethane microcapsules provided by the invention have glutathione responsiveness.
4. Stability: storing the glutathione responsive polyurethane microcapsule suspension in an oven at 54 +/-2 ℃ for 14 days, wherein the result shows that no layering and precipitation exist, which indicates that the heat storage stability is qualified; the glutathione response polyurethane microcapsule suspension is stored for 7 days at the temperature of 0 +/-2 ℃, and the result shows that no layering and precipitation exist, which indicates that the low-temperature stability is qualified.
The stability results of the glutathione-responsive polyurethane microcapsule suspensions of the various examples are detailed in table 2. As can be seen from Table 2, the glutathione responsive polyurethane microcapsule suspension provided by the invention has better stability.
5. Prevention of wheat scab: the method is characterized in that the control effect of the glutathione-responsive polyurethane microcapsule suspension is tested by taking the wheat scab as a control object, and specifically, 250g/L pyraclostrobin missible oil preparation (sold in the market) and the glutathione-responsive polyurethane microcapsule suspension are adopted to treat more than 5 wheat scabs, clear water is set for comparison, each treatment is repeated for 3 times, the pesticide effect is checked before and after pesticide application, and the control effect is calculated according to formulas 2 and 3.
Control effect (%) - (control disease index-treatment disease index)/control disease index × 100 formula 2;
the disease index ∑ (number of onset at each stage × representative value at the stage)/(total number of examined leaves × number of highest stage) × 100 formula 3.
The result shows that the initial control effect (specifically, the control effect 3 days after the application) of the glutathione-responsive polyurethane microcapsule suspension prepared in the example 1 and the pyraclostrobin missible oil preparation is 80%; 15 days after application, the control effect of the glutathione responsive polyurethane microcapsule suspension prepared in the example 1 is 68%, while the control effect of the pyraclostrobin missible oil preparation is only 40%, and is reduced to 1/2 of the initial control effect, which indicates that the control effect of the glutathione responsive polyurethane microcapsule suspension provided by the invention is remarkably higher than that of the pyraclostrobin missible oil preparation.
The initial control results of the glutathione-responsive polyurethane microcapsule suspensions prepared in each example are shown in table 2. As can be seen from Table 2, the glutathione-responsive polyurethane microcapsule suspension provided by the invention has excellent control effect on wheat scab.
Table 2 Performance test results of glutathione-responsive polyurethane microcapsule suspensions and glutathione-responsive polyurethane microcapsules prepared in examples 1 to 4
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. The glutathione response polyurethane microcapsule suspension comprises the following preparation raw materials in percentage by mass:
1-25% of pyraclostrobin, 3-15% of a capsule core solvent, 2-15% of an oily capsule wall material, 1-12% of a water-based capsule wall material, 2-10% of an emulsifier, 0.5-4% of a dispersant, 0.02-4% of an antifreezing agent, 0.01-0.1% of an antifoaming agent and the balance of water;
wherein the oil capsule wall material is polyisocyanate;
the water-based capsule wall material comprises a first monomer and a second monomer, wherein the first monomer is a disulfide compound, and the second monomer is an alcohol monomer and/or an amine monomer.
2. The glutathione-responsive polyurethane microcapsule suspension according to claim 1, wherein the polyisocyanate comprises at least one of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and lysine diisocyanate.
3. The glutathione-responsive polyurethane microcapsule suspension according to claim 1, wherein the disulfide-based compound comprises at least one of 2-hydroxyethyl disulfide and 1,1 '-dihydroxy-3, 3' -dihexyl disulfide.
4. The glutathione-responsive polyurethane microcapsule suspension according to claim 1, wherein the alcohol monomer comprises at least one of ethylene glycol, glycerol and polyethylene glycol, and the amine monomer comprises at least one of ethylenediamine, hexamethylenediamine, 1, 2-propanediamine, butanediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
5. The glutathione-responsive polyurethane microcapsule suspension of claim 4, wherein the molecular weight of the polyethylene glycol is 200-1600.
6. The glutathione-responsive polyurethane microcapsule suspension of claim 4 or 5, wherein the content of the disulfide compounds in the aqueous capsule wall material is 30-70 wt%.
7. The glutathione-responsive polyurethane microcapsule suspension of claim 1, wherein the capsule core solvent comprises at least one of solvent oil, alcohol solvent, ketone solvent, ester solvent, alkane solvent and substituted alkane solvent.
8. The glutathione-responsive polyurethane microcapsule suspension according to claim 1, wherein the emulsifier comprises at least one of a farm milk-series emulsifier, a tween-series emulsifier, an AEO-series emulsifier, an OP-series emulsifier, an NP-series emulsifier, and an EL-series emulsifier;
the dispersant comprises at least one of sodium lignosulfonate, sodium alkyl sulfate, sodium alkyl benzene sulfonate and polycarboxylate;
the antifreeze comprises at least one of ethylene glycol and sodium chloride;
the antifoaming agent comprises at least one of FAG-470 antifoaming agent, LD-205 antifoaming agent, GP-330 antifoaming agent and LD-02 antifoaming agent.
9. The preparation method of the glutathione-responsive polyurethane microcapsule suspension liquid as claimed in any one of claims 1 to 8, which comprises the following steps:
mixing pyraclostrobin, a capsule core solvent and an oily capsule wall material to obtain an oil phase;
mixing an emulsifier, water and part of a dispersant to obtain a water phase;
mixing the oil phase and the water phase for emulsification to obtain emulsion;
mixing the emulsion, the defoaming agent and the water-based capsule wall material, and carrying out polymerization reaction to obtain a polymerization reaction product system;
and mixing the polymerization reaction product system, the antifreezing agent and the dispersing agent to obtain the glutathione-responsive polyurethane microcapsule suspension.
10. The glutathione-responsive polyurethane microcapsule suspension of any one of claims 1 to 8 or the glutathione-responsive polyurethane microcapsule suspension prepared by the preparation method of claim 9 is applied to prevention and treatment of wheat scab.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110430411.4A CN113115786B (en) | 2021-04-21 | 2021-04-21 | Glutathione-responsive polyurethane microcapsule suspension and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110430411.4A CN113115786B (en) | 2021-04-21 | 2021-04-21 | Glutathione-responsive polyurethane microcapsule suspension and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113115786A true CN113115786A (en) | 2021-07-16 |
| CN113115786B CN113115786B (en) | 2021-12-14 |
Family
ID=76778561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110430411.4A Active CN113115786B (en) | 2021-04-21 | 2021-04-21 | Glutathione-responsive polyurethane microcapsule suspension and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113115786B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103734162A (en) * | 2014-02-18 | 2014-04-23 | 陕西上格之路生物科学有限公司 | Pyraclostrobin microcapsule suspending agent |
| CN104823996A (en) * | 2015-05-13 | 2015-08-12 | 山东农业大学 | Preparation method of pyraclostrobin microcapsules |
| CN105310998A (en) * | 2015-11-03 | 2016-02-10 | 吉林大学 | Microcapsule containing functionalized graphene in capsule wall and preparation method of microcapsule |
-
2021
- 2021-04-21 CN CN202110430411.4A patent/CN113115786B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103734162A (en) * | 2014-02-18 | 2014-04-23 | 陕西上格之路生物科学有限公司 | Pyraclostrobin microcapsule suspending agent |
| CN104823996A (en) * | 2015-05-13 | 2015-08-12 | 山东农业大学 | Preparation method of pyraclostrobin microcapsules |
| CN105310998A (en) * | 2015-11-03 | 2016-02-10 | 吉林大学 | Microcapsule containing functionalized graphene in capsule wall and preparation method of microcapsule |
Non-Patent Citations (3)
| Title |
|---|
| CHEN FAN 等: "Pectin-conjugated silica microcapsules as dual-responsive carriers for increasing the stability and antimicrobial efficacy of kasugamycin", 《CARBOHYDRATE POLYMERS》 * |
| 冯龙宝 等: "一种谷胱甘肽响应型的药物基因共递送聚合物胶束载体", 《中国化学会2017全国高分子学术论文报告会摘要集——主题G：药物控释载体高分子》 * |
| 刘同金 等: "吡唑醚菌酯对小麦赤霉病的防效及在小麦籽粒中的残留", 《中国农学通报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113115786B (en) | 2021-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69823257T2 (en) | Spherical polyamide particles and process for their manufacture | |
| EP2201836B1 (en) | Microencapsulation of biocides and antifouling agents | |
| KR100869489B1 (en) | Blends of Encapsulated Biocides | |
| JP5523826B2 (en) | Microcapsules with acetylenecarbamide-polyurea polymers and their formulations for controlled release | |
| US4409201A (en) | Pressure-resistant microcapsules with a polyamide shell and a polyurethane-polyurea inner mass and process for their manufacture | |
| EP1569513A1 (en) | Microcapsules with amine adjusted release rates | |
| JP2009531169A5 (en) | ||
| CN107841048B (en) | A kind of polypropene composition of sensitization discoloration and its preparation method and application | |
| CN113115786B (en) | Glutathione-responsive polyurethane microcapsule suspension and preparation method and application thereof | |
| US5378413A (en) | Process for preparing microcapsules having gelatin walls crosslinked with quinone | |
| CN109692635B (en) | Isocyanate microcapsule and preparation method thereof | |
| US9622473B2 (en) | Herbicidal compositions | |
| CN114867798A (en) | Water-based ink composition for ballpoint pen | |
| JP5213040B2 (en) | Method for producing dispersion | |
| EP0686425B1 (en) | Process for producing microcapsule of hydrophobic drug | |
| CN106942218A (en) | Microcapsule formulation, soil treatment nematode micro-capsule suspension and preparation method thereof | |
| Kulkarni et al. | Polyurea and polyurethane microcapsules containing mosquito repellent DEET: preparation and characterization | |
| CN112169716A (en) | Preparation method of microcapsule coated with solid microparticles | |
| JP2006061802A (en) | Isocyanate-containing microcapsule and its manufacturing method, and coating composition, adhesive composition, and plastic modifying agent containing isocyanate-containing microcapsule | |
| CN114308065B (en) | Monodisperse Fe 30 Mo 1 Preparation method of Pt catalyst microspheres | |
| WO2003042274A1 (en) | Method for the production of microcapsules | |
| CN118027304A (en) | Unsaturated polyester resin hollow structure microsphere and preparation method thereof | |
| CN107602204B (en) | Moisture absorption preventing surface modification method for cetyl alcohol coated ammonium nitrate | |
| DE102020110905A1 (en) | Core-shell capsules for textile finishing | |
| CN112438263A (en) | Preparation method of microcapsule suspension-suspending agent containing s-metolachlor and topramezone, product and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |