CN109221107A - A kind of sustained releasing pesticide granule and preparation method thereof - Google Patents
A kind of sustained releasing pesticide granule and preparation method thereof Download PDFInfo
- Publication number
- CN109221107A CN109221107A CN201811059501.1A CN201811059501A CN109221107A CN 109221107 A CN109221107 A CN 109221107A CN 201811059501 A CN201811059501 A CN 201811059501A CN 109221107 A CN109221107 A CN 109221107A
- Authority
- CN
- China
- Prior art keywords
- pesticide
- activity component
- inorganic porous
- porous property
- pesticide activity
- 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.)
- Pending
Links
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
- 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
-
- 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
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of sustained releasing pesticide granules and preparation method thereof, the granule is in core-shell structure, the core is inorganic porous property substance and the pesticide activity component being carried on inorganic porous property substance, the shell is controlled release layer, wherein: the pesticide activity component includes pesticide activity component A and pesticide activity component B, and the weight ratio 2-4:1 of pesticide activity component A and pesticide activity component B;The BET specific surface area of the inorganic porous property substance is 600-950m2/ g and aperture are 5-30nm;The load capacity of the pesticide activity component is 100m2The BET specific surface area of inorganic porous property substance be 0.05-0.15ml;The shell is thermoplastic resin, and it is 10-20% that the gross mass of the thermoplastic resin, which accounts for the percentage of the granule gross mass,.The present invention is high, at low cost with utilization ratio of drug, pollution is low, and reduces the number for discharging pesticide.
Description
Technical field
The present invention relates to technical field of pesticide more particularly to a kind of sustained releasing pesticide granule and preparation method thereof.
Background technique
Slow-release pesticide refers to using natural, biodegradable high-molecular compound as slow-release material, by some interior suctions
Property insecticide, fungicide or growth regulator are compound with it, the pesticide with slow release performance being processed into.It is effective by pesticide
The release characteristics of ingredient are classified, and pesticide slow-release dosage form can be divided into the conventional type freely discharged and control release type two major classes.It is conventional
The effective percentage of type pesticide only has 20-30%, and loss late by all means is up to 50-60%, this is economically not only
A kind of waste, and the environmental pollution caused.Therefore, burst size, release time and Free up Memory are controllable, are always chemistry
One important directions of pesticides new formulation research.
The core of control release technic is that high-molecular compound and pesticide is made to interact, and pesticide activity component can be according to pre-
The concentration first set and time (needing to formulate according to the prevention and control of plant diseases, pest control) continue and are slowly released into environment, and can be long when
Between maintain a specific concentration.Therefore, the sustained-release dosage type of pesticide can make medicament due to the protective effect of polymer substance
Can be more stable, reduce the influence of the environmental factors such as water, air;Secondly, slow release method can greatly prolong same dose pesticide
Lasting period, thus can reduce pesticide access times and total dosage, make residual and significant decrease a possibility that environmental pollution;Again
Secondary, slow release method can reduce the toxicity and phytotoxicity of pesticide, therefore pesticide slow-release technology receives significant attention.
(application number: a kind of pesticide micro capsule sustained release agent and its preparation side 201610453420.4) are disclosed in Chinese patent
Method first passes through pesticide/silica microcapsules that the preparation of sol-gel method in-stiu coating has core-shell structure, then with coupling
Agent processing, makes its functional base of surface band, recycles function base and natural polymer to be crosslinked, prepares pesticide/silica/day
Right macromolecule bilayer cyst wall coats pesticide micro capsule.Although the pesticide micro capsule sustained release agent has, drugloading rate is high, sustained release performance is good,
The double-deck wall material cladding, the lasting period is long, wall material is environmentally friendly harmless, but its preparation process is complicated, and higher cost, in economy
On still lack competitiveness, it is difficult to widely promoted the use of.
And Chinese patent (application number: 201210197492.9) discloses a kind of slow control property pesticide grain of tool and non-slow control property agriculture
The mixing granules agent of powder, it by pesticidal active substance and filler material, surfactant after mixing, using package different-thickness
Clothing film and part not coating processing method preparation.The mixing granules agent of the pesticide grain had both retained the original speed of pesticide effective active
Effect property, and the physical and chemical stability of the pesticide effective active can be improved;But the mixing granules agent of the pesticide grain uses surface-active
Agent may cause solvent contamination to soil, in addition reach sustained release and quick-release with package different-thickness clothing film between different layers
Control, to its technique require it is harsher.
Therefore, it is necessary to provide a kind of sustained releasing pesticide granule and preparation method thereof, have that utilization ratio of drug is high, cost
It is low, pollution it is low, and reduce discharge pesticide number.
Summary of the invention
It is an object of the present invention in view of the deficiencies of the prior art, a kind of sustained releasing pesticide granule and its preparation are improved
Method, have utilization ratio of drug it is high, it is at low cost, pollution it is low, and reduce release pesticide number.
The present invention is achieved by the following technical solutions:
A kind of sustained releasing pesticide granule, the granule are in core-shell structure, and the core is inorganic porous property substance and load
Pesticide activity component on inorganic porous property substance, the shell are controlled release layer, in which:
The pesticide activity component includes pesticide activity component A and pesticide activity component B, and pesticide activity component A and agriculture
The weight ratio 2-4:1 of medicine active constituent B;
The BET specific surface area of the inorganic porous property substance is 600-950m2/ g and aperture are 5-30nm;
The load capacity of the pesticide activity component is 100m2The BET specific surface area of inorganic porous property substance be 0.05-
0.15ml;
The shell is thermoplastic resin, and the gross mass of the thermoplastic resin accounts for the percentage of the granule gross mass
For 10-20%.
Preferably, the pesticide activity component A and pesticide activity component B is selected from Insecticides (tech) & Herbicides (tech), sterilization
One or more of agent, acaricide, nematicide or plant growth regulator.
Specifically, the insecticide be selected from avermectin, ivermectin, multiple killing teichomycin, Diacloden, thiacloprid, flufenoxuron,
Capillary, fenazaquin, Nitenpyram, gamma cyhalothrin, fenvalerate, effective cypermethrin, cypermethrin, bromine cyanogen chrysanthemum
Ester, Fenpropathrin, Biphenthrin, ethofenprox, Buprofezin, Acetamiprid, Nitenpyram, butene-fipronil, lufenuron, flubenzuron,
Chlorfluazuron, flufenoxuron, diflubenzuron, chlopyrifos, Hostathion, phoxim, methidathion, diazinon, carbosulfan, Bassa, worm
One of hydrazides, Mobucin, Envidor, fenpyroximate, fenisobromolate, methamidophos, tebufenpyrad, Hexythiazox, propargite are any more
Kind can be used cooperatively the combination of drug.
The herbicide is selected from Acetochlor, pretilachlor, butachlor, fenoxapropPethyl, Quizalotop-ethyl, efficient fluorine pyrrole
One of the spirit of first standing grain, efficient fluazifop, cyhalofop-butyl, isopropyl methoxalamine, clomazone, oxadiazon any a variety of are matched
Close the combination for using drug.
The acaricide is selected from the one or more of fenbutatin oxide, quinoline mite spy, Hexythiazox and azacyclotin.
The nematicide is selected from one kind or several selected from fenamiphos, ethoprop, cadusafos, isazofos and Isofenphos methyl
Kind.
The plant growth regulator is selected from casing coupling peace, the one or more of uniconazole P, paclobutrazol and cycocel.
Preferably, the pesticide activity component B is solid content raw medicine, and has the thermal stability higher than 100 DEG C.
Preferably, the pesticide activity component B is pre-processed by overlay film, and the pretreated method of overlay film are as follows: is pressed
According to mass fraction, 20 parts of pesticide activity component B are heated to 90-100 DEG C in autoclave, then be added 4.5 parts of polyethylene waxes,
5 parts of methyl methacrylates, 2 parts of Arabic gums and 0.4 part of Emulsifier EL-60 are sufficiently stirred reaction 18-22min, obtain
2 parts of polyalkylene terephthalates, 1.5 parts of Linseed oils and 50 parts of deionized waters are mixed evenly, obtain by mixture A
To mixture B, mixture A and mixture B are passed through into different feed inlets respectively and put into emulsifying kettle, to be higher than 100 DEG C
Temperature high speed dispersion handles 30-50min, is then cooled to product and is discharged lower than 50 DEG C, is then filtered by vacuum, is dry, obtaining
Pesticide activity component B by coating processing.
Preferably, the inorganic porous property substance is selected from silicate compound, silica gel, zeolite and phosphate chemical combination
At least one of object.
Preferably, the thermoplastic resin is selected from vinylite, polyvinyl acetate, polyvinyl alcohol, poly- second
One or more of vinyl pyrrolidone, Pioloform, polyvinyl acetal, vinyl methylacetamide.
Preferably, the present invention also provides a kind of preparation methods of sustained releasing pesticide granule, comprising the following steps:
(1) inorganic porous property substance is put into ethyl alcohol and is stirred, be subsequently placed in centrifuge realize it is inorganic porous
Property substance and acetone separation, are dried after finally handling inorganic porous property substance with clear water;
(2) hydroxyethyl cellulose is configured to 5% solution, then by the inorganic porous property substance after above-mentioned drying process
Investment is wherein stirred, and is then carried out centrifugal treating and is realized that inorganic porous property substance is separated with carboxyethyl cellulose solution, will
Pesticide activity component A is adsorbed in the surface micropore of inorganic porous property substance;
(3) pesticide activity component B is adsorbed on inorganic porous property substance again;
(4) the inorganic porous property of pesticide activity component A and pesticide activity component B will be adsorbed in step (3) with adhesive
Spherical particle is made in substance, is dried for standby, as core;
(5) core described in step (4) is wrapped up into one layer of thermoplastic resin with adhesive again, obtains shell, drying is sustained
Pesticide granules.
Preferably, in step (2) centrifugal treating condition: revolving speed 4000-5000r/min, centrifugal treating time
12-14min。
Preferably, described adhesive is one or more of sodium alginate, starch, epoxy glue, gelatine.
Compared with prior art, the present invention have it is following the utility model has the advantages that
(1) active constituent of pesticide slow-release granule of the invention is by preset concentration and time (according to pest and disease damage
Prevention and treatment needs to formulate) continue and is slowly released into environment, there is no the drug injury problem to plant, and the effect of active constituent
Fruit can maintain one long time, extend the lasting period of pesticide, reduce spraying times, save laxative cost.
(2) present invention imposes in soil, adheres in this way by the way that pesticide activity component to be carried in inorganic porous property substance
Medicament in inorganic porous will slow release come out, to achieve the purpose that sustained release, and by by the agriculture of non-coating processing
Medicine active components A is placed in the aperture of inorganic porous property substance, and the pesticide activity component B of overlay film is then coated on pesticide again and is lived
On property ingredient A, it is thus formed with the release of gradient, it can be according to the demand in each stage of crop to pesticide activity component A and agriculture
Medicine active constituent B is adjusted, so that granular pesticide of the invention can control entire Growing season (or certain growth
Phase) pest and disease damage.
(3) polyethylene wax, methyl methacrylate, hydroxy-ethyl acrylate and polyoxy second are utilized in technical solution of the present invention
The ingredients such as alkene castor oil form a kind of special functional film layer in pesticide activity component B surface, the functional membrane can to drug into
Row effectively cladding, achievees the purpose that sustained release, and then improve the slow release effect of granular pesticide of the invention, and then play drug effect.
Specific embodiment
Below by specific embodiment, the present invention is further described, it is noted that for the ordinary skill of this field
For personnel, without departing from the principle of the present invention, several variations and modifications can also be made, these also should be regarded as belonging to
Protection scope of the present invention.
Embodiment 1
The sustained releasing pesticide granule of the present embodiment, the granule are in core-shell structure, and the core is inorganic porous property substance
And it is carried on the pesticide activity component on inorganic porous property substance, the shell is controlled release layer, in which:
The pesticide activity component includes pesticide activity component A and pesticide activity component B, and pesticide activity component A and agriculture
The weight ratio 2:1 of medicine active constituent B;
The BET specific surface area of the inorganic porous property substance is 600-950m2/ g and aperture are 5-30nm;
The load capacity of the pesticide activity component is 100m2The BET specific surface area of inorganic porous property substance be 0.05-
0.15ml;
The shell is thermoplastic resin, and the gross mass of the thermoplastic resin accounts for the percentage of the granule gross mass
It is 10%.
Wherein, the pesticide activity component A and pesticide activity component B be selected from Insecticides (tech) & Herbicides (tech), fungicide, acaricide,
One or more of nematicide or plant growth regulator.
Wherein, the pesticide activity component B is solid content raw medicine, and has the thermal stability higher than 100 DEG C.
Wherein, the pesticide activity component B is pre-processed by overlay film, and the pretreated method of overlay film are as follows: according to mass parts
20 parts of pesticide activity component B are heated to 90 DEG C by number in autoclave, and 4.5 parts of polyethylene waxes, 5 parts of metering systems are then added
Sour methyl esters, 2 parts of Arabic gums and 0.4 part of Emulsifier EL-60 are sufficiently stirred reaction 18min, obtain mixture A, poly- by 2 parts
Terephthalic acid (TPA) alkylene ester, 1.5 parts of Linseed oils and 50 parts of deionized waters are mixed evenly, and obtain mixture B, will mix
Object A and mixture B passes through different feed inlets respectively and puts into emulsifying kettle, is handled with the temperature high speed dispersion higher than 100 DEG C
Then product is cooled to and is discharged lower than 50 DEG C by 30min, be then filtered by vacuum, be dry, and the pesticide obtained by coating processing is living
Property ingredient B.
Wherein, the inorganic porous property substance in silicate compound, silica gel, zeolite and phosphate compounds extremely
Few one kind.
Wherein, the thermoplastic resin is selected from vinylite, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidine
One or more of alkanone, Pioloform, polyvinyl acetal, vinyl methylacetamide.
Wherein, the present invention also provides a kind of preparation methods of sustained releasing pesticide granule, comprising the following steps:
(1) inorganic porous property substance is put into ethyl alcohol and is stirred, be subsequently placed in centrifuge realize it is inorganic porous
Property substance and acetone separation, are dried after finally handling inorganic porous property substance with clear water;
(2) hydroxyethyl cellulose is configured to 5% solution, then by the inorganic porous property substance after above-mentioned drying process
Investment is wherein stirred, and is then carried out centrifugal treating and is realized that inorganic porous property substance is separated with carboxyethyl cellulose solution, will
Pesticide activity component A is adsorbed in the surface micropore of inorganic porous property substance;
(3) pesticide activity component B is adsorbed on inorganic porous property substance again;
(4) the inorganic porous property of pesticide activity component A and pesticide activity component B will be adsorbed in step (3) with adhesive
Spherical particle is made in substance, is dried for standby, as core;
(5) core described in step (4) is wrapped up into one layer of thermoplastic resin with adhesive again, obtains shell, drying is sustained
Pesticide granules.
Wherein, in step (2) centrifugal treating condition: revolving speed 4000r/min, centrifugal treating time 12min.
Wherein, described adhesive is one or more of sodium alginate, starch, epoxy glue, gelatine.
Embodiment 2
The sustained releasing pesticide granule of the present embodiment, the granule are in core-shell structure, and the core is inorganic porous property substance
And it is carried on the pesticide activity component on inorganic porous property substance, the shell is controlled release layer, in which:
The pesticide activity component includes pesticide activity component A and pesticide activity component B, and pesticide activity component A and agriculture
The weight ratio 4:1 of medicine active constituent B;
The BET specific surface area of the inorganic porous property substance is 600-950m2/ g and aperture are 5-30nm;
The load capacity of the pesticide activity component is 100m2The BET specific surface area of inorganic porous property substance be 0.05-
0.15ml;
The shell is thermoplastic resin, and the gross mass of the thermoplastic resin accounts for the percentage of the granule gross mass
It is 20%.
Wherein, the pesticide activity component A and pesticide activity component B be selected from Insecticides (tech) & Herbicides (tech), fungicide, acaricide,
One or more of nematicide or plant growth regulator.
Wherein, the pesticide activity component B is solid content raw medicine, and has the thermal stability higher than 100 DEG C.
Wherein, the pesticide activity component B is pre-processed by overlay film, and the pretreated method of overlay film are as follows: according to mass parts
20 parts of pesticide activity component B are heated to 100 DEG C by number in autoclave, and 4.5 parts of polyethylene waxes, 5 parts of metering systems are then added
Sour methyl esters, 2 parts of Arabic gums and 0.4 part of Emulsifier EL-60 are sufficiently stirred reaction 22min, obtain mixture A, poly- by 2 parts
Terephthalic acid (TPA) alkylene ester, 1.5 parts of Linseed oils and 50 parts of deionized waters are mixed evenly, and obtain mixture B, will mix
Object A and mixture B passes through different feed inlets respectively and puts into emulsifying kettle, is handled with the temperature high speed dispersion higher than 100 DEG C
Then product is cooled to and is discharged lower than 50 DEG C by 50min, be then filtered by vacuum, be dry, and the pesticide obtained by coating processing is living
Property ingredient B.
Wherein, the inorganic porous property substance in silicate compound, silica gel, zeolite and phosphate compounds extremely
Few one kind.
Wherein, the thermoplastic resin is selected from vinylite, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidine
One or more of alkanone, Pioloform, polyvinyl acetal, vinyl methylacetamide.
Wherein, the present invention also provides a kind of preparation methods of sustained releasing pesticide granule, comprising the following steps:
(1) inorganic porous property substance is put into ethyl alcohol and is stirred, be subsequently placed in centrifuge realize it is inorganic porous
Property substance and acetone separation, are dried after finally handling inorganic porous property substance with clear water;
(2) hydroxyethyl cellulose is configured to 5% solution, then by the inorganic porous property substance after above-mentioned drying process
Investment is wherein stirred, and is then carried out centrifugal treating and is realized that inorganic porous property substance is separated with carboxyethyl cellulose solution, will
Pesticide activity component A is adsorbed in the surface micropore of inorganic porous property substance;
(3) pesticide activity component B is adsorbed on inorganic porous property substance again;
(4) the inorganic porous property of pesticide activity component A and pesticide activity component B will be adsorbed in step (3) with adhesive
Spherical particle is made in substance, is dried for standby, as core;
(5) core described in step (4) is wrapped up into one layer of thermoplastic resin with adhesive again, obtains shell, drying is sustained
Pesticide granules.
Wherein, in step (2) centrifugal treating condition: revolving speed 5000r/min, centrifugal treating time 14min.
Wherein, described adhesive is one or more of sodium alginate, starch, epoxy glue, gelatine.
Embodiment 3
The sustained releasing pesticide granule of the present embodiment, the granule are in core-shell structure, and the core is inorganic porous property substance
And it is carried on the pesticide activity component on inorganic porous property substance, the shell is controlled release layer, in which:
The pesticide activity component includes pesticide activity component A and pesticide activity component B, and pesticide activity component A and agriculture
The weight ratio 3:1 of medicine active constituent B;
The BET specific surface area of the inorganic porous property substance is 600-950m2/ g and aperture are 5-30nm;
The load capacity of the pesticide activity component is 100m2The BET specific surface area of inorganic porous property substance be 0.05-
0.15ml;
The shell is thermoplastic resin, and the gross mass of the thermoplastic resin accounts for the percentage of the granule gross mass
It is 15%.
Wherein, the pesticide activity component A and pesticide activity component B be selected from Insecticides (tech) & Herbicides (tech), fungicide, acaricide,
One or more of nematicide or plant growth regulator.
Wherein, the pesticide activity component B is solid content raw medicine, and has the thermal stability higher than 100 DEG C.
Wherein, the pesticide activity component B is pre-processed by overlay film, and the pretreated method of overlay film are as follows: according to mass parts
20 parts of pesticide activity component B are heated to 95 DEG C by number in autoclave, and 4.5 parts of polyethylene waxes, 5 parts of metering systems are then added
Sour methyl esters, 2 parts of Arabic gums and 0.4 part of Emulsifier EL-60 are sufficiently stirred reaction 20min, obtain mixture A, poly- by 2 parts
Terephthalic acid (TPA) alkylene ester, 1.5 parts of Linseed oils and 50 parts of deionized waters are mixed evenly, and obtain mixture B, will mix
Object A and mixture B passes through different feed inlets respectively and puts into emulsifying kettle, is handled with the temperature high speed dispersion higher than 100 DEG C
Then product is cooled to and is discharged lower than 50 DEG C by 40min, be then filtered by vacuum, be dry, and the pesticide obtained by coating processing is living
Property ingredient B.
Wherein, the inorganic porous property substance in silicate compound, silica gel, zeolite and phosphate compounds extremely
Few one kind.
Wherein, the thermoplastic resin is selected from vinylite, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidine
One or more of alkanone, Pioloform, polyvinyl acetal, vinyl methylacetamide.
Wherein, the present invention also provides a kind of preparation methods of sustained releasing pesticide granule, comprising the following steps:
(1) inorganic porous property substance is put into ethyl alcohol and is stirred, be subsequently placed in centrifuge realize it is inorganic porous
Property substance and acetone separation, are dried after finally handling inorganic porous property substance with clear water;
(2) hydroxyethyl cellulose is configured to 5% solution, then by the inorganic porous property substance after above-mentioned drying process
Investment is wherein stirred, and is then carried out centrifugal treating and is realized that inorganic porous property substance is separated with carboxyethyl cellulose solution, will
Pesticide activity component A is adsorbed in the surface micropore of inorganic porous property substance;
(3) pesticide activity component B is adsorbed on inorganic porous property substance again;
(4) the inorganic porous property of pesticide activity component A and pesticide activity component B will be adsorbed in step (3) with adhesive
Spherical particle is made in substance, is dried for standby, as core;
(5) core described in step (4) is wrapped up into one layer of thermoplastic resin with adhesive again, obtains shell, drying is sustained
Pesticide granules.
Wherein, in step (2) centrifugal treating condition: revolving speed 4500r/min, centrifugal treating time 13min.
Wherein, described adhesive is one or more of sodium alginate, starch, epoxy glue, gelatine.
Embodiment 4
The sustained releasing pesticide granule of the present embodiment, the granule are in core-shell structure, and the core is inorganic porous property substance
And it is carried on the pesticide activity component on inorganic porous property substance, the shell is controlled release layer, in which:
The pesticide activity component includes pesticide activity component A and pesticide activity component B, and pesticide activity component A and agriculture
The weight ratio 2.5:1 of medicine active constituent B;
The BET specific surface area of the inorganic porous property substance is 600-950m2/ g and aperture are 5-30nm;
The load capacity of the pesticide activity component is 100m2The BET specific surface area of inorganic porous property substance be 0.05-
0.15ml;
The shell is thermoplastic resin, and the gross mass of the thermoplastic resin accounts for the percentage of the granule gross mass
It is 13%.
Wherein, the pesticide activity component A and pesticide activity component B be selected from Insecticides (tech) & Herbicides (tech), fungicide, acaricide,
One or more of nematicide or plant growth regulator.
Wherein, the pesticide activity component B is solid content raw medicine, and has the thermal stability higher than 100 DEG C.
Wherein, the pesticide activity component B is pre-processed by overlay film, and the pretreated method of overlay film are as follows: according to mass parts
20 parts of pesticide activity component B are heated to 92 DEG C by number in autoclave, and 4.5 parts of polyethylene waxes, 5 parts of metering systems are then added
Sour methyl esters, 2 parts of Arabic gums and 0.4 part of Emulsifier EL-60 are sufficiently stirred reaction 19min, obtain mixture A, poly- by 2 parts
Terephthalic acid (TPA) alkylene ester, 1.5 parts of Linseed oils and 50 parts of deionized waters are mixed evenly, and obtain mixture B, will mix
Object A and mixture B passes through different feed inlets respectively and puts into emulsifying kettle, is handled with the temperature high speed dispersion higher than 100 DEG C
Then product is cooled to and is discharged lower than 50 DEG C by 35min, be then filtered by vacuum, be dry, and the pesticide obtained by coating processing is living
Property ingredient B.
Wherein, the inorganic porous property substance in silicate compound, silica gel, zeolite and phosphate compounds extremely
Few one kind.
Wherein, the thermoplastic resin is selected from vinylite, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidine
One or more of alkanone, Pioloform, polyvinyl acetal, vinyl methylacetamide.
Wherein, the present invention also provides a kind of preparation methods of sustained releasing pesticide granule, comprising the following steps:
(1) inorganic porous property substance is put into ethyl alcohol and is stirred, be subsequently placed in centrifuge realize it is inorganic porous
Property substance and acetone separation, are dried after finally handling inorganic porous property substance with clear water;
(2) hydroxyethyl cellulose is configured to 5% solution, then by the inorganic porous property substance after above-mentioned drying process
Investment is wherein stirred, and is then carried out centrifugal treating and is realized that inorganic porous property substance is separated with carboxyethyl cellulose solution, will
Pesticide activity component A is adsorbed in the surface micropore of inorganic porous property substance;
(3) pesticide activity component B is adsorbed on inorganic porous property substance again;
(4) the inorganic porous property of pesticide activity component A and pesticide activity component B will be adsorbed in step (3) with adhesive
Spherical particle is made in substance, is dried for standby, as core;
(5) core described in step (4) is wrapped up into one layer of thermoplastic resin with adhesive again, obtains shell, drying is sustained
Pesticide granules.
Wherein, in step (2) centrifugal treating condition: revolving speed 4200r/min, centrifugal treating time 13min.
Wherein, described adhesive is one or more of sodium alginate, starch, epoxy glue, gelatine.
Embodiment 5
The sustained releasing pesticide granule of the present embodiment, the granule are in core-shell structure, and the core is inorganic porous property substance
And it is carried on the pesticide activity component on inorganic porous property substance, the shell is controlled release layer, in which:
The pesticide activity component includes pesticide activity component A and pesticide activity component B, and pesticide activity component A and agriculture
The weight ratio 3.5:1 of medicine active constituent B;
The BET specific surface area of the inorganic porous property substance is 600-950m2/ g and aperture are 5-30nm;
The load capacity of the pesticide activity component is 100m2The BET specific surface area of inorganic porous property substance be 0.05-
0.15ml;
The shell is thermoplastic resin, and the gross mass of the thermoplastic resin accounts for the percentage of the granule gross mass
It is 18%.
Wherein, the pesticide activity component A and pesticide activity component B be selected from Insecticides (tech) & Herbicides (tech), fungicide, acaricide,
One or more of nematicide or plant growth regulator.
Wherein, the pesticide activity component B is solid content raw medicine, and has the thermal stability higher than 100 DEG C.
Wherein, the pesticide activity component B is pre-processed by overlay film, and the pretreated method of overlay film are as follows: according to mass parts
20 parts of pesticide activity component B are heated to 98 DEG C by number in autoclave, and 4.5 parts of polyethylene waxes, 5 parts of metering systems are then added
Sour methyl esters, 2 parts of Arabic gums and 0.4 part of Emulsifier EL-60 are sufficiently stirred reaction 21min, obtain mixture A, poly- by 2 parts
Terephthalic acid (TPA) alkylene ester, 1.5 parts of Linseed oils and 50 parts of deionized waters are mixed evenly, and obtain mixture B, will mix
Object A and mixture B passes through different feed inlets respectively and puts into emulsifying kettle, is handled with the temperature high speed dispersion higher than 100 DEG C
Then product is cooled to and is discharged lower than 50 DEG C by 45min, be then filtered by vacuum, be dry, and the pesticide obtained by coating processing is living
Property ingredient B.
Wherein, the inorganic porous property substance in silicate compound, silica gel, zeolite and phosphate compounds extremely
Few one kind.
Wherein, the thermoplastic resin is selected from vinylite, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidine
One or more of alkanone, Pioloform, polyvinyl acetal, vinyl methylacetamide.
Wherein, the present invention also provides a kind of preparation methods of sustained releasing pesticide granule, comprising the following steps:
(1) inorganic porous property substance is put into ethyl alcohol and is stirred, be subsequently placed in centrifuge realize it is inorganic porous
Property substance and acetone separation, are dried after finally handling inorganic porous property substance with clear water;
(2) hydroxyethyl cellulose is configured to 5% solution, then by the inorganic porous property substance after above-mentioned drying process
Investment is wherein stirred, and is then carried out centrifugal treating and is realized that inorganic porous property substance is separated with carboxyethyl cellulose solution, will
Pesticide activity component A is adsorbed in the surface micropore of inorganic porous property substance;
(3) pesticide activity component B is adsorbed on inorganic porous property substance again;
(4) the inorganic porous property of pesticide activity component A and pesticide activity component B will be adsorbed in step (3) with adhesive
Spherical particle is made in substance, is dried for standby, as core;
(5) core described in step (4) is wrapped up into one layer of thermoplastic resin with adhesive again, obtains shell, drying is sustained
Pesticide granules.
Wherein, in step (2) centrifugal treating condition: revolving speed 4800r/min, centrifugal treating time 13min.
Wherein, described adhesive is one or more of sodium alginate, starch, epoxy glue, gelatine.
Comparative example 1
The controlled release layer of sustained releasing pesticide granule is removed, only retains nuclear structure, other material contents and preparation method with real
It is consistent to apply example 1.
Comparative example 2
The overlay film pre-treatment step of pesticide activity component B is saved, other material contents and the preparation method is the same as that of Example 1 one
It causes.
Comparative example 3
In addition to changing inorganic porous property substance into inorganic substances, other material contents and that the preparation method is the same as that of Example 1 is consistent.
Test example 1
The test of pesticide activity component rate of release:
Granular pesticide made from embodiment 1-5 and comparative example 1-3 is put in respectively in the beaker of 1000ml, then is distinguished
1000ml distilled water is poured into beaker.After 1,3,5,7,9,16,24 day, 10ml water is taken out, using high performance liquid chromatography
It analyzes from the concentration for the pesticide activity component being discharged into preparation in water.As a result it is listed in the table below in 1.
Table 1
As shown in Table 1, the slow release effect of granular pesticide made from 1-5 of the embodiment of the present invention is better than comparative example 1-3, and real
The slow release effect for applying example 3 is optimal, and by comparative example 1 it is found that granular pesticide is without coating processing, the not formed controlled release in surface
Layer, the speed spread in water so as to cause it is fast, and slow release effect is poor;And by comparative example 2 it is found that due to pesticide activity component B
Pre-processed without overlay film, at the beginning its diffusion velocity is slower in water, after preparative layer to be controlled is completely dissolved, spread in water
Speed is accelerated, and slow release effect is deteriorated;It, can be by pesticide activity and by comparative example 3 it is found that inorganic porous property substance is since there are apertures
Ingredient is adsorbed in its surface apertures, to improve the slow release effect of granular pesticide.
Test example 2
The test of field control tomato root-knot eelworm disease:
Medicament uniformly imposed in plant hole in tomato transplanting and earthing 2-3cm, then root-knot nematode will be there is no to endanger
Tomato transplantation of seedlings is in plant hole, and earthing is steady and sure, pours root water.Route selection worm is evenly distributed and the continuous cropping plot for medium weighting of causing harm
It is tested, plot area 2m × 5m, every cell plants 40 plants, and every cell applies 0.5% sustained release agriculture prepared with embodiment 3 respectively
Comparison medicament processing: medicine granule 75g applies 0.5% sustained release agriculture prepared by comparative example 1 and comparative example 2 as experimental group respectively
Medicine granule 75g as a control group 1 and control group 2, CK be blank control, repeat three times.In application before and application after 30d,
60d, 90d, 120d choose root system 5 plants of plant of uniform size in every cell crop respectively, take the soil of 5-15cm depth bounds
200mL counts wherein root-knot nematode, calculates control efficiency.Test result is listed in the table below 2.
Table 2
As shown in Table 2, the granular pesticide of the embodiment of the present invention 3 has good control efficiency to tomato root-knot eelworm
With good sustained release performance;Granular pesticide made from comparative example 1 has tomato root-knot eelworm due to uncoated controlled release layer
Good control efficiency is gradually reduced;And granular pesticide made from comparative example 2, since the overlay film of pesticide activity component B being walked
Suddenly it saves, the granular pesticide after causing 60 days there is good control efficiency to be gradually reduced tomato root-knot eelworm.
In conclusion creativeness of the invention is mainly reflected in the following aspects:
(1) active constituent of pesticide slow-release granule of the invention is by preset concentration and time (according to pest and disease damage
Prevention and treatment needs to formulate) continue and is slowly released into environment, there is no the drug injury problem to plant, and the effect of active constituent
Fruit can maintain one long time, extend the lasting period of pesticide, reduce spraying times, save laxative cost.
(2) present invention imposes in soil, adheres in this way by the way that pesticide activity component to be carried in inorganic porous property substance
Medicament in inorganic porous will slow release come out, to achieve the purpose that sustained release, and by by the agriculture of non-coating processing
Medicine active components A is placed in the aperture of inorganic porous property substance, and the pesticide activity component B of overlay film is then coated on pesticide again and is lived
On property ingredient A, it is thus formed with the release of gradient, it can be according to the demand in each stage of crop to pesticide activity component A and agriculture
Medicine active constituent B is adjusted, so that granular pesticide of the invention can control entire Growing season (or certain growth
Phase) pest and disease damage.
(3) polyethylene wax, methyl methacrylate, hydroxy-ethyl acrylate and polyoxy second are utilized in technical solution of the present invention
The ingredients such as alkene castor oil form a kind of special functional film layer in pesticide activity component B surface, the functional membrane can to drug into
Row effectively cladding, achievees the purpose that sustained release, and then improve the slow release effect of granular pesticide of the invention, and then play drug effect.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of sustained releasing pesticide granule, which is characterized in that the granule is in core-shell structure, and the core is inorganic porous property object
Matter and the pesticide activity component being carried on inorganic porous property substance, the shell are controlled release layer, in which:
The pesticide activity component includes pesticide activity component A and pesticide activity component B, and pesticide activity component A and pesticide are living
The weight ratio 2-4:1 of property ingredient B;
The BET specific surface area of the inorganic porous property substance is 600-950m2/ g and aperture are 5-30nm;
The load capacity of the pesticide activity component is 100m2The BET specific surface area of inorganic porous property substance be 0.05-0.15ml;
The shell is thermoplastic resin, and the gross mass of the thermoplastic resin accounts for the percentage of the granule gross mass and is
10-20%.
2. sustained releasing pesticide granule according to claim 1, which is characterized in that the pesticide activity component A and pesticide are living
Property ingredient B be selected from one or both of Insecticides (tech) & Herbicides (tech), fungicide, acaricide, nematicide or plant growth regulator
More than.
3. sustained releasing pesticide granule according to claim 2, which is characterized in that the pesticide activity component B is solid content
Raw medicine, and there is the thermal stability higher than 100 DEG C.
4. sustained releasing pesticide granule according to claim 3, which is characterized in that the pesticide activity component B passes through overlay film
Pretreatment, and the pretreated method of overlay film are as follows:
According to mass fraction, 20 parts of pesticide activity component B are heated to 90-100 DEG C in autoclave, are then added 4.5 parts and gather
Reaction 18- is sufficiently stirred in ethylene waxes, 5 parts of methyl methacrylates, 2 parts of Arabic gums and 0.4 part of Emulsifier EL-60
22min obtains mixture A, and 2 parts of polyalkylene terephthalates, 1.5 parts of Linseed oils and 50 parts of deionized waters are mixed and stirred
It mixes uniformly, obtains mixture B, mixture A and mixture B are passed through into different feed inlets respectively and put into emulsifying kettle, with height
30-50min is handled in 100 DEG C of temperature high speed dispersions, then product is cooled to and is discharged lower than 50 DEG C, be then filtered by vacuum,
It is dry, obtain the pesticide activity component B by coating processing.
5. sustained releasing pesticide granule according to claim 1, which is characterized in that the inorganic porous property substance is selected from silicic acid
At least one of salt compound, silica gel, zeolite and phosphate compounds.
6. sustained releasing pesticide granule according to claim 1, which is characterized in that the thermoplastic resin is selected from vinyl tree
Rouge, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, Pioloform, polyvinyl acetal, in vinyl methylacetamide
It is one or more kinds of.
7. the preparation method of sustained releasing pesticide granule according to claim 1-6, which is characterized in that including following
Step:
(1) inorganic porous property substance is put into ethyl alcohol and is stirred, be subsequently placed in centrifuge and realize inorganic porous property object
Matter and acetone separation are dried after finally handling inorganic porous property substance with clear water;
(2) hydroxyethyl cellulose is configured to 5% solution, then puts into the inorganic porous property substance after above-mentioned drying process
It is wherein stirred, then carries out centrifugal treating and realize that inorganic porous property substance is separated with carboxyethyl cellulose solution, by pesticide
Active components A is adsorbed in the surface micropore of inorganic porous property substance;
(3) pesticide activity component B is adsorbed on inorganic porous property substance again;
(4) the inorganic porous property substance of pesticide activity component A and pesticide activity component B will be adsorbed in step (3) with adhesive
Spherical particle is made, is dried for standby, as core;
(5) core described in step (4) is wrapped up into one layer of thermoplastic resin with adhesive again, obtains shell, drying obtains sustained-release pesticides
Particle.
8. the preparation method of sustained releasing pesticide granule according to claim 7, which is characterized in that in step (2) at centrifugation
The condition of reason: revolving speed 4000-5000r/min, centrifugal treating time 12-14min.
9. the preparation method of sustained releasing pesticide granule according to claim 7, which is characterized in that described adhesive is seaweed
One or more of sour sodium, starch, epoxy glue, gelatine.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811059501.1A CN109221107A (en) | 2018-09-12 | 2018-09-12 | A kind of sustained releasing pesticide granule and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811059501.1A CN109221107A (en) | 2018-09-12 | 2018-09-12 | A kind of sustained releasing pesticide granule and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109221107A true CN109221107A (en) | 2019-01-18 |
Family
ID=65067562
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811059501.1A Pending CN109221107A (en) | 2018-09-12 | 2018-09-12 | A kind of sustained releasing pesticide granule and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109221107A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114804563A (en) * | 2022-06-27 | 2022-07-29 | 珠江水利委员会珠江水利科学研究院 | Method for synchronously removing carbon, nitrogen and sulfur pollutants in polluted bottom mud |
CN114931791A (en) * | 2022-06-02 | 2022-08-23 | 江苏春江润田农化有限公司 | Bifenthrin purification and dehydration device |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102134174A (en) * | 2011-04-07 | 2011-07-27 | 枣庄市沃丰化工有限公司 | Organic insecticide envelope pesticide fertilizer and manufacturing technique |
CN102210302A (en) * | 2011-04-13 | 2011-10-12 | 华南理工大学 | Porous inorganic material with insecticidal and mothproof function and preparation method thereof |
CN102276356A (en) * | 2011-07-11 | 2011-12-14 | 广西田园生化股份有限公司 | Stable controlled release particle pesticide-containing fertilizer |
CN102351608A (en) * | 2011-07-11 | 2012-02-15 | 广西田园生化股份有限公司 | Controlled release particle fertilizer used for controlling crop insect disease |
CN102461498A (en) * | 2010-11-08 | 2012-05-23 | 河南好年景生物发展有限公司 | Preparation method of slow-release pesticide |
CN102696587A (en) * | 2012-06-15 | 2012-10-03 | 河南好年景生物发展有限公司 | Compound controlled-release granular pesticide preparation and preparation method thereof |
CN102718606A (en) * | 2012-07-12 | 2012-10-10 | 广西田园生化股份有限公司 | Fipronil-containing slow-release insecticidal fertilizer granule |
CN102823619A (en) * | 2012-09-20 | 2012-12-19 | 贵州大学 | Imidacloprid sustained-release granules and preparation and application thereof |
CN104430399A (en) * | 2014-11-14 | 2015-03-25 | 中国农业科学院植物保护研究所 | Preparation method and application of metalaxyl and abamectin controlled-release granules |
CN106278515A (en) * | 2015-05-29 | 2017-01-04 | 拜城县富康猪业有限责任公司 | A kind of spacetabs type micro organism composite fertilizer and preparation method thereof |
CN107372516A (en) * | 2017-07-26 | 2017-11-24 | 南通功成精细化工有限公司 | A kind of hygienic biocide granule and preparation method thereof |
CN108314543A (en) * | 2018-04-16 | 2018-07-24 | 安徽梅兰园林景观工程有限公司 | A kind of soil improvement fertilizer of flower planting and preparation method thereof |
-
2018
- 2018-09-12 CN CN201811059501.1A patent/CN109221107A/en active Pending
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102461498A (en) * | 2010-11-08 | 2012-05-23 | 河南好年景生物发展有限公司 | Preparation method of slow-release pesticide |
CN102134174A (en) * | 2011-04-07 | 2011-07-27 | 枣庄市沃丰化工有限公司 | Organic insecticide envelope pesticide fertilizer and manufacturing technique |
CN102210302A (en) * | 2011-04-13 | 2011-10-12 | 华南理工大学 | Porous inorganic material with insecticidal and mothproof function and preparation method thereof |
CN102276356A (en) * | 2011-07-11 | 2011-12-14 | 广西田园生化股份有限公司 | Stable controlled release particle pesticide-containing fertilizer |
CN102351608A (en) * | 2011-07-11 | 2012-02-15 | 广西田园生化股份有限公司 | Controlled release particle fertilizer used for controlling crop insect disease |
CN102696587A (en) * | 2012-06-15 | 2012-10-03 | 河南好年景生物发展有限公司 | Compound controlled-release granular pesticide preparation and preparation method thereof |
CN102718606A (en) * | 2012-07-12 | 2012-10-10 | 广西田园生化股份有限公司 | Fipronil-containing slow-release insecticidal fertilizer granule |
CN102823619A (en) * | 2012-09-20 | 2012-12-19 | 贵州大学 | Imidacloprid sustained-release granules and preparation and application thereof |
CN104430399A (en) * | 2014-11-14 | 2015-03-25 | 中国农业科学院植物保护研究所 | Preparation method and application of metalaxyl and abamectin controlled-release granules |
CN106278515A (en) * | 2015-05-29 | 2017-01-04 | 拜城县富康猪业有限责任公司 | A kind of spacetabs type micro organism composite fertilizer and preparation method thereof |
CN107372516A (en) * | 2017-07-26 | 2017-11-24 | 南通功成精细化工有限公司 | A kind of hygienic biocide granule and preparation method thereof |
CN108314543A (en) * | 2018-04-16 | 2018-07-24 | 安徽梅兰园林景观工程有限公司 | A kind of soil improvement fertilizer of flower planting and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
张一宾: "农药剂型的设计和新剂型的开发", 《世界农药》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114931791A (en) * | 2022-06-02 | 2022-08-23 | 江苏春江润田农化有限公司 | Bifenthrin purification and dehydration device |
CN114931791B (en) * | 2022-06-02 | 2024-04-16 | 江苏春江润田农化有限公司 | Bifenthrin purification dewatering device |
CN114804563A (en) * | 2022-06-27 | 2022-07-29 | 珠江水利委员会珠江水利科学研究院 | Method for synchronously removing carbon, nitrogen and sulfur pollutants in polluted bottom mud |
CN114804563B (en) * | 2022-06-27 | 2022-10-11 | 珠江水利委员会珠江水利科学研究院 | Method for synchronously removing carbon, nitrogen and sulfur pollutants in polluted bottom mud |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107306942B (en) | Preparation method of controlled release type nano pesticide preparation | |
CN107347881B (en) | Pesticide nanocapsule and preparation method thereof | |
CN107258778B (en) | Preparation method of pesticide nanocapsule | |
US8026196B2 (en) | Delayed-effect agronomic treatment agent, in particular for seed germination and plant development | |
CN103070166B (en) | Micro-capsule suspension-water emulsion ZW and preparation method thereof | |
CN107156119B (en) | Nano pesticide preparation and preparation method thereof | |
JPH0310372B2 (en) | ||
ZA200203697B (en) | A method of microencapsulation. | |
US5725869A (en) | Microsphere reservoirs for controlled release application | |
MX2011000682A (en) | Microcapsules comprising active ingredients and a metal oxide shell, a method for their preparation and uses thereof. | |
CN103798232A (en) | Emamectin benzoate microsphere and preparation method thereof | |
CN102939964B (en) | Load-controllable hydrophobic pesticide sustained-release microcapsule and preparation method thereof | |
CN107455492A (en) | A kind of method that nano-silicon dioxide modified microcapsule wall material prepares microcapsules | |
CN109221107A (en) | A kind of sustained releasing pesticide granule and preparation method thereof | |
CN101773112B (en) | Preparation method of pesticide diuron slow controlled release nanometer composite material | |
CN108029686A (en) | A kind of pirimiphos-methyl microcapsule pesticide and preparation method thereof | |
CN109258632A (en) | A kind of nano pesticide composition and preparation method thereof | |
CN114097777B (en) | Double-layer drug-loaded sustained-release microcapsule and preparation method and application thereof | |
Sharifi et al. | Formulation and agricultural application of bacterial volatile compounds | |
CN101828555B (en) | Method for preparing pyraflufen-ethyl pesticide sustained or controlled release composite material | |
EP0018119B1 (en) | Encapsulated pesticidal composition and a method for making it | |
CN108739872A (en) | A kind of natural pyrethrin microcapsules and preparation method thereof | |
CN105746509B (en) | A kind of nematicide microcapsules and preparation method thereof | |
CN1775039A (en) | Nim oil micro capsule and its preparing method | |
Beixing et al. | Research advances and application prospects of microencapsulation techniques in pesticide |
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 | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190118 |