CN109953021A - Pyrethroids microcapsules, preparation method and insect prevention preparation - Google Patents
Pyrethroids microcapsules, preparation method and insect prevention preparation Download PDFInfo
- Publication number
- CN109953021A CN109953021A CN201711435674.4A CN201711435674A CN109953021A CN 109953021 A CN109953021 A CN 109953021A CN 201711435674 A CN201711435674 A CN 201711435674A CN 109953021 A CN109953021 A CN 109953021A
- Authority
- CN
- China
- Prior art keywords
- pyrethroids
- microcapsules
- solution
- preparation
- softgel shell
- 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
- A01N25/28—Microcapsules or nanocapsules
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Abstract
The invention discloses pyrethroids microcapsules and preparation method thereof and the insect prevention preparations obtained with pyrethroids microcapsules.The microcapsules include softgel shell and capsule-core, wherein softgel shell is poly-dopamine, and capsule-core is pyrethroids, and the pyrethroids is one of gamma cyhalothrin, betacyfluthrin, Biphenthrin or alphamethrin or a variety of, and capsule-core is wrapped in softgel shell.Preparation method of the present invention, including, step (1), hollow poly-dopamine softgel shell is provided, step (2) provides pyrethroids solution into the softgel shell and forms capsule-core, the solvent of the solution is n,N-Dimethylformamide or N-METHYLFORMAMIDE.It present invention improves the chemical stability of pyrethrin pesticide and releases the control, extends the lasting period, reduces toxic side effect and improve bioavilability.
Description
Technical field
The present invention relates to pyrethroids microcapsules, preparation method and the insect prevention preparations obtained with pyrethroids microcapsules.
Background technique
Gamma cyhalothrin (Universal Chinese character name, English general entitled Lambda-Cyhalothrin, CAS:91465-
08-6), molecular formula C23H19ClF3NO3, chemical name is 3- (2- chloro-3,3,3 ,-trifluoropropene base) -2,2- dimethyl cyclopropyl
Alkane carboxylic acid alpha-cyano -3- phenoxybenzyl ester is a kind of efficient, wide spectrum, quick-acting pyrethroid Insecticidal and acaricidal agents, with touching
Kill with stomach poison function based on, no systemic action.
Betacyfluthrin (Universal Chinese character name, English general entitled Beta-Cyfluthrin, CAS:68359-37-
5), molecular formula C22H18Cl2FNO3, chemical name is cyano-(the fluoro- 3- benzyloxy phenoxy base of 4-)-methyl-(2,2- dichloroethylene)-
2,2- dimethyl cyclopropane carboxylic acid's esters.It is a kind of pyrethroid insecticides of synthesis, has and tag and stomach poison function, desinsection
Spectrum is wide, knocks down rapidly, the lasting period is long, and plant has good drug resistance to it.
Biphenthrin (Universal Chinese character name, English general entitled Bifenthrin, CAS:82657-04-3), molecular formula
C46H44Cl2F6O4, to light stablize, it is also more stable in acid medium, at normal temperature store 1 year it is still more stable, but alkalinity be situated between
It can be decomposed in matter.
Alphamethrin (Universal Chinese character name, English general entitled Alphacypermethrin, CAS:67375-30-
8), molecular formula C22H19Cl2NO3, chemical name be (RS)-cyano (3- phenoxy phenyl) methyl (IRS) cis trans -3- (2,
2- dichloroethylene) -2,2- dimethyl cyclopropane carboxylic acid's ester.It is hydrolyzed under neutral and stable under acidic conditions, basic conditions.Heat
Stability is preferable, and normal temperature storage can be stablized 2 years or more.
The mechanism of action of above-mentioned pyrethroids be inhibit insect neural axon position conduction, to insect have walk quickly and keep away, knock down and
The characteristics of poisoning, insecticidal spectrum is wide, and activity is higher, and drug effect is rapid, resistance of rainwater washing against after sprinkling.Gamma cyhalothrin is to elytrum
The various pests such as mesh, Lepidoptera, Semiptera and mite class have good insecticidal, simultaneous can control when worm, mite are concurrent.Above-mentioned pyrethroids
Cotton, vegetables, fruit tree and a variety of earth's surfaces and public health pest can also be prevented and treated.
The conventional dosage forms that existing above-mentioned pyrethroids uses include missible oil, synergy missible oil, wettable powder, water dispersible granules, water
Emulsion, microemulsion and the compound preparation with other insecticides.For these dosage forms based on missible oil dosage form, content is mostly mass percent
2.5% or 10%.There is all kinds of defects for these dosage forms, and the storage stability such as preparation is poor, are unable to control release, and need
It consumes a large amount of organic solvent and storage and transportation and use is dangerous, suspensibility is low so that purposes is restricted.
In addition, being directed to the daily production and living environment of people, the dosage form of existing pyrethroids has certain murder by poisoning to human body, strong to human body
Health and ecological protection damage.
Summary of the invention
The technical problem to be solved by the present invention is how to improve gamma cyhalothrin, betacyfluthrin,
The chemical stability of Biphenthrin or alphamethrin, formation control release, and how to extend the lasting period, reduce poison pair work
With and improve bioavilability.
The first aspect of the present invention is to provide a kind of pyrethroids microcapsules, including softgel shell and capsule-core, wherein
The softgel shell is poly-dopamine, and the capsule-core is pyrethroids, and the pyrethroids is gamma cyhalothrin, efficient cyfluthrin
One of pyrethroids, Biphenthrin or alphamethrin are a variety of, and capsule-core is wrapped in softgel shell.
Preferably, microcapsules average grain diameter is less than or equal to 20 microns, shell thickness is less than or equal to 1 micron.More preferably, micro- glue
Capsule average grain diameter is less than or equal to 5 microns, and shell thickness is less than or equal to 0.5 micron.More preferably preferred, microcapsules average grain diameter is
0.05-5 microns, shell thickness is 5-100 nanometers.More preferably preferred, microcapsules average grain diameter is 50-350 nanometers, shell thickness
It is 5-100 nanometers.
Preferably, the pyrethroids is gamma cyhalothrin.Preferably, the drugloading rate of the microcapsules is 20-70%.More
Good, the drugloading rate of the microcapsules is 26-58%.
Preferably, the shape of the microcapsules is spherical in shape, one of rugby shape or grain shape or a variety of.
The second aspect of the present invention is to provide a kind of preparation method of pyrethroids microcapsules, including,
Step (1) provides hollow poly-dopamine softgel shell；
Step (2) provides pyrethroids solution into the softgel shell and forms capsule-core, and the pyrethroids is gamma cyhalothrin, height
One of cyfloxylate, Biphenthrin or alphamethrin or a variety of are imitated, the solvent of the pyrethroids solution is N, N- bis-
Methylformamide or N-METHYLFORMAMIDE.
Preferably, the pyrethroids, which is dissolved in the solvent, forms pyrethroids solution.
Preferably, the pyrethroids is gamma cyhalothrin.Preferably, the concentration of the pyrethroids solution is 10-100mg/
mL.More preferably, the concentration of the pyrethroids solution is 10-50mg/mL.
Preferably, the mass volume ratio of the hollow poly-dopamine softgel shell and pyrethroids solution is 0.1-2g/L, more preferably,
Volume ratio is 0.67-1.12g/L.
Preferably, the hollow poly-dopamine softgel shell uses DOPA amine monomers after mould material surface aggregate, to change
It learns after caustic solution removes mould material and obtains.
Preferably, the DOPA amine monomers include in mould material surface aggregate step, mould material and DOPA amine monomers
After Tris buffer solution is added, DOPA amine monomers are formed on mould material surface to be polymerize.More preferably, the surface aggregate step packet
It includes, after Tris buffer solution is added in mould material, adds DOPA amine monomers, DOPA amine monomers form poly- on mould material surface
It closes；Or Tris buffer solution is added simultaneously in mould material and DOPA amine monomers, DOPA amine monomers are formed on mould material surface
Polymerization.More preferably, content of the DOPA amine monomers in Tris buffer solution is 1-20mg/mL, more preferably preferably, described more
Bar content of the amine monomers in Tris buffer solution is 1-5mg/mL.More preferably, the pH value for adjusting the Tris buffer solution is
8.4-8.6.More preferred, the concentration of Tris buffer solution is 5-20mmol/L.
Preferably, the mould material is silicon dioxide granule.More preferably, the silicon dioxide granule is using commercially available or biography
Alkoxide hydrolysis of uniting is made.The alkoxide hydrolysis is alkoxide hydrolysis-precipitation method, is to prepare the easy-to-use method of silica,
Under room temperature can fast reaction, i.e., using ethyl orthosilicate under the catalysis of alkali, reacted with water, can by hydrolytic polymerization process
Generate silica.More preferably, the silicon dioxide granule is pre-processed, is centrifuged, is dispersed again using Tris buffer solution.
Preferably, the time of the polymerization is 6-72 hours.More preferably, the time of the polymerization is 12-24 hours.More preferably
, the polymerization methods are using stirring.
Preferably, obtaining product after the polymerization through over cleaning, separation.More preferably, the cleaning is buffered molten using Tris
Liquid and double distilled water, the separation is using centrifugation.
Preferably, it is molten using hydrofluoric acid or hydrofluoric acid-ammonium fluoride buffering that the chemical corrosion method, which removes mould material,
Liquid dissolves mould material.
Preferably, obtaining product after the removing mould material through over cleaning, separation.More preferably, the cleaning is using weight
Distilled water, the separation is using centrifugation.
Preferably, pyrethroids solution is added using softgel shell in the step (2).Pass through preferably, the step (2) obtains product
Separation, cleaning, drying.More preferably, the separation uses double distilled water using centrifugation, the cleaning.
Preferably, pyrethroids solution is added using softgel shell in the step (2).More preferably, it is stirred after addition.More preferably,
The time of stirring is 6-48 hours.More preferably preferred, the time of stirring is 12-24 hours.
The third aspect of the present invention is to provide a kind of microcapsules obtained by preparation method of the present invention.
Preferably, the microcapsules average grain diameter is less than or equal to 20 microns, shell thickness is less than or equal to 1 micron.More preferably,
Microcapsules average grain diameter is less than or equal to 5 microns, and shell thickness is less than or equal to 0.5 micron.It is more preferably preferred, microcapsules average grain diameter
It is 0.05-5 microns, shell thickness is 5-100 nanometers.More preferably preferred, microcapsules average grain diameter is 50-350 nanometers, and softgel shell is thick
Degree is 5-100 nanometers.
Preferably, the drugloading rate of the microcapsules is 20-70%.More preferably, the drugloading rate of the microcapsules is 26-
58%.
Preferably, the shape of the microcapsules is spherical in shape, one of rugby shape or grain shape or a variety of.
The fourth aspect of the present invention is to provide a kind of insect prevention preparation, contains pyrethroids microcapsules as described in the present invention.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
(1) microcapsules prepared effectively reduce ultraviolet light to gamma cyhalothrin, betacyfluthrin, biphenyl chrysanthemum
The decomposition of ester or alphamethrin has preferable room temperature and high-temperature storage stability, and storage drugloading rate is unknown within 30 days
Aobvious to reduce, microcapsules thermal decomposition temperature is 200 DEG C or so.
(2) the pyrethroids microcapsules carrier being prepared has good control releasing effect, and 30 days deinsectization effects are better than existing
There is product, improve the bioavilability of pyrethroids, reduces times for spraying and dosage, save the cost.
(3) microcapsule structure prepared reduces the use of organic solvent in conventional formulation, does not use and appoint in preparation process
What surfactant, alleviates the pollution and burden to environment.
(4) effective component of pyrethroids and solvent concentrate in capsule-core, reduce the acute toxicity of raw medicine, and further effectively
Preparation is reduced to the toxicity of non-target organism, and make using and Transport Safety.
(5) preparation of microcapsules is completed in normal pressure state, and method is simple, and it is higher to obtain drugloading rate.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of 1 microcapsules of the embodiment of the present invention.
Fig. 2 is the transmission electron microscope photo for 1 microcapsules of embodiment that the present invention amplifies.
Fig. 3 is fast sustained release curve of the microcapsules in different solvents made from the embodiment of the present invention 5.
Fig. 4 be the embodiment of the present invention 5 made from the aerial thermogravimetric curve of microcapsules, wherein 1 be pyrethroids microcapsules, 2
For blank microcapsules.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.It is obtained using the preparation and application disclosed in embodiment of the present invention one or more with excellent
The characteristic or aspect of gesture.These characteristics or aspect are usually all suitable for entire disclosure.Cited by any one claim
Single or multiple characteristics or aspect can be combined or arrange with the characteristic or aspect of other one or more claims
Column.
"include", "comprise" or similar terms used herein refer to including but not limited to that is, comprising non-exclusive.
Embodiment 1
(1) 10mmol/L Tris buffer solution is prepared, adjusts pH to 8.5 or so with 0.5mol/L HCl solution.It will
60mgSiO2Particle is pre-processed with 10mmol/LTris buffer solution, and centrifugation disperses again.Treated, and 15mL is added in particle
In 10mmol/L Tris buffer solution, 30mg dopamine is added, is stirred 24 hours.Product centrifuge separation, and buffered with Tris
Solution and double distilled water are rinsed, are centrifuged, until supernatant is colourless.
(2) product obtained in (1) is added in 2mol/L hydrofluoric acid/8mol/L ammonium fluoride buffer solution, magnetic force stirs
It mixes 12 hours, removes mould material, and rinsed with redistilled water, be dried in vacuo 12 hours at 40 DEG C.
(3) gamma cyhalothrin for taking the product obtained in 30mg (2) to be added to 45mL 10mg/mL is dissolved in N, N- bis-
In the pyrethroids solution that methylformamide is formed, magnetic agitation 24 hours, it is centrifugated and is rinsed repeatedly with double distilled water, obtained
It is dried in vacuo 12 hours at 40 DEG C of solid and obtains gamma cyhalothrin microcapsules.
Gamma cyhalothrin microcapsules drugloading rate is 26%, within 350 nanometers of average grain diameter.
Embodiment 2
(1) 10mmol/L Tris buffer solution is prepared, adjusts pH to 8.5 or so with 0.5mol/L HCl solution.By 60mg
SiO2Particle is pre-processed with 10mmol/LTris buffer solution, and centrifugation disperses again.Treated, and 15mL is added in particle
In 10mmol/L Tris buffer solution, 30mg dopamine is added, is stirred 24 hours.Product centrifuge separation, and buffered with Tris
Solution and double distilled water are rinsed, are centrifuged, until supernatant is colourless.
(2) product obtained in (1) is added in 2mol/L hydrofluoric acid/8mol/L ammonium fluoride buffer solution, magnetic force stirs
It mixes 12 hours, removes mould material, and rinsed with redistilled water, be dried in vacuo 12 hours at 40 DEG C.
(3) gamma cyhalothrin for taking the product obtained in 30mg (2) to be added to 45mL 20mg/mL is dissolved in N, N- bis-
In the pyrethroids solution that methylformamide is formed, magnetic agitation 24 hours, it is centrifugated and is rinsed repeatedly with double distilled water, obtained
It is dried in vacuo 12 hours at 40 DEG C of solid and obtains gamma cyhalothrin microcapsules.
Gamma cyhalothrin microcapsules drugloading rate is 28%, within 350 nanometers of average grain diameter.
Embodiment 3
(1) 10mmol/L Tris buffer solution is prepared, adjusts pH to 8.5 or so with 0.5mol/L HCl solution.By 60mg
SiO2Particle is pre-processed with 10mmol/L Tris buffer solution, and centrifugation disperses again.Treated, and 15mL is added in particle
In 10mmol/L Tris buffer solution, 30mg dopamine is added, is stirred 24 hours.Product centrifuge separation, and buffered with Tris
Solution and double distilled water are rinsed, are centrifuged, until supernatant is colourless.
(2) product obtained in (1) is added in 2mol/L hydrofluoric acid/8mol/L ammonium fluoride buffer solution, magnetic force stirs
It mixes 12 hours, removes mould material, and rinsed with redistilled water, be dried in vacuo 12 hours at 40 DEG C.
(3) gamma cyhalothrin for taking the product obtained in 30mg (2) to be added to 45mL 30mg/mL is dissolved in N, N- bis-
In the pyrethroids solution that methylformamide is formed, magnetic agitation 24 hours, it is centrifugated and is rinsed repeatedly with double distilled water, obtained
It is dried in vacuo 12 hours at 40 DEG C of solid and obtains gamma cyhalothrin microcapsules.
Gamma cyhalothrin microcapsules drugloading rate is 47%, within 350 nanometers of average grain diameter.
Embodiment 4
(1) 10mmol/L Tris buffer solution is prepared, adjusts pH to 8.5 or so with 0.5mol/L HCl solution.By 60mg
SiO2Particle is pre-processed with 10mmol/L Tris buffer solution, and centrifugation disperses again.Treated, and 15mL is added in particle
In 10mmol/L Tris buffer solution, 30mg dopamine is added, is stirred 24 hours.Product centrifuge separation, and buffered with Tris
Solution and double distilled water are rinsed, are centrifuged, until supernatant is colourless.
(2) product obtained in (1) is added in 2mol/L hydrofluoric acid/8mol/L ammonium fluoride buffer solution, magnetic force stirs
It mixes 12 hours, removes mould material, and rinsed with redistilled water, be dried in vacuo 12 hours at 40 DEG C.
(3) gamma cyhalothrin for taking the product obtained in 50mg (2) to be added to 45mL 50mg/mL is dissolved in N, N- bis-
In the pyrethroids solution that methylformamide is formed, magnetic agitation 24 hours, it is centrifugated and is rinsed repeatedly with double distilled water, obtained
It is dried in vacuo 12 hours at 40 DEG C of solid and obtains gamma cyhalothrin microcapsules.
Gamma cyhalothrin microcapsules drugloading rate is 42%, within 350 nanometers of average grain diameter.
Embodiment 5
(1) 10mmol/L Tris buffer solution is prepared, adjusts pH to 8.5 or so with 0.5mol/L HCl solution.By 60mg
SiO2Particle is pre-processed with 10mmol/L Tris buffer solution, and centrifugation disperses again.Treated, and 15mL is added in particle
In 10mmol/L Tris buffer solution, 30mg dopamine is added, is stirred 24 hours.Product centrifuge separation, and buffered with Tris
Solution and double distilled water are rinsed, are centrifuged, until supernatant is colourless.
(2) product obtained in (1) is added in 2mol/L hydrofluoric acid/8mol/L ammonium fluoride buffer solution, magnetic force stirs
It mixes 12 hours, removes mould material, and rinsed with redistilled water, be dried in vacuo 12 hours at 40 DEG C.
(3) gamma cyhalothrin for taking the product obtained in 20mg (2) to be added to 45mL 50mg/mL is dissolved in N, N- bis-
In the pyrethroids solution that methylformamide is formed, magnetic agitation 24 hours, it is centrifugated and is rinsed repeatedly with double distilled water, obtained
It is dried in vacuo 12 hours at 40 DEG C of solid and obtains gamma cyhalothrin microcapsules.
Gamma cyhalothrin microcapsules drugloading rate is 58%, within 350 nanometers of average grain diameter.
Embodiment 6
(1) 10mmol/L Tris buffer solution is prepared, adjusts pH to 8.5 or so with 0.5mol/L HCl solution.By 60mg
SiO2Particle is pre-processed with 10mmol/L Tris buffer solution, and centrifugation disperses again.Treated, and 15mL is added in particle
In 10mmol/L Tris buffer solution, 30mg dopamine is added, is stirred 24 hours.Product centrifuge separation, and buffered with Tris
Solution and double distilled water are rinsed, are centrifuged, until supernatant is colourless.
(2) product obtained in (1) is added in 2mol/L hydrofluoric acid/8mol/L ammonium fluoride buffer solution, magnetic force stirs
It mixes 12 hours, removes mould material, and rinsed with redistilled water, be dried in vacuo 12 hours at 40 DEG C.
(3) gamma cyhalothrin for taking the product obtained in 20mg (2) to be added to 45mL 50mg/mL is dissolved in N- methyl
In the pyrethroids solution that formamide is formed, magnetic agitation 24 hours, it is centrifugated and is rinsed repeatedly with double distilled water, obtained solid
It is dried in vacuo 12 hours at 40 DEG C and obtains gamma cyhalothrin microcapsules.
Gamma cyhalothrin microcapsules drugloading rate is 51%, within 350 nanometers of average grain diameter.
Embodiment 7
(1) 10mmol/L Tris buffer solution is prepared, adjusts pH to 8.5 or so with 0.5mol/L HCl solution.By 60mg
SiO2Particle is pre-processed with 10mmol/L Tris buffer solution, and centrifugation disperses again.Treated, and 15mL is added in particle
In 10mmol/L Tris buffer solution, 30mg dopamine is added, is stirred 24 hours.Product centrifuge separation, and buffered with Tris
Solution and double distilled water are rinsed, are centrifuged, until supernatant is colourless.
(2) product obtained in (1) is added in 2mol/L hydrofluoric acid/8mol/L ammonium fluoride buffer solution, magnetic force stirs
It mixes 12 hours, removes mould material, and rinsed with redistilled water, be dried in vacuo 12 hours at 40 DEG C.
(3) betacyfluthrin for taking the product obtained in 20mg (2) to be added to 45mL 50mg/mL is dissolved in N, N- bis-
In the pyrethroids solution that methylformamide is formed, magnetic agitation 24 hours, it is centrifugated and is rinsed repeatedly with double distilled water, obtained
It is dried in vacuo 12 hours at 40 DEG C of solid and obtains betacyfluthrin microcapsules.
Betacyfluthrin microcapsules drugloading rate is 53%, within 350 nanometers of average grain diameter.
Embodiment 8
(1) 10mmol/L Tris buffer solution is prepared, adjusts pH to 8.5 or so with 0.5mol/L HCl solution.By 60mg
SiO2Particle is pre-processed with 10mmol/L Tris buffer solution, and centrifugation disperses again.Treated, and 15mL is added in particle
In 10mmol/L Tris buffer solution, 30mg dopamine is added, is stirred 24 hours.Product centrifuge separation, and buffered with Tris
Solution and double distilled water are rinsed, are centrifuged, until supernatant is colourless.
(2) product obtained in (1) is added in 2mol/L hydrofluoric acid/8mol/L ammonium fluoride buffer solution, magnetic force stirs
It mixes 12 hours, removes mould material, and rinsed with redistilled water, be dried in vacuo 12 hours at 40 DEG C.
(3) Biphenthrin for taking the product obtained in 20mg (2) to be added to 45mL 50mg/mL is dissolved in N, N- dimethyl methyl
In the pyrethroids solution that amide is formed, magnetic agitation 24 hours, it is centrifugated and is rinsed repeatedly with double distilled water, obtained solid 40
It is dried in vacuo 12 hours at DEG C and obtains Biphenthrin microcapsules.
Biphenthrin microcapsules drugloading rate is 50%, within 350 nanometers of average grain diameter.
Embodiment 9
(1) 10mmol/L Tris buffer solution is prepared, adjusts pH to 8.5 or so with 0.5mol/L HCl solution.By 60mg
SiO2Particle is pre-processed with 10mmol/L Tris buffer solution, and centrifugation disperses again.Treated, and 15mL is added in particle
In 10mmol/L Tris buffer solution, 30mg dopamine is added, is stirred 24 hours.Product centrifuge separation, and buffered with Tris
Solution and double distilled water are rinsed, are centrifuged, until supernatant is colourless.
(2) product obtained in (1) is added in 2mol/L hydrofluoric acid/8mol/L ammonium fluoride buffer solution, magnetic force stirs
It mixes 12 hours, removes mould material, and rinsed with redistilled water, be dried in vacuo 12 hours at 40 DEG C.
(3) alphamethrin for taking the product obtained in 20mg (2) to be added to 45mL 50mg/mL is dissolved in N, N- diformazan
In the pyrethroids solution that base formamide is formed, magnetic agitation 24 hours, it is centrifugated and is rinsed repeatedly with double distilled water, what is obtained consolidates
It is dried in vacuo 12 hours at 40 DEG C of body and obtains alphamethrin microcapsules.
Alphamethrin microcapsules drugloading rate is 51%, within 350 nanometers of average grain diameter.
Comparative example 1
It using the method for embodiment 1, uses dehydrated alcohol for solvent, forms 10mg/L gamma cyhalothrin ethanol solution
It is prepared, obtains gamma cyhalothrin microcapsules, gamma cyhalothrin microcapsules drugloading rate is lower than 1%.
Comparative example 2
Certain commercially available gamma cyhalothrin microcapsule product using traditional interfacial polymerization, the kaolin particle of 30g
Grinding 30 seconds is added in 30mL water；Homogeneous 30 seconds, it is diluted to 5% (w/w), obtains kaolin aqueous solution.It will be dense in mixed system
Degree is respectively 10% (w/w) Suprasec 5025 (poly methylene poly phenyl poly isocyanate) solution, 45% (w/w) efficient chlorine
Flucythrinate solution and 45% (w/w) Solvesso 200ND (aromatic solvent) solution under high speed shear (5000rpm) drip
Enter in kaolin aqueous solution, high speed shear (20000rpm, 2 minutes) obtains oil/water lotion, then crosslinks reaction, obtain
The microcapsules of single layer.
It is added under 25% (w/w) DETA (diethylenetriamine, diethylenetriamine) aqueous solution low velocity shear above-mentioned
Single-layer microcapsules system, formation bilayered microcapsule, 171 microns of average grain diameter.
Comparative example 3
Certain commercially available gamma cyhalothrin microcapsules using traditional interfacial polymerization, the kaolin particle grinding of 30g
It 30 seconds, is added in 30mL water；Homogeneous 30 seconds, it is diluted to 5% (w/w), obtains kaolin aqueous solution.It respectively will be dense in mixed system
Degree is respectively 10% (w/w) Suprasec 5025 (poly methylene poly phenyl poly isocyanate) solution, and 47.5% (w/w) is efficient
Lambda-cyhalothrin solution and 47.5% (w/w) Solvesso 200ND (aromatic solvent) solution are under high speed shear
(5000rpm) is instilled in kaolin aqueous solution, and high speed shear (20000rpm, 2 minutes) obtains oil/water lotion, then hands over
Connection reaction, obtains the microcapsules of single layer.
It is added under 25% (w/w) DETA (diethylenetriamine, diethylenetriamine) aqueous solution low velocity shear above-mentioned
Single-layer microcapsules system, formation bilayered microcapsule, 31.7 microns of average grain diameter.
The measurement of room temperature and high-temperature storage stability
By pyrethroids microcapsules made from embodiment 1-5, drugloading rate, the test knot of storage stability are surveyed after being stored at room temperature 30 days
Fruit is shown in Table 1.Drugloading rate is determined as " qualification " there is no quantity variation.
Pyrethroids microcapsules and blank capsules prepared by embodiment 5 carry out thermogravimetic analysis (TGA), in 200 DEG C or so the micro- glue of pyrethroids
Capsule starts to decompose weightlessness, compares blank microcapsules weight-loss curve, and thermogravimetic analysis (TGA) test result is shown in Fig. 3.Poly-dopamine microcapsules
Good thermal stability, 200 DEG C or so just start to decompose, and the pyrethroids poly-dopamine microcapsules thermal decomposition temperature after carrying medicine is also higher,
The temperature requirement that can satisfy storage and use.
Embodiment 1-4 and embodiment 6-9 has the impact of performance similarly to Example 5.
Control release performance measurement and irritant experiment
Releasing degree of the pyrethroids microcapsules in different concentration ethanol aqueous solution made from testing example 5.Concrete operations
Are as follows: precision weighs a certain amount of pyrethroids microcapsules, is added in different concentration ethanol aqueous solution, magnetic agitation.In different time points,
4mL is sampled, with the concentration of ultraviolet spectrophotometer method measurement sustained-release liquid.Examination obtains control release performance measurement result and sees Fig. 4.
Sample dilutes 40 times, and 2cm × 3cm size area is drawn at the back of the hand, dilution 0.03g is taken uniformly to be applied to region
Interior, irritation within observation 4 hours obtains rapid stimulation experimental result and is shown in Table 2.40% microcapsule powder occurred light at 3 hours
Meagre lotus sense, has irritation, and confirmation 40% microcapsule powder control release performance is good.
Embodiment 1-4 and embodiment 6-9 has the impact of performance similarly to Example 5.
The measurement of pharmacodynamic test
Pyrethroids microcapsules carrier is prepared according to embodiment 5, certain the commercially available pyrethroids prepared using traditional interfacial polymerization
Microcapsule product as a comparison case 2 or comparative example 3, by the room referring to GB13917.1-2009 agriculture chemical registration hygienic insecticide
Interior pharmacodynamic test and evaluation method are measured with the indoor harmacological effect that forced contactor does residual spray, needed for every square metre of recommendation
The amount of application medicament effective component, amount of formulation needed for being converted into contact surface, be equably added dropwise after test formulation is diluted,
It is applied on contact surface, dries spare, coating plate face should be protected from light natural storage indoors.
The baffle of forced contactor is pulled to top.By test worm (housefly 20) with putting after light anaesthesia with diethyl ether from putting worm channel
Enter in the space between forced contactor baffle and pulling plate, after test worm restores normal activity, forced contactor is placed in contact
On panel, baffle, while pushing drawing rod are pulled out in the case where not injuring test worm, baffle is pushed into bottom, force test worm and are applied
The plate face of medicine contacts, and whole test worms 30 minutes, are collected into clean dependent insect cage or vessel by timing immediately.The test of acquisition is strong
Urgent contact test the results are shown in Table 3.
The measurement of drugloading rate
Precision measures embodiment 1-5, pyrethroids microcapsules W1 obtained, is added appropriate dehydrated alcohol, and water bath sonicator 30 minutes,
Centrifuging and taking supernatant is settled to 10mL with dehydrated alcohol dissolution, measures wherein pyrethroids content with ultraviolet specrophotometer, that is, be negative
The pyrethroids quality W2 of load.
Drugloading rate is calculated as follows: PL (%)=W2/W1 × 100%.
Note: PL is the drugloading rate of pyrethroids microcapsules, and Wl is pyrethroids microcapsules gross mass obtained in each embodiment, and W2 is negative
The quality of the pyrethroids of load.
Table 1
Table 2
Table 3
Claims (10)
1. a kind of pyrethroids microcapsules, including softgel shell and capsule-core, wherein
The softgel shell is poly-dopamine, and the capsule-core is pyrethroids, and the pyrethroids is gamma cyhalothrin, efficient cyfluthrin chrysanthemum
One of ester, Biphenthrin or alphamethrin are a variety of, and capsule-core is wrapped in softgel shell.
2. pyrethroids microcapsules according to claim 1, which is characterized in that it is micro- that the microcapsules average grain diameter is less than or equal to 20
Rice, shell thickness are less than or equal to 1 micron；And/or the drugloading rate of the microcapsules is 20-70%.
3. pyrethroids microcapsules according to claim 1, which is characterized in that the pyrethroids is gamma cyhalothrin；And/or
The microcapsules average grain diameter is less than or equal to 5 microns, and shell thickness is less than or equal to 0.5 micron；And/or the load of the microcapsules
Dose is 26-58%.
4. a kind of preparation method of pyrethroids microcapsules, including,
Step (1) provides hollow poly-dopamine softgel shell；
Step (2) provides pyrethroids solution into the softgel shell and forms capsule-core, and the pyrethroids is gamma cyhalothrin, efficient fluorine
One of cypermethrin, Biphenthrin or alphamethrin are a variety of, and the solvent of the pyrethroids solution is N, N- dimethyl
Formamide or N-METHYLFORMAMIDE.
5. preparation method according to claim 4, which is characterized in that the pyrethroids is gamma cyhalothrin；And/or institute
The concentration for stating pyrethroids solution is 10-100mg/mL；And/or pyrethroids solution is added using softgel shell in step (2)；And/or step (2)
Product is obtained by centrifugation, cleaning, drying.
6. preparation method as described in claim 5, which is characterized in that the concentration of the pyrethroids solution is 10-50mg/mL；With/
Or, the mass volume ratio of the softgel shell and pyrethroids solution is 0.1-2g/L；And/or the softgel shell uses DOPA amine monomers in mould
After plate material surface aggregate, mould material is removed with chemical corrosion method and is obtained.
7. preparation method according to claim 6, which is characterized in that the step of polymerization includes mould material and DOPA
After Tris buffer solution is added in amine monomers, DOPA amine monomers are formed on mould material surface to be polymerize；And/or the chemical attack
It is to dissolve mould material using hydrofluoric acid or hydrofluoric acid-ammonium fluoride buffer solution that method, which removes mould material,.
8. preparation method according to claim 7, which is characterized in that DOPA amine monomers the containing in Tris buffer solution
Amount is 1-20mg/mL；The mould material is silicon dioxide granule；And/or the time of the polymerization is 6-72 hours；With/
Or, the pH value for adjusting the Tris buffer solution is 8.4-8.6.
9. a kind of pyrethroids microcapsules by the described in any item preparation method preparations of claim 4-8.
10. a kind of insect prevention preparation contains pyrethroids microcapsules according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711435674.4A CN109953021A (en) | 2017-12-26 | 2017-12-26 | Pyrethroids microcapsules, preparation method and insect prevention preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711435674.4A CN109953021A (en) | 2017-12-26 | 2017-12-26 | Pyrethroids microcapsules, preparation method and insect prevention preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109953021A true CN109953021A (en) | 2019-07-02 |
Family
ID=67022407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711435674.4A Pending CN109953021A (en) | 2017-12-26 | 2017-12-26 | Pyrethroids microcapsules, preparation method and insect prevention preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109953021A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111616142A (en) * | 2020-06-10 | 2020-09-04 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Pesticide nano preparation and preparation method thereof |
| CN115581240A (en) * | 2022-10-25 | 2023-01-10 | 江苏艾津作物科技集团有限公司 | Preparation method of high-adhesion cypermethrin microcapsule suspending agent |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102845455A (en) * | 2012-03-29 | 2013-01-02 | 广东中迅农科股份有限公司 | High-efficient cyhalothrin microcapsule suspending agent and preparation method thereof |
| CN102976855A (en) * | 2012-12-18 | 2013-03-20 | 石河子大学 | Polydopamine coated controlled-release fertilizer |
| CN103329897A (en) * | 2013-07-10 | 2013-10-02 | 中国科学院新疆生态与地理研究所 | Pyrethroid insecticide controlled-release polymer microcapsule synthesis method |
| CN104621102A (en) * | 2014-06-26 | 2015-05-20 | 石河子大学 | Method for preparing adhesive abamectin polydopamine microcapsule by employing emulsion interface polymerization method |
| CN104984693A (en) * | 2015-07-24 | 2015-10-21 | 扬州大学 | Preparation method of nanometer magnetism capsule |
| CN105017257A (en) * | 2014-04-30 | 2015-11-04 | 华东理工大学 | Derivative of tetrahydroindeno-6-vinyl-1,3a-diazapentalene and preparation method and application thereof |
| CN105076188A (en) * | 2014-05-21 | 2015-11-25 | 南通联农农药制剂研究开发有限公司 | High-efficiency cyhalothrin microcapsule suspension and preparation method thereof |
| CN105557741A (en) * | 2016-03-04 | 2016-05-11 | 扬州大学 | Beta-cypermethrin microcapsule and preparation method thereof |
| CN106900703A (en) * | 2017-01-13 | 2017-06-30 | 华南理工大学 | A kind of lignin-base polyureas pesticide micro capsule and preparation method thereof |
| WO2017221237A1 (en) * | 2016-06-19 | 2017-12-28 | Avner Barazani - Innovative Advanced Development Ltd. | Fungicidal compositions and methods for controlling plant pathogens |
| JP2018039803A (en) * | 2016-09-06 | 2018-03-15 | アース製薬株式会社 | Spider egg sac treatment agent and method for treating spider egg sac |
-
2017
- 2017-12-26 CN CN201711435674.4A patent/CN109953021A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102845455A (en) * | 2012-03-29 | 2013-01-02 | 广东中迅农科股份有限公司 | High-efficient cyhalothrin microcapsule suspending agent and preparation method thereof |
| CN102976855A (en) * | 2012-12-18 | 2013-03-20 | 石河子大学 | Polydopamine coated controlled-release fertilizer |
| CN103329897A (en) * | 2013-07-10 | 2013-10-02 | 中国科学院新疆生态与地理研究所 | Pyrethroid insecticide controlled-release polymer microcapsule synthesis method |
| CN105017257A (en) * | 2014-04-30 | 2015-11-04 | 华东理工大学 | Derivative of tetrahydroindeno-6-vinyl-1,3a-diazapentalene and preparation method and application thereof |
| CN105076188A (en) * | 2014-05-21 | 2015-11-25 | 南通联农农药制剂研究开发有限公司 | High-efficiency cyhalothrin microcapsule suspension and preparation method thereof |
| CN104621102A (en) * | 2014-06-26 | 2015-05-20 | 石河子大学 | Method for preparing adhesive abamectin polydopamine microcapsule by employing emulsion interface polymerization method |
| CN104984693A (en) * | 2015-07-24 | 2015-10-21 | 扬州大学 | Preparation method of nanometer magnetism capsule |
| CN105557741A (en) * | 2016-03-04 | 2016-05-11 | 扬州大学 | Beta-cypermethrin microcapsule and preparation method thereof |
| WO2017221237A1 (en) * | 2016-06-19 | 2017-12-28 | Avner Barazani - Innovative Advanced Development Ltd. | Fungicidal compositions and methods for controlling plant pathogens |
| JP2018039803A (en) * | 2016-09-06 | 2018-03-15 | アース製薬株式会社 | Spider egg sac treatment agent and method for treating spider egg sac |
| CN106900703A (en) * | 2017-01-13 | 2017-06-30 | 华南理工大学 | A kind of lignin-base polyureas pesticide micro capsule and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YUE SHEN等: "Preparation and Physicochemical Characteristics of Thermo-Responsive Emamectin BenzoateMicrocapsules", 《POLYMERS》 * |
| 尹媛媛等: "乳液液滴为模板制备载药聚多巴胺微胶囊", 《微量元素与健康研究》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111616142A (en) * | 2020-06-10 | 2020-09-04 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Pesticide nano preparation and preparation method thereof |
| CN115581240A (en) * | 2022-10-25 | 2023-01-10 | 江苏艾津作物科技集团有限公司 | Preparation method of high-adhesion cypermethrin microcapsule suspending agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2623888C (en) | Methods for crop protection | |
| AU2017227529B2 (en) | Insect repellent | |
| ES2527187T3 (en) | Microcapsules comprising a pyrethroid and / or a neonicotinoid and a synergistic agent | |
| AU2012365434B2 (en) | Variable release water dispersible granule composition | |
| CN101268782A (en) | Insecticidal mixture containing gamma-cyhalothrin | |
| JP2008536891A (en) | Innovative formulation | |
| JP2013513663A (en) | Sustained release silica microcapsules | |
| EP2249648B1 (en) | A method for modulating the release rate of microencapsulated actives | |
| PT902724E (en) | MICROENCAPSULATED COMPOSITIONS | |
| CN109953021A (en) | Pyrethroids microcapsules, preparation method and insect prevention preparation | |
| ITMI20121206A1 (en) | INSECTICIDE FORMULATIONS OF MICROCAPSULES | |
| JP2001181116A (en) | Insect repellent composition and insect repellent coating using the same | |
| BR112016019257B1 (en) | COMPOSITION OF WATER DISPERSABLE BEADS | |
| CN108430220A (en) | A kind of composition and method of pest control | |
| CN110050788A (en) | Gamma cyhalothrin poly-dopamine micro-capsule suspension and preparation method thereof | |
| Stejskal et al. | Brief exposure of Blattella germanica (Blattodea) to insecticides formulated in various microcapsule sizes and applied on porous and non‐porous surfaces | |
| US5527823A (en) | Pesticidal formulations | |
| KR20160145603A (en) | Agrochemical formulation | |
| CN108184833A (en) | Pyrethrins microcapsule formulations with beta-cyclodextrin or derivatives thereof for wall material and its preparation method and application | |
| KR20220100636A (en) | Combination of phenothrine and pralethrine | |
| CN113923989A (en) | Double-activity insecticidal composition | |
| JP2002205903A (en) | Method for applying insecticidal composition to insect proof net and insecticidal composition | |
| Oliveira Filho | New alternatives for Chagas' disease control | |
| JP2009227611A (en) | Method for controlling dermanyssus gallinae | |
| US20190350196A1 (en) | Microcapsules encapsulating lambda-cyhalothrin |
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 |
Application publication date: 20190702 |
|
| RJ01 | Rejection of invention patent application after publication |