CN107156118A - Pesticide action-controlling composition and nanometer formula bactericide and preparation method thereof - Google Patents
Pesticide action-controlling composition and nanometer formula bactericide and preparation method thereof Download PDFInfo
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- CN107156118A CN107156118A CN201710383782.5A CN201710383782A CN107156118A CN 107156118 A CN107156118 A CN 107156118A CN 201710383782 A CN201710383782 A CN 201710383782A CN 107156118 A CN107156118 A CN 107156118A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
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Abstract
The present invention relates to field of pesticide preparation, disclose pesticide action-controlling composition and nanometer formula bactericide and preparation method thereof, contain alginate, nanometer silicon source, polyvalent cation and pesticide activity component in said composition, wherein, on the basis of the gross weight of the composition, the content of the alginate is 10~90 weight %, and the content of the nanometer silicon source is 2~60 weight %, the content of polyvalent cation is 2~40 weight %, and the content of the pesticide activity component is 5~80 weight %.The nanometer formula bactericide that the present invention is provided has the function of the pesticide activity component including antifungal agent, insecticide and herbicide packaged by Intelligent controlled release.
Description
Technical field
The present invention relates to field of pesticide preparation, and in particular to a kind of pesticide action-controlling composition, a kind of nanometer formula bactericide
And preparation method thereof.
Background technology
The active component of many agricultural chemicals has high toxicity to non-target organism, or many agricultural chemicals active component water-soluble
The characteristics of dissolubility is bad is relatively shown in liquid, moreover, the active component of some agricultural chemicals is gone back under severe field condition
It can show unstable and reduce its preventive effect to target organismses.
In order to effectively in Field information agricultural chemicals, it is necessary to which adjust agricultural chemicals is formulated so that active component therein can
Drug effect is fully played in various field conditions and its toxicity to any non-target organism can be reduced.
Pyraclostrobin is a kind of antifungal agent, and it, which belongs to, can suppress the methoxy acrylic of mitochondrial respiratory and kill
Microbial inoculum (mitochondrial respiratory inhibitor).Richness of the pyraclostrobin required for by reducing a series of basic processes in fungal cell
The ATP of energy and produce antibiotic property.
The structural formula of pyraclostrobin is as follows：
Pyraclostrobin is mainly administered by spraying, for preventing and treating the crops such as paddy rice, veterinary antibiotics, corn, citrus
Fungal disease, it is safe to vegetables and fruit.But, pyraclostrobin missible oil has severe toxicity to a variety of fish, and
There is hypotoxicity to bird, honey and earthworm, therefore, must not be in the water sources such as pond and water body using the crop of pyraclostrobin missible oil
Middle washing, also, dispenser raffinate must not be poured into water source and water body, and this safety for being significant adverse to pyraclostrobin extensively should
With.
The content of the invention
The invention aims to pair for the pesticide activity component presence such as pyraclostrobin for overcoming prior art
The not high defect of the security of non-target organism contains the pesticide action-controlling composition there is provided a kind of pesticide action-controlling composition and one kind
Nanometer formula bactericide and preparation method thereof.
To achieve these goals, the first aspect of the present invention is provided contains in a kind of pesticide action-controlling composition, said composition
There are alginate, nanometer silicon source, polyvalent cation and pesticide activity component, wherein, on the basis of the gross weight of the composition,
The content of the alginate is 10~90 weight %, and the content of the nanometer silicon source is 2~60 weight %, polyvalent cation
Content is 2~40 weight %, and the content of the pesticide activity component is 5~80 weight %.
The second aspect of the present invention is provided in a kind of nanometer formula bactericide, nanometer formula bactericide containing the present invention the
Composition described in one side, and this nanometer formula bactericide formulation for wettable powder, microcapsule suspending agent, aqueous suspension agent,
At least one of dispersible oil-suspending agent, aqueous emulsion, granule and microemulsion.
The third aspect of the present invention provides a kind of method that nanometer prepared described in second aspect is formulated bactericide, including：
(1) nanometer silicon source is contacted with water to form mixture A, and pesticide activity component is contacted to be formed with solvent
Solution A；
(2) solution A is contacted to obtain solution B with the mixture A under agitation；
(3) under agitation alginate is contacted to obtain suspension A with the solution B；
(4) solution C of the aqueous solution containing polyvalent cation is contacted to obtain suspension B with the suspension A.
The advantage of present invention exploitation pesticide action-controlling composition and nanometer formula bactericide mainly includes：
1st, toxicity of the pesticide activity component to non-target aquatic animals and plants can be significantly decreased；
2nd, the release of pesticide activity component can be controlled in conventional practical environment (such as field conditions), and run into
When pest and disease damage is invaded and harassed, enter pest and disease damage it is internal when can speed up the release of pesticide activity component quickly to kill disease pest
Evil, so as to realize its Intelligent controlled release；
3rd, pesticide activity component can be separated from aquatic environment by precipitating edman degradation Edman；
4th, pesticide activity component is protected to protect it from the influence of the adverse environment condition such as sunlight, moisture and temperature, so that
Extend its activity cycle in field conditions.
Further, the nanometer formula bactericide that the present invention is provided is a kind of nanometer formulation, and there is Intelligent controlled release to be sealed for it
The function of the pesticide activity component including antifungal agent, insecticide and herbicide of dress.
Brief description of the drawings
Fig. 1 is the SEM figures for the preparation that embodiments of the invention 1 are prepared；
Fig. 2 is the TEM figures for the preparation that embodiments of the invention 1 are prepared.
Embodiment
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
As it was previously stated, the first aspect of the present invention, which is provided in a kind of pesticide action-controlling composition, said composition, contains marine alga
Hydrochlorate, nanometer silicon source, polyvalent cation and pesticide activity component, wherein, on the basis of the gross weight of the composition, the sea
The content of alginates is 10~90 weight %, and the content of the nanometer silicon source is 2~60 weight %, and the content of polyvalent cation is
2~40 weight %, and the content of the pesticide activity component is 5~80 weight %.
It is highly preferred that on the basis of the gross weight of the composition, the content of the alginate is 15~60 weight %,
The content of the nanometer silicon source is 5~25 weight %, and the content of polyvalent cation is 20~40 weight %, and the agricultural chemicals is lived
Property composition content be 8~60 weight %.
The content of polyvalent cation in the composition of the present invention is in terms of in the form of the salt containing the polyvalent cation
Calculate.
It should be strongly noted that in the content of each composition of the composition of the present invention, being used as the composition of benchmark
It is not include solvent wherein that may be present in weight, for example, when containing the water as solvent in the composition, in meter
When calculating the content of pesticide activity component in the composition, the weight of said composition in itself is not include the weight of water therein.
Preferably, the alginate is at least one of sodium alginate, calcium alginate and potassium alginate.Particularly preferably
In the case of, the alginate is sodium alginate.
The alginate of the present invention can be by commercially available, or extracts what is obtained from marine alga or bacterium
Alginate.
Preferably, the nanometer silicon source is nanometer silicon dioxide particle and/or nano silicon structure.
Under preferable case, the average grain diameter of the nanometer silicon source is 10~500nm；The more preferably nanometer silicon source is averaged
Particle diameter is 20~300nm.
Preferably, the polyvalent cation is selected from Ca2+、Mg2+、Cu2+、Mn2+、Zn2+And Fe+3At least one of.Especially
Under preferable case, the polyvalent cation is Ca2+And/or Mg2+。
In the present invention, the polyvalent cation can be by halide salt (such as chlorate, nitric acid containing polyvalent cation
Salt etc.) provide.Exemplarily polyvalent cation is provided in embodiments of the invention using calcium chloride and magnesium chloride.
Under preferable case, the pesticide activity component is selected from pyraclostrobin, chlopyrifos (Chlorpyrifos), chlorine cyanogen chrysanthemum
Ester (Cypermethrin), basudin (Diazinon), 5a,6,9,9a-hexahydro-6,9-methano-2,4 (Endosulfan), phosmet (Phosmet), malathion
(Malathion), Methomyl (Methomyl), 2-dichloroethylk dimethyl phosphate (Naled), novaluron (Novaluron), Deltamethrin
(Deltamethrin), in imidacloprid (imidacloprid), Permethrin (Permethrin) and thimet (Phorate) extremely
Lack a kind of insecticide and/or for selected from Fluoxastrobin (Azoxystrobin), Difenoconazole (Difenconazole), Bravo
(Chlorothalonil), Propamocarb (Propamocarb), Fenamidone (Fenamidone), fluopicolide
(Fluopicolide), Mancozeb (Mancozeb), metalaxyl (Metalaxyl), Carbatene (Metiram), pyrazoles bacterium amine
(Penthiopyrad), zoxamide (Zoxamide), benzene azoles mepanipyrim (Ametoctradin), dimethomorph
(Dimethomorph), copper agent (Copper), cymoxanil (Cymoxanil), famoxadones (Famoxadone) and fluazinam
At least one of (Fluazinam) antiseptic.It is particularly preferred that the pesticide activity component is pyraclostrobin.
The pesticide action-controlling composition that the present invention is provided is using alginate as encapsulation agent, base material centered on silicon source, multivalence sun from
Son is crosslinking agent.The pesticide action-controlling composition of the present invention can encapsulate 5~80 weight % pesticide activity component.
It can also contain in the foregoing of the present invention in the additives such as a small amount of solvent, stabilizer and emulsifying agent extremely
Few one kind.Further contain under preferable case, in said composition and be selected from emulsifying agent, stabilizer, solvent, dispersant, wetting agent, exhibition
At least one of agent, defoamer, synergist, bleeding agent, sticker, safener, carrier and filler additive.
The emulsifying agent for example can for Tween 80, polysorbate60, polysorbas20, farm chemical emulgent 500, pesticide emulsifier 600,
Farm chemical emulgent 601, farm chemical emulgent 700, farm chemical emulgent 33 and farm chemical emulgent 300.In the composition of the present invention
The content of emulsifying agent for example can be 0~0.5 weight %.
The stabilizer for example can be in polyethylene glycol diglycidyl ether, epoxidized soybean oil and epoxychloropropane
At least one.The content of stabilizer in the composition of the present invention for example can be 0~0.1 weight %.
The solvent for example can for methanol, acetone, DMSO, toluene, ethanol, isopropanol, mineral oil, trimethylbenzene, No. 100
At least one of solvent naphtha, No. 150 solvent naphthas, No. 200 solvent naphthas, epoxy esterified vegetable oil and heavy aromatic solvent oil.This hair
The content of solvent in bright composition for example can be 0~1 weight %.
Can also the silica flour containing 0~10 weight % in the composition of the present invention.Under preferable case, the silica flour
Average grain diameter is 5~50nm.
The second aspect of the present invention, which provides a kind of nanometer and is formulated in bactericide, nanometer formula bactericide, contains foregoing the
Composition described in one side, and this nanometer formula bactericide formulation for wettable powder, microcapsule suspending agent, aqueous suspension agent,
At least one of dispersible oil-suspending agent, aqueous emulsion, granule and microemulsion.
In the method for the invention, the method for obtaining the formulation described in the second aspect is had no particular limits, this
Art personnel can obtain foregoing formulation using the method for this area routine application.
The nanometer formula bactericide of the present invention has the biocompatibility of height, and nontoxic, low cost, can drop naturally
Solution.
Also, the third aspect of the present invention provides a kind of nanometer formula bactericide prepared described in foregoing second aspect
The method of preferred embodiment, the bactericide of the invention obtained using the preferred method is ensureing good antibacterial work
Significantly more efficient Intelligent controlled release in the presence of a harsh environment can be realized on the premise of property, this method includes：
(1) nanometer silicon source is contacted with water to form mixture A, and pesticide activity component is contacted to be formed with solvent
Solution A；
(2) solution A is contacted to obtain solution B with the mixture A under agitation；
(3) under agitation alginate is contacted to obtain suspension A with the solution B；
(4) solution C of the aqueous solution containing polyvalent cation is contacted to obtain suspension B with the suspension A.
The situation of relevant composition described in the third aspect of the present invention and complete phase in aforementioned first aspect of the present invention
Together, the present invention will not be repeated here, and those skilled in the art should not be construed as limiting the invention.
Preferably, in the method for the invention, it is described on the basis of the gross weight of composition described in first aspect present invention
The consumption of alginate is 10~90 weight %, and the consumption of the nanometer silicon source is 2~60 weight %, the consumption of polyvalent cation
It is 5~80 weight % for 2~40 weight %, and the pesticide activity component consumption；It is highly preferred that with the composition
On the basis of gross weight, the consumption of the alginate is 15~60 weight %, and the consumption of the nanometer silicon source is 5~25 weights
% is measured, the consumption of polyvalent cation is 20~40 weight %, and the consumption of the pesticide activity component is 8~60 weight %.
In case of no particular description, the step such as contact, mixing in the method described in second aspect of the present invention can
To be carried out under room temperature environment, for example, it can be carried out at 5~45 DEG C.
The water of the present invention can be deionized water.
In the present invention, the mixture A can add 5~2000mg silicon source and be formed in every 100mL water；Institute
5~5000mg pesticide activity component can be added and be formed in every 2mL solvent by stating solution A.
In the solution A, the solvent used is set according to the hydrophily and hydrophobicity of pesticide activity component.
According to preferred embodiment 1, the pesticide activity component is hydrophilic composition, and the solvent can be
Water.
According to preferred embodiment 2, the pesticide activity component is hydrophobic combination, and the solvent can be peace
Quan Xinggao and the low organic solvent of cost, for example, can be methanol, acetone, DMSO, toluene, ethanol, isopropanol, mineral oil, three
In toluene, No. 100 solvent naphthas, No. 150 solvent naphthas, No. 200 solvent naphthas, epoxy esterified vegetable oil and heavy aromatic solvent oils at least
It is a kind of.Under preferable case, in the preferred embodiment, emulsifying agent, stabilizer etc. can also be contained in the solution A
Aforementioned additive in the composition of the present invention.
Stirring in the preceding method of the present invention can be carried out using such as magnetic stirring apparatus.
In the method for the invention, in step (2), stirring is until the favorable dispersibility of the solution B.
In the method for the invention, in step (3), under agitation alginate is contacted to obtain with the solution B
Suspension A, and the suspension A is preferably a kind of uniform and smooth gel.
The present invention can also use the method for drying that the suspension B of acquisition is dried and be obtained with being prepared into expectation
Formulation.The method of the drying of the present invention is preferably spray drying, fluidized bed drying and freeze-drying.
It was found by the inventors of the present invention that the granule of the bactericide of the invention obtained by using spray drying process has
More preferable controlled-release effect.It is therefore preferable that in the case of, method of the invention further comprises：Removed by spray drying process described
Solvent in suspension B to obtain dry powder, then by the dry powder drying to constant weight to obtain granular preparation.
The method of the present invention can also include being ground the intermediate obtained after drying using the method for such as grinding；
But, during according to spray drying process to be dried, preferably the product obtained after spray drying is not ground.
Under preferable case, the average grain diameter of the granular preparation is 200~900nm.
It is particularly preferred that the present invention method provide nanometer formula bactericide structure preferably using nanometer silicon source in
Wrapped up around heart material, the center material by the alginate of multilayer ring-type, it is bonded by polyvalent cation between layers,
And pesticide activity component is wrapped between the multilayer loop formed by alginate and ring, the nanometer that method of the invention is provided is matched somebody with somebody
Square bactericide can realize the envelop rate for being up to 5~80 weight % to pesticide activity component.
Preferably, the spray drying is carried out in spray dryer, and the condition of the spray drying includes：Import temperature
Spend for 100~250 DEG C, outlet temperature is lower than the inlet temperature 40~60 DEG C.For example, the condition of the spray drying includes：
Inlet temperature is 200 DEG C, and outlet temperature is 150 DEG C；Or the condition of the spray drying includes：Inlet temperature is 150 DEG C, is gone out
Mouth temperature is 100 DEG C；Or the condition of the spray drying includes：Inlet temperature is 125 DEG C, and outlet temperature is 75 DEG C.
Preferably, the dry powder drying to constant weight can be carried out in vacuum drying oven drying machine.Vacuum drying oven is dried
There is no particular limitation for design temperature in machine, and those skilled in the art can be selected according to the ordinary temperature of this area.
The method of the present invention can also include being sieved the granular preparation of foregoing acquisition, and will obtain after screening
Particle diameter mixes for 200~900nm granular preparation with silica flour is formulated bactericide with the foregoing nanometer for obtaining the present invention.Preferable case
Under, the mixing of the granular preparation and silica flour can be carried out in high-shear mixer, rotating speed for example can for 200~
5000rpm。
The nanometer formula bactericide product that the present invention is obtained can be stored in drying receptacle with standby.
Specifically, the nanometer formula bactericide that the present invention is provided also has following specific advantage：
Toxicity of the pesticide active ingredient to non-target organism is reduced, the water solubility of agricultural chemicals is improved, extends agricultural chemicals
Shelf-life.Also, the nanometer formula bactericide that the present invention is provided can be applied to the blade face of crop in the way of directly contacting.
In the preferred case, nanometer of the invention formula bactericide is alternatively arranged as wettable powder or is further modified as
Waterborne suspension mating surface activating agent or wetting agent.The present invention product can effectively prevent and treat paddy rice, veterinary antibiotics, corn,
The pest and disease damage of the crops such as citrus is without damage to the environment.
The present invention will be described in detail by way of examples below.
In following examples, in case of no particular description, the various raw materials used are all from commercially available.
The measure of the envelop rate (EE) of following pesticide activity component is adopted to be carried out with the following method：(peace is prompt for high performance liquid chromatography
Human relations, the U.S.) use Eclipse XDB C8Post (150 × 4.6mm, 5 μm；ZORBAX, the U.S.), mobile phase (acetonitrile：Water=65:
35, volume ratio) flow be 1mL/min, injection volume be 0.5 μ L.The complete analysis time of sample is 10min.Pyraclostrobin
Retention time is 6.2min (254.4nm wavelength).
Particle size and pattern are determined：
(a) transmission electron microscope (TEM)：H-7000fa (Hitachi, Japan)；
(b) SEM (SEM)：JEOL JSM 6700F, Japan.
Particle size distribution：
Dynamic laser scattering (DLS)：It is many to determine using DynaPro Nano Star (equipment of Wyatt science and technology, Britain)
Monodispersity index.Particle size distribution data is analyzed by editing machine V7 softwares.
Embodiment 1：Prepare nanometer formula bactericide
(1) 100mg nanometer silicon dioxide particles (average grain diameter is 50nm) are contacted with 100mL water to form mixture A,
And 100mg pyraclostrobins and 2mL are contained into emulsifying agent (Tween 80) and stabilizer (polyethylene glycol 2-glycidyl
Ether) methanol solution (in the methanol solution, methanol content is 88.98 weight %, and the content of Tween 80 is 8.47 weight %, is gathered
The content of ethylene glycol diglycidyl ether is 2.55 weight %) contact to form solution A；
(2) solution A of step (1) is contacted to obtain solution B with the mixture A of step (1) under agitation；
(3) under agitation 300mg sodium alginates are contacted to obtain suspension A with the solution B of step (2)；
(4) 300mg magnesium chlorides are dissolved in 10mL water, obtain solution C, by the suspension of the solution C and step (4)
A contacts to obtain suspension B；
(5) described be suspended is removed by spray drying process (drying machine inlet temperature is 200 DEG C, and outlet temperature is 150 DEG C)
Then solvent in liquid B is dried the dry powder to constant weight to obtain granular preparation, by institute with obtaining dry powder in vacuum drying oven
State granular preparation to be sieved to obtain white dry powder, it is standby that the dry powder and silica flour then are mixed to get into preparation.
The grain for the dry powder that the present embodiment is obtained is measured by SEM (result is as shown in Figure 1) and TEM (result is as shown in Figure 2)
Footpath scope is 200~900nm, is distributed around at most in 660.6nm by the DLS particle diameters for measuring dry powder, and measured by HPLC
Envelop rate is 14.0%.
Comparative example 1
This comparative example is carried out using method similar to Example 1, except that, using 300mg's in this comparative example
Molecular weight is the sodium alginate of the 300mg in 400 polyethylene glycol alternative embodiment 1, and remaining is in the same manner as in Example 1.
As a result, it can not obtain being enclosed with pesticide activity component as shown in Fig. 1 and Fig. 2 of embodiment 1 in this comparative example
Nanometer formula bactericide.
Comparative example 2
This comparative example is carried out using method similar to Example 1, except that, the consumption of nanometer silicon dioxide particle
For 3000mg, remaining is in the same manner as in Example 1.
As a result, obtained in this comparative example be enclosed with pesticide activity component nanometer formula bactericide envelop rate be only
0.3%.
Embodiment 2：Prepare nanometer formula bactericide
(1) 100mg nanometer silicon dioxide particles (average grain diameter is 50nm) are contacted with 100mL water to form mixture A,
And 500mg pyraclostrobins and 8mL are contained into emulsifying agent (Tween 80) and stabilizer (polyethylene glycol 2-glycidyl
Ether) methanol solution (in the methanol solution, methanol content is 87.69 weight %, and the content of Tween 80 is 6.39 weight %, is gathered
The content of ethylene glycol diglycidyl ether is 5.92 weight %) contact to form solution A；
(2) solution A of step (1) is contacted to obtain solution B with the mixture A of step (1) under agitation；
(3) under agitation 500mg sodium alginates are contacted to obtain suspension A with the solution B of step (2)；
(4) 320mg calcium chloride is dissolved in 10mL water, obtains solution C, by the suspension of the solution C and step (4)
A contacts to obtain suspension B；
(5) described be suspended is removed by spray drying process (drying machine inlet temperature is 150 DEG C, and outlet temperature is 100 DEG C)
Then solvent in liquid B is dried the dry powder to constant weight to obtain granular preparation, by institute with obtaining dry powder in vacuum drying oven
State granular preparation to be sieved to obtain white dry powder, it is standby that the dry powder and silica flour then are mixed to get into preparation.
The particle size range that the dry powder that the present embodiment is obtained is measured by SEM and TEM is 200~900nm, is measured by DLS
The particle diameter of dry powder is distributed around at most in 669.5nm, and it is 32.0% to measure envelop rate by HPLC.
Embodiment 3：Prepare nanometer formula bactericide
(1) 150mg silicon nanoparticles (average grain diameter is 60nm) are contacted with 100mL water to form mixture A, and will
720mg pyraclostrobins contain the first of emulsifying agent (Tween 80) and stabilizer (polyethylene glycol diglycidyl ether) with 10mL
(in the methanol solution, methanol content is 89.31 weight % to alcoholic solution, and the content of Tween 80 is 6.92 weight %, polyethylene second two
The content of alcohol diglycidyl ether is 3.77 weight %) contact to form solution A；
(2) solution A of step (1) is contacted to obtain solution B with the mixture A of step (1) under agitation；
(3) under agitation 600mg sodium alginates are contacted to obtain suspension A with the solution B of step (2)；
(4) 380mg magnesium chlorides are dissolved in 10mL water, obtain solution C, by the suspension of the solution C and step (4)
A contacts to obtain suspension B；
(5) suspension is removed by spray drying process (drying machine inlet temperature is 125 DEG C, and outlet temperature is 75 DEG C)
Then solvent in B is dried the dry powder to constant weight to obtain granular preparation with obtaining dry powder in vacuum drying oven, will be described
Granular preparation is sieved to obtain white dry powder, and it is standby that the dry powder and silica flour then are mixed to get into preparation.
The particle size range that the dry powder that the present embodiment is obtained is measured by SEM and TEM is 200~900nm, is measured by DLS
The particle diameter of dry powder is distributed around at most in 673.2nm, and it is 54.1% to measure envelop rate by HPLC.
Embodiment 4：Prepare nanometer formula bactericide
The present embodiment is carried out using method similar to Example 2, except that：
In the present embodiment using 500mg Difenoconazole alternative embodiment 2 in pyraclostrobin, remaining with implementation
It is identical in example 2, obtain dry powder formulations.
The particle size range that the dry powder that the present embodiment is obtained is measured by SEM and TEM is 200~900nm, is measured by DLS
The particle diameter of dry powder is distributed around at most in 645.6nm, and it is 29.6% to measure envelop rate by HPLC.
Embodiment 5：Prepare nanometer formula bactericide
The present embodiment is carried out using method similar to Example 3, except that：
The consumption of magnesium chloride in the present embodiment is 320mg, and remaining is in the same manner as in Example 3, obtains dry powder formulations.
The particle size range that the dry powder that the present embodiment is obtained is measured by SEM and TEM is 200~900nm, is measured by DLS
The particle diameter of dry powder is distributed around at most in 676.2nm, and it is 48.3% to measure envelop rate by HPLC.
Evaluating drug effect：
1st, antifungal activity is tested
The nanometer formula bactericide that embodiment is prepared is dispersed in water.
On superclean bench, with diameter 0.4cm card punch (advance 75% ethanol calcination of the libation at an ancient wedding ceremony 3 times to sterilize) in culture
Good cuts culture block-bacteria cake of carrying disease germs for examination strain bacterium colony outer rim, with transfer needle (advance 75% ethanol calcination of the libation at an ancient wedding ceremony 3 times) by bacterium
Cake reverse (have mycelia one fits with culture medium downwards) is transplanted to the nanometer formula with embodiment 1-5 and comparative example 2 and killed
(consumption of nanometer formula bactericide causes the pesticide activity component concentration in culture medium on the culture medium (PDA culture medium) of microbial inoculum
As shown in table 1).Per decoction, processing is repeated 3 times (3 culture dishes), and 1 bacteria cake is placed at the center of each culture dish.
Culture dish is sealed with sealed membrane, is placed in insulating box and cultivates.
The diameter of bacterium is measured with cross：Each bacterium colony (bacteria growing four days) measures two directly with ruler with crossing method
Footpath, per two data of bacteria cake, takes its average value to represent bacterium colony size.
Diameter average value (the mm) -4.0mm (bacteria cake diameter) of colony growth diameter (mm)=twice；
Mycelial growth inhibition rate % (bacteriostasis rate)=(control colony growth diameter-processing colony growth diameter)/control bacterium
Fall growth diameter × 100
(it is respectively citrus anthracnose to 2 kinds of pathomycetes using the nanometer formula bactericide of embodiment 1-5 and comparative example 2
Bacterium (Colletotrichum glecosporioides) and Rhizoctonia solani Kuhn (Rhizoctonia solani)) carry out above-mentioned resist
Fungicidal activity, bacteriostasis rate result is as shown in table 1.
And it is used as control 2 using pyraclostrobin active compound as control 1 and using difenoconazole technical material.
Table 1
The nanometer formula bactericide that the present invention is provided it can be seen from the result of table 1 has good bactericidal effect, example
Such as, the bactericidal effect suitable with the active compound for compareing can be realized.The nanometer pharmaceutical formulation energy that this explanation present invention is provided
Enough easily enter into germ body, and said preparation can realize timely and effectively pesticide activity after entering in germ body
The release of composition, so as to realize excellent bactericidal effect.
2nd, the endotoxic experiment of fish body
Bactericide is formulated to carp (Cyprinuscarpio) using embodiment 1-3, embodiment 5 and comparative example 2 nanometer
Tested.
Experimental method is specially：
Carp is purchased from Nanning Jiangnan District Ting Hong roads fry market.It is average that per tail fish 2.8g, average length is 43mm,
Normal after buying back to raise 2 days, packet (every group of 10 tails) is standby after its natural mortality rate is stable.
Reagent agent is：
A：The nanometer formula bactericide that embodiment 1-3, embodiment 5 and comparative example 2 are prepared, consumption causes pesticide activity
The content of composition is 200mg (for example, the nanometer formula bactericide consumption that the embodiment 1 that envelop rate is 14% is prepared is
1.42g)；
B：9 weight % pyraclostrobin suspending agent 2.22g；
C：25 weight % pyraclostrobin missible oil agent 0.8g；
D：25 weight % pyraclostrobin suspension emulsion 0.8g.
Take above-mentioned A, B, C, D one-level mother liquor 3mL to be respectively placed in constant volume in 200mL volumetric flasks respectively, and be configured to agricultural chemicals work
Property composition (pyraclostrobin) equivalent for 30mg/L secondary mother liquor it is standby.
The feeding water of each treatment group is 5L, and the consumption of secondary mother liquor causes pesticide activity component in each treatment group
Final concentration of 0.036mg/L, and clear water control group is set, respectively handled every 24h and water is changed 1 time using same concentrations decoction.Point
Each processing dead fish quantity of 5h, 7h, 24h, 48h, 72h, 96h investigation not after medicine, and calculate the death rate, the death rate (%)=(individual
Body accumulation The dead quantity) individual total quantity × 100 of/feeding.
Above-mentioned experiment in triplicate, results averaged, as shown in table 2.
Table 2
| Preparation | The death rate/% |
| Embodiment 1 | 40.0 |
| Embodiment 2 | 36.7 |
| Embodiment 3 | 33.3 |
| Embodiment 5 | 40.0 |
| Comparative example 2 | 33.3 |
| B | 70.0 |
| C | 90.0 |
| D | 100.0 |
| Clear water is compareed | 40.0 |
The nanometer that the present invention is provided it can be seen from the result of table 2 is formulated small toxicity of the bactericide to fish, and fish toxicity
The formulations such as suspending agent, emulsifiable concentrate significantly lower than pesticide activity component commonly used in the prior art, also, embodiments of the invention
The death rate it is suitable with the death rate of clear water control group, it can be confirmed that, under above-mentioned consumption concentration, nanometer of the invention is matched somebody with somebody
It is high and nontoxic that square bactericide can be described as safety to non-target organism body.
3rd, environmental behaviour evaluation
The preparation release that this experiment is prepared in following several 1-5 of testing example under different conditions and comparative example 2
The rate behavior of pesticide activity component, in each test environment, the consumption of nanometer formula bactericide causes pesticide activity component
Concentration is 2ppm, and as a result (the micro release in table 3 represents that release is less than 0.01%, when release %=is tested as shown in table 3
Under concentration/initial situation of the pesticide activity component in environmental system nanometer formula bactericide Pesticides active component concentration ×
100)。
Table 3
It can be seen that by the result of table 3：Stability of the nanometer formula bactericide that the present invention is provided in practical environment is good
It is good, wherein the release for the pesticide activity component encapsulated is extremely low.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited thereto.In the skill of the present invention
In art concept, technical scheme can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and these simple variants and combination should equally be considered as content disclosed in this invention, belong to
Protection scope of the present invention.
Claims (10)
1. contain alginate, nanometer silicon source, polyvalent cation and pesticide activity in a kind of pesticide action-controlling composition, said composition
Composition, wherein, on the basis of the gross weight of the composition, the content of the alginate is 10~90 weight %, described to receive
The content of rice silicon source is 2~60 weight %, and the content of polyvalent cation is 2~40 weight %, and the pesticide activity component
Content be 5~80 weight %.
2. composition according to claim 1, wherein, the content of the alginate is 15~60 weight %, described to receive
The content of rice silicon source is 5~25 weight %, and the content of polyvalent cation is 20~40 weight %, and the pesticide activity component
Content be 8~60 weight %.
3. composition according to claim 1 or 2, wherein, the alginate is sodium alginate, calcium alginate and marine alga
At least one of sour potassium；Preferably,
The nanometer silicon source is nano silicon and/or nano-silicon；Preferably,
The polyvalent cation is selected from Ca2+、Mg2+、Cu2+、Mn2+、Zn2+And Fe+3At least one of.
4. composition according to claim 1 or 2, wherein, the pesticide activity component is selected from pyraclostrobin, poisoned with poison
Tick, cypermethrin, basudin, 5a,6,9,9a-hexahydro-6,9-methano-2,4, phosmet, malathion, Methomyl, 2-dichloroethylk dimethyl phosphate, novaluron, Deltamethrin, pyrrole worm
At least one of quinoline, Permethrin and thimet insecticide and/or for selected from Fluoxastrobin, Difenoconazole, Bravo, downy mildew
Prestige, Fenamidone, fluopicolide, Mancozeb, metalaxyl, Carbatene, pyrazoles bacterium amine, zoxamide, benzene azoles mepanipyrim, alkene acyl
At least one of morpholine, copper agent, cymoxanil, famoxadones and fluazinam antiseptic.
5. composition according to claim 1 or 2, wherein, further contain selected from emulsifying agent, stably in said composition
In agent, solvent, dispersant, wetting agent, spreader-sticker, defoamer, synergist, bleeding agent, sticker, safener, carrier and filler
At least one additive.
6. a kind of nanometer, which is formulated in bactericide, this nanometer formula bactericide, contains the group described in any one in claim 1-5
Compound, and this nanometer formula bactericide formulation for wettable powder, microcapsule suspending agent, aqueous suspension agent, dispersible oil-suspending agent,
At least one of aqueous emulsion, granule and microemulsion.
7. a kind of method that nanometer prepared described in claim 6 is formulated bactericide, including：
(1) nanometer silicon source is contacted with water to form mixture A, and pesticide activity component is contacted to form solution with solvent
A；
(2) solution A is contacted to obtain solution B with the mixture A under agitation；
(3) under agitation alginate is contacted to obtain suspension A with the solution B；
(4) solution C of the aqueous solution containing polyvalent cation is contacted to obtain suspension B with the suspension A.
8. method according to claim 7, wherein, this method further comprises：Removed by spray drying process described mixed
Solvent in suspension B to obtain dry powder, then by the dry powder drying to constant weight to obtain granular preparation.
9. method according to claim 8, wherein, the particle diameter of the granular preparation is 200~900nm.
10. the method according to any one in claim 7-9, wherein, the spray drying is entered in spray dryer
OK, and the condition of the spray drying includes：Inlet temperature is 100~250 DEG C, outlet temperature is lower than the inlet temperature by 40~
60℃。
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