CN103858862B - A kind of environmentally friendly emamectin-benzoate water solube powder and preparation method thereof - Google Patents
A kind of environmentally friendly emamectin-benzoate water solube powder and preparation method thereof Download PDFInfo
- Publication number
- CN103858862B CN103858862B CN201410051692.2A CN201410051692A CN103858862B CN 103858862 B CN103858862 B CN 103858862B CN 201410051692 A CN201410051692 A CN 201410051692A CN 103858862 B CN103858862 B CN 103858862B
- Authority
- CN
- China
- Prior art keywords
- benzoate
- water
- emamectin
- environmentally friendly
- weight portion
- 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.)
- Active
Links
Abstract
The present invention provides a kind of and provides new environmentally friendly emamectin-benzoate water solube powder, and raw material composition includes: 17 weight portion emamectin-benzoates, 1 10 weight portion agent A；Can also include 16 weight portion agent B and/or other improve, improve the composition of preparation performance.The present invention also provides for the preparation method of described water solube powder.Water solube powder good water solubility of the present invention, obtains clarification, thermodynamically stable, solution without any organic solvent after adding water, hence it is evident that be better than in prior art the solid preparations such as emamectin-benzoate wettable powder.And the indoor insecticidal effect of water solube powder of the present invention is suitable with the emamectin-benzoate cream of same concentration.
Description
Technical field
The invention belongs to pesticides new formulation field, particularly to a kind of new environmentally friendly methylamino Avermectin
Element benzoate water solube powder and preparation method thereof.
Background technology
Along with the raising of environmental consciousness, efficiently the most eco-friendly requirement is proposed pesticidal preparations.Research is sent out
Existing, for pesticide original medicine of the same race, pesticidal preparations plays the height of drug effect, depends on its types of formulation and agriculture
The dispersity of medicine microgranule and size.Scientific common sense teaches that, when other condition is identical, and pesticide original medicine
Microgranule dispersion size the least, its surface area is the biggest, the widest with the contact area of plant leaf blade and insect, medicine
Effect plays the most abundant, and the usage amount of pesticide will reduce accordingly.
A kind of formulations of pesticide whether environmental friendliness, its evaluation criterion had both related to the character of pesticide original medicine itself, also
Relate to whether dosage form uses organic solvent, and whether the solvent and the auxiliary agent that use belong to green matter.Respectively
Although kind of a water baseization pesticidal preparations pertains generally to environmental friendliness dosage form, but the evaluation of environmentally friendly degree should
With reference to above-mentioned standard.In August, 2010, national four ministries and commissions combine appearance " pesticide industrial policy ", Qi Zhongming
Really point out: " country passes through the measures such as science and technology support, technological transformation, economic policy guiding, support efficiently,
Pesticide new product safe, economic, eco-friendly develop, accelerate high pollution, the replacement of excessive risk product and
Eliminate, promote that breed structure is continued to optimize.”；" promote energetically agricultural dosage form to water baseization, dustlessization,
Control efficient, the safe directions such as release to develop ... strict control poisonous and harmful solvent and the use of auxiliary agent.”
In the recent period, Ministry of Industry and Information has put into effect again " pesticide industry " 12 " development plan ", wherein emphasizes: " tight
Lattice control, containing the poisonous and harmful solvent such as toluene, dimethylbenzene and the use of auxiliary agent, develop and promote the agent such as water baseization
Type ".Therefore, do not use or reduce use organic solvent as far as possible, select and use Green Additives, should become
Develop and promote a kind of developing direction and the trend of the environmental friendliness formulations of pesticide.
In the water baseization formulations of pesticide, the only pesticide original medicine in aqueous pharmaceutical (water preparation) dosage form belongs to single point
Son dispersion, size is minimum.But the pesticide species that can be prepared as water preparation is little, and the pesticide species having is at water
In easily hydrolyze, which limits its application.Because most of pesticide are oil-soluble, have can only be dissolved in
Organic solvent, being even difficult to of having is dissolved in conventional organic solvent.It is prepared into water base agent type, logical
Often can only be prepared as microemulsion, aqueous emulsion, suspending agent and suspension emulsion.In these four dosage form, pesticide is at water
In scattered particle size increase successively.Microemulsion, aqueous emulsion are to dissolve the molten of pesticide original medicine with organic solvent
Liquid drop form is dispersed in water, and wherein the drop size of microemulsion is minimum, below 100 nanometers,
Less than 1/4th of visible wavelength, thus system is transparent, belongs to thermodynamic stable system；And aqueous emulsion
Solution droplets size more than hundreds of nanometer to micron, close or larger than visible wavelength, system is opaque,
And poor stability.Suspending agent is typically the pesticide microgranule by being ground into micron-scale by macromolcular dispersant
Effect is suspended in water, and this system has the tendency that the cohesion of pesticide crystal grain occurs.Suspension emulsion is then suspending agent
Combining form with aqueous emulsion.In these four dosage form, in addition to suspending agent, all contain the organic of 10%-20%
Solvent, this reduces their environmental friendliness performance to varying degrees.
Emamectin-benzoate, (being called for short emamectin benzoate, Emamectin benzoate, EB), structure
Formula is as indicated with 2.Emamectin benzoate is from biological antibiotic pesticide avermectin B1a, obtains through chemical modification
A kind of ultra high efficiency insecticidal/acaricidal agent.Compared with parent Avermectin B1a, emamectin-benzoate
Insecticidal activity improves tens times, has ultra high efficiency, wide spectrum, the most nontoxic, noresidue, spy that Drug resistance is little
Point.The test of pesticide effectiveness shows, emamectin-benzoate has other pesticide to a lot of insects cannot be compared
Intend activity, especially to Lepidoptera, Diptera ultra high efficiency, insect include red tape leaf roller, cigarette aphid noctuid,
Noctuid, confused Autographa spp, Caulis et Folium Brassicae capitatae silver are coveted in bollworm, maduca sexta, diamondback moth mythimna separata, beet armyworm, nonirrigated farmland
Autographa spp, cabbage butterfly, Brassica campestris L. ssp.chinensis snout moth's larva, Caulis et Folium Brassicae capitatae horizontal stripe snout moth's larva, Fructus Lycopersici esculenti hawkmoth, colorado potato bug, Mexico ladybug
Deng.Emamectin-benzoate antagonism bollworm and pickles spy moth effect, under low-down dosage
Also there is good insecticidal effect.Along with the disabling of high-toxic pesticide, emamectin-benzoate becomes
The main product of insecticide on market.
Emamectin-benzoate is soluble in the organic solvents such as acetone, methanol, toluene, dimethylbenzene,
But being insoluble in water, the dissolubility in water is about only 0.024g/L(25 DEG C).Therefore its dosage form is presently mainly breast
Oil, microemulsion, aqueous emulsion and water dispersion granule.The cream dosage form of emamectin-benzoate makes
With a large amount of poisonous and hazardous toluene, dimethylbenzene equal solvent, clearly it is classified as superseded backward agent by Ministry of Industry and Information of country
Type.Solid water baseization preparation is because it is without organic solvent, it is simple to packs, store, transport, and by market
Welcome.And existing water dispersion granule can not be dissolved in water on market, simply disperse in water, due at water
In the size of scattered pesticide microgranule big, be unfavorable for the performance of drug effect.
In prior art, the solid preparation with emamectin-benzoate as pesticide original medicine has, open
Number CN101361479A(publication date on February 11st, 2009) application for a patent for invention " methylamino avermectin
The water dispersion granule of benzoate ", and publication number CN1775027A(publication date on May 24th, 2006)
Application for a patent for invention " containing the disinsection soluble granules of emamectin-benzoate ".Above-mentioned
Preparation, either water dispersion granule or soluble granule, after adding water, Affirm (Merck Co.) benzene first
Hydrochlorate is suspended in water by the effect of macromolcular dispersant, is a kind of thermodynamic unstable system, there is crystalline substance
The tendency of grain cohesion, places relatively for a long time easily precipitation；And the technological process prepared is long, production technology includes air-flow
Pulverizing, kneading, pelletize, be dried etc., need investment produce equipment accordingly, each of which increases preparation
Production cost.
Therefore, it is necessary to develop the water-soluble solid of a kind of environmental friendliness emamectin-benzoate
Preparation, it can dissolve rapidly after adding water, obtain thermodynamically stable diluent.
It addition, there is the feature meeting light fast degradation in emamectin-benzoate self, commonly containing first
Lasting period after the pesticidal preparations of amino abamectin benzoate sprays is short, typically at about 7 days.Therefore,
Also it is necessary to improve further photodegradation and the oxidative resistance of emamectin-benzoate solid preparation
Energy.
Summary of the invention
The primary and foremost purpose of the present invention is to overcome the deficiencies in the prior art, it is provided that new environmentally friendly methylamino
Abamectin benzoate water solube powder.The water soluble characteristic of described water solube powder is superior, add suitably than
The water of example, i.e. can get clear, thermodynamically stable diluent；Thus overcome in prior art,
Emamectin-benzoate liquid preparation contains poisonous, harmful organic solvent, and methylamino A Wei
Rhzomorph benzoate solid preparation add water after the big defect of pesticide particle size.
It addition, on the basis of emamectin-benzoate water solube powder, add various further
Water-solubility function agent, not only can extend the lasting period of parasite killing, reduces spraying times, reduces its consumption, and
And also can give emamectin-benzoate water solube powder more function.
A further object of the invention, is to provide described environmentally friendly emamectin-benzoate
The preparation method of water solube powder.
In order to realize foregoing invention purpose, present invention employs following technical scheme:
A kind of environmentally friendly emamectin-benzoate water solube powder, including methylamino Avermectin
Element benzoate, does not include filler.
Preferably, described environmentally friendly emamectin-benzoate water solube powder, raw material forms
Including:
1-7 weight portion emamectin-benzoate, 1-10 weight portion agent A；
Preferably, described environmentally friendly emamectin-benzoate water solube powder raw material composition bag
Include:
1-7 weight portion emamectin-benzoate, 2-8 weight portion agent A；
Wherein, described agent A is selected from the anionic surfactant containing sulfonic acid group, sulfur acid group
Anionic surfactant and carboxyl group anion surfactant in one or more.
Preferably, state agent A described in selected from straight or branched aliphatic group sulfonic acid and salt, straight chain or to prop up
Chain fatty alkyl ether sulfonic acid and salt, straight or branched aliphatic group sulphuric acid and salt thereof, straight or branched fat
One or more in hydrocarbyl ether sulphuric acid and salt thereof and straight or branched aliphatic group carboxylic acid and salt thereof.
It is furthermore preferred that described agent A is selected from the compound of structural formula 1,
CH3(CH2)n(OCH2CHR')mOk(CO2)j(SO3)iM
1
Wherein, n=7-17, preferably n=11,13,15, or 17,
R '=H or CH3,
M=0,1,2,3, or 4,
K=0 or 1,
J=0 or 1,
I=0 or 1, and i ≠ j,
M=H, K, Na, or NH4。
Accordingly, as the preferred embodiment of the present invention, described agent A is selected from following compound
Plant or several:
I. dodecyl, myristyl, cetyl and octadecyl sulfonic acid and potassium, sodium or ammonium salt;
II. dodecyl, myristyl, cetyl and octadecyl sulfonic acid ether and potassium, sodium or ammonium salt;
III. dodecyl, myristyl, cetyl and octadecyl sulphuric acid and potassium, sodium or ammonium salt;
IV. dodecyl, myristyl, cetyl and octadecyl sulphuric acid ether and potassium, sodium or ammonium salt；
V. dodecyl, myristyl, cetyl and octadecyl carboxylic acid and potassium, sodium or ammonium salt.
Environmentally friendly emamectin-benzoate water solube powder of the present invention, it is also possible to bag
Include 1-6 weight portion agent B；Described agent B selected from containing ethylene oxide unit, propylene oxide unit or
The nonionic surfactant of glucose unit and/or natural polymeric surface active agent.
Preferably, described nonionic surfactant is selected from polyethylene glycol oxide, polypropylene oxide, polyethylene
One or more in alcohol and polyvinylpyrrolidone；More preferably from straight chain fatty polyoxyethylenated alcohol, straight chain
Polyoxyethylene carboxylate, straight-chain fatty amine polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether,
One or more in APG and castor oil polyoxyethylene ether.
Preferably, described natural polymeric surface active agent is selected from water soluble starch derivatives, water-soluble fibre
One or more in element derivant and Chitosan-phospholipid complex；More preferably from dextrin, carboxymethyl starch,
One or more in carboxymethyl cellulose, chitosan, carboxymethyl chitosan and Quaternary Ammonium Salt of Chitosan.
Environmentally friendly emamectin-benzoate water solube powder of the present invention, also includes 1-5
Weight portion functionalizers.
Described functionalizers selected from have potentiation, sterilization, degeneration-resistant, stimulate plant growth, improve drug effect, press down
Residual hazard processed, the chemosynthesis material improving the function of agricultural product quality or natural product；Preferably tea saponin, corruption
In phytic acid, Chitosan-phospholipid complex, alginate, hyaluronic acid, Fructus Gleditsiae Abnormalis extract, matrine one
Plant or several.
Environmentally friendly emamectin-benzoate water solube powder of the present invention, it is also possible to bag
Include 0.1-10 weight portion insecticides adjuvant.Preferably, described insecticides adjuvant includes that light stabilizer and/or drift control
Agent.
It is furthermore preferred that described light stabilizer is 0.1-0.4 weight portion；Selected from salicylic acid esters, benzophenone,
One or more in benzotriazole and hindered amine light stabilizer；Further preferably benzophenone light is steady
Determine agent；Most preferably from 2,4-dihydroxy-5-sulfonic group benzophenone, 2,2`, 4,4`-tetrahydroxybenzophenone and 2,3,
One or more in 4,4`-tetrahydroxybenzophenone.
It is furthermore preferred that the weight portion of described drift control agents is 1-3；Selected from the surface that can reduce spray droplet
Tension force, increases viscoelasticity, improves the deposition of medicine, reduces the water solublity synthetic high polymer matter of drop bounce-back
And natural high molecular substance；The most described water-soluble natural polymer substance；Most preferably from water-soluble
One in property cellulose derivative, water solublity guar gum and derivant thereof and water soluble starch and derivant thereof
Several.
Environmentally friendly emamectin-benzoate water solube powder of the present invention, also includes
0.01-0.1 weight portion defoamer；Preferably, described defoamer selected from organic silicon defoamer, carbon atom quantity is
C7-C9Fatty alcohol and tributyl phosphate in one or more.
Another object of the present invention, is to provide described environmentally friendly emamectin-benzoate
The preparation method of water solube powder, is prepared by following method I or II:
Method I: each raw material components mix homogeneously of emamectin-benzoate will be included；
Method II: include, first by described soluble in water at agent A, adding Affirm (Merck Co.) benzene first
Hydrochlorate, other raw material components and water, the concentration expressed in percentage by weight obtaining emamectin-benzoate is
The solution of 1%-7%, dehydration, to obtain final product.
Preferably, described method II specifically includes following steps:
A. various raw materials are prepared according to formula；
B. described agent A is dissolved in the water of 20-60 weight portion, stirring, makes dissolving, obtain solution A；
C., in addition to defoamer, raw material is included, and other each component of emamectin-benzoate adds
Described solution A, addition water makes the concentration expressed in percentage by weight of emamectin-benzoate be 1%-7%, stirs
Mix, make dissolving, obtain solution B；
D. defoamer is added solution B, gentle agitation, static, filter, obtain solution C;
E. solution C is dried, preferably spray drying, to obtain final product.
Emamectin-benzoate is in the chemical constitution of antibiotics avilamycin, introduces first ammonia
This characteristic group of base also is allowed to become salt with benzoic acid.Emamectin-benzoate dissolving in water
Spend the least, only 0.024g/L.
In order to solve the water of environmentally friendly emamectin-benzoate water solube powder of the present invention
Dissolubility problem so that it is add and can be dissolved in rapidly water after water, become real thermodynamic stable system, this
Bright first having to solves to improve the water miscible problem of emamectin-benzoate.Agent of the present invention
A, is that a class can improve emamectin-benzoate dissolubility and material of separating degree in water.Send out
A person of good sense is found by research, and some specific compound can function as described above, thus without by organic
Solvent, it is possible to prepare the water preparation of emamectin-benzoate.Therefore, inventor is by following real
Test and agent A has been carried out preferably.
Quantitative different types of compound and quantitative Affirm (Merck Co.) benzene first is added in 10ml water
Hydrochlorate, stirs under room temperature, observes dissolving situation, preferably goes out the material type of agent A.The results are shown in Table 1.
Table 1 agent screening formula and result
By above-mentioned experiment, described agent A be preferably the anionic surfactant containing sulfonic acid group,
The anionic surfactant of sulfur acid group and the anion surfactant of carboxyl group.
By further experiment, find that described agent A is more preferably from straight or branched aliphatic group sulfonic acid
And salt, straight or branched aliphatic group sulfonic acid ether and salt, straight or branched aliphatic group sulphuric acid and salt thereof,
Straight or branched aliphatic group ether sulphuric acid and salt, straight or branched aliphatic group carboxylic acid and salt thereof.
Most preferably, described agent A is selected from the compound of structural formula 1,
CH3(CH2)n(OCH2CHR')mOk(CO2)j(SO3)iM
1
Wherein, n=7-17, preferably n=11,13,15, or 17,
R '=H or CH3,
M=0,1,2,3, or 4,
K=0 or 1,
J=0 or 1,
I=0 or 1, and i ≠ j,
M=H, K, Na, or NH4。
In order to improve emamectin-benzoate dispersibility in water, raising preparation stability,
Opposing hard water, the surface tension reducing inhibitor dilutions and increase sprawl effect, institute of the present invention at plant leaf surface
State environmentally friendly emamectin-benzoate water solube powder and can also include the work of 1-6 weight portion
Use agent B.
The present invention passes through preferred functionalizers, gives novel environmental close friend's Affirm (Merck Co.) benzoic acid
The function that water-soluble powder is new so that it is there is the effects such as sterilization, degeneration-resistant, potentiation, stimulating growth.For
Realize this purpose, including chemosynthesis material or natural product, preferably be selected from tea saponin, humic acids and shell
One or more in polysaccharide.Tea saponin is a kind of natural nonionic surfactant, has good breast
Change, disperse, foam, the function such as moisten, can as the wetting agent of pesticidal preparations, synergist and spreader-sticker,
And there is certain parasite killing, bactericidal action.Humic acids is produced through microbial action by plant and animal residues
Natural polymer organic acid, wherein fulvic acid molecular weight is little, is dissolved in water, and activity is high, has enhancing crop and resists
Characteristic of disease, to pesticide slow-release potentiation, reduces toxicity, extends drug effect, effectively reduces the effects such as agriculture is residual.Chitosan
It is the alkaline polysaccharide that uniquely there is cation in nature in a large number, there is disease resistance effective, safe, micro-
Amount, efficient feature, it is possible to degeneration-resistant, resist pest and disease damage, increase production, improve quality of agricultural product.Have with other
The natural polymer of similar effect substitutes functionalizers of the present invention, also at spirit of the invention and spirit model
In enclosing.
In order to improve the performance of emamectin-benzoate water solube powder of the present invention further,
Preparation of the present invention also includes insecticides adjuvant, accounts for 0.1-10 weight portion.Methylamino Avermectin of the present invention
Element benzoate water solube powder typically adds water after being made into suitable concentration solution, uses with Sprayable；In order to
Extend emamectin-benzoate action time on crop blade face, improve pulverability, described
Insecticides adjuvant preferably includes to include light stabilizer and/or drift control agents.
Described light stabilizer refers to reduce emamectin-benzoate and quickly divides under sunlight irradiates
The material solved, the light stabilizer such as including salicylic acid esters, benzophenone, benzotriazole, hindered amines.
Consider from environmental friendliness angle, be preferably applicable to the light stabilizer of the benzophenone of cosmetics.From this
The feature of bright dosage form considers, preferably benzophenone light stabilizer is concrete, preferably is selected from 2,4-dihydroxy-5-
In sulfonic group benzophenone, 2,2`, 4,4`-tetrahydroxybenzophenone and 2,3,4,4`-tetrahydroxybenzophenone one
Plant or several.In preparation of the present invention, described light stabilizer consumption is 0.1-0.4 weight portion.
Described drift control agents refers to reduce the surface tension of spray droplet, increases viscoelasticity, improves medicine
The deposition of thing, reduces the auxiliary agent of drop bounce-back, selected from synthetic high polymer matter and natural high molecular substance.From
The environmental friendliness of dosage form considers, prioritizing selection water-soluble natural polymer substance, as water-soluble cellulose derives
One or more in thing, water solublity guar gum and derivant thereof and water soluble starch and derivant thereof.At this
Inventing in described preparation, the consumption of described drift control agents is 1-3 weight portion.
Environmentally friendly emamectin-benzoate water solube powder of the present invention, needs during use
Add water and be configured to aqueous solution.Environmentally friendly emamectin-benzoate water solublity the most of the present invention
Powder is formulated state when a kind of transport and storage, and actual being still uses with aqueous pesticide solution form.In order to full
The formulation requirements of foot aqueous pesticide solution, also includes defoamer in the composition of raw materials of water preparation of the present invention.
Defoamer of the present invention refer to water preparation manufacture last during eliminate the material of foam, choosing
It is C from organic silicon defoamer commonly used in the art, carbon atom quantity7～C9Fatty alcohol, tributyl phosphate etc.,
Its weight portion is 0.01-0.1.
Along with the addition of above-mentioned functions agent, finally, the invention provides a kind of several functions that integrates
Environmentally friendly emamectin-benzoate water solube powder.
Various raw materials can directly be mixed by emamectin-benzoate water solube powder of the present invention
Conjunction prepares.But, during use, adding water needs to stir the long time and just can obtain the solution of clarification.
For the ease of using, currently preferred preparation method is first to be prepared as water preparation, removes moisture removal the most again,
Powder to solid.
Environmentally friendly emamectin-benzoate water solube powder of the present invention, technique is simple,
Produce workable.Capital equipment is the general production equipment stirred tank of the water baseization formulations of pesticide；In order to
Improve production efficiency, can separately add a spray dryer.
Environmentally friendly emamectin-benzoate water solube powder of the present invention, can apply to
The crop such as veterinary antibiotics, Folium Camelliae sinensis, Oryza sativa L., Semen Maydis, Cotton Gossypii preventing and treating Lepidoptera, Diptera, Homoptera,
The insects such as coleoptera.
The emamectin-benzoate water solube powder prepared with currently preferred method, average particle
Footpath is at 50～150 microns.By regulating the consumption of auxiliary agent, can be by Affirm (Merck Co.) benzene first in powder body
The content of hydrochlorate effective ingredient controls 15～35% scope.According to emamectin-benzoate to not
The concentration requirement sprayed with crop, by a certain amount of environmentally friendly Affirm (Merck Co.) benzene first of the present invention
Hydrochlorate water solube powder is even added in corresponding water, and described water solube powder can disperse rapidly also at the water surface
Infiltrated, through stirring just can be the most soluble in water a little, clarified, transparent aqueous solution, the most just may be used
For spraying.
The present invention will be insoluble in the emamectin-benzoate of water and preferred anion surfactant
It is grouped compound, improves its performance with preferred nonionic surfactant, by Affirm (Merck Co.) simultaneously
The dissolubility in water of benzoate improves two orders of magnitude, thus obtains stable methylamino Avermectin
Element benzoate high concentration solution.This aqueous solution can be directly used as water preparation dosage form.There is provided on this basis
A kind of novel environmental close friend's emamectin-benzoate water solube powder.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings, the present invention is elaborated.
The photo of Fig. 1 is shown that the environmentally friendly emamectin-benzoate of embodiment 1 preparation
Water solube powder.
The photo of Fig. 2 is shown that the environmentally friendly emamectin-benzoate of embodiment 3 preparation
Water solube powder is dissolved in water, the 3% emamectin-benzoate aqueous solution obtained.
Fig. 3 is shown that the environmentally friendly emamectin-benzoate water solublity of embodiment 5 preparation
Powder is dissolved in water, the 5% emamectin-benzoate solution obtained.
The photo of Fig. 4 is shown that the environmentally friendly methylamino Avermectin of embodiment 1 preparation in test example 1
The course of dissolution of element benzoate water solube powder；Wherein:
The photo of Fig. 4 A is shown that the environmentally friendly emamectin-benzoate of embodiment 1 preparation
The situation that water solube powder has just been added to the water；
The photo of Fig. 4 B is shown that the situation after gentle agitation；
The photo of Fig. 4 C is shown that the water-soluble of 1 ‰ emamectin-benzoates that test example 1 obtains
Liquid.
The photo of Fig. 5 is shown that the Tyndall phenomenon in test example 2；Wherein:
Being test sample 1 in the conical flask of the nearly laser pen in left side, i.e. the embodiment of the present invention 1 preparation is environmentally friendly
Emamectin-benzoate water preparation is diluted with water to the solution of 1% concentration；
Right side, away from the conical flask of laser pen being test sample 2, i.e. makes 1% Affirm (Merck Co.) benzoic acid by oneself
Salt microemulsion.
Fig. 6 is shown that 5% emamectin-benzoate water preparation and 1% methylamino A Wei in test example 3
The toxicity regression line of rhzomorph benzoate cream.
Detailed description of the invention
Below, by preferred embodiment, the present invention is described in detail.But the present invention is not restricted to
Following embodiment.
Various raw materials used in embodiment all can be by what commercial channel obtained.
Embodiment 1A kind of Multifunctional environment friendly emamectin-benzoate water solube powder
Raw material composition (unit: kg)
Dodecyl sodium sulfate, cetyl ether ammonium sulfate are joined in stirred tank, add 50kg deionization,
It is stirred at room temperature, is allowed to dissolve, be then added thereto to AEO-20, APG, tea saponin, Huang
Rotten acid, chitosan, glycerol, stir under room temperature, obtain solution A.It is subsequently adding Affirm (Merck Co.) benzene
Formates, stirs under room temperature, is allowed to dissolve.Add 25kg deionized water dissolving hydroxyethyl cellulose and
2,4-dihydroxy-5-sulfonic groups, are stirred at room temperature, are allowed to dissolve, obtain solution B.Add in solution B
Organic silicon defoamer, gentle agitation, static, filter, obtain the Affirm (Merck Co.) of the transparent shape of outward appearance
Benzoate content is the solution C of 5%.
Solution C is spray-dried, and obtains mean diameter at 50～150 microns, Multifunctional environment friendly first
Amino abamectin benzoate water solube powder, sample is as shown in Figure 1.In water solube powder, first ammonia
The content of base abamectin benzoate is about 20%.
Embodiment 2A kind of Multifunctional environment friendly emamectin-benzoate water solube powder
Raw material: (unit: g)
Use preparation method similar to Example 1 and step, obtain mean diameter at 50～150 microns,
Multifunctional environment friendly emamectin-benzoate water solube powder.Difference is, preparation
During solution A, add 55g deionized water；During preparation solution B, add 30g deionized water.
Embodiment 3The emamectin-benzoate water solube powder that a kind of Multifunctional environment is friendly
Raw material: (unit: g)
Use preparation method similar to Example 2 and step, obtain mean diameter at 50～150 microns,
Multifunctional environment friendly emamectin-benzoate water solube powder.
Adding water, the weight percent concentration making emamectin-benzoate is 3%, is gently mixed,
Clarified, transparent solution, as shown in Figure 2.
Embodiment 4The emamectin-benzoate water solube powder that a kind of Multifunctional environment is friendly
Raw material: (unit: g)
Use preparation method similar to Example 2 and step, obtain mean diameter at 50～150 microns,
Multifunctional environment friendly emamectin-benzoate water solube powder.
Embodiment 5The emamectin-benzoate water solube powder that a kind of Multifunctional environment is friendly
Raw material: (unit: g)
Use preparation method similar to Example 2 and step, obtain mean diameter at 50～150 microns,
Multifunctional environment friendly emamectin-benzoate water solube powder.
Adding water, the weight percent concentration making emamectin-benzoate is 5%, is gently mixed,
Clarified, transparent solution, as shown in Figure 3.
Embodiment 6A kind of eco-friendly emamectin-benzoate water solube powder
Raw material: (unit: g)
Use preparation method similar to Example 2 and step, obtain mean diameter at 50～150 microns,
Multifunctional environment friendly emamectin-benzoate water solube powder.
Test example 1Environmentally friendly emamectin-benzoate water solube powder of the present invention
Dissolution experiment
1) beaker adds 100ml water, add the environmentally friendly Affirm (Merck Co.) of embodiment 1 preparation
Benzoate water solube powder, the weight percent concentration making emamectin-benzoate is 1 ‰.
When described water solube powder is added to the water, the most spontaneously spreads to water surface surrounding and infiltrated, some
The powder ball that volume is bigger swims in the water surface, as shown in Figure 4 A.Subsequently, after Glass rod mild agitation, powder ball is fast
Speed dispersing and dissolving, and form a small amount of bubble at the edge of solution, bubble can rupture voluntarily, as shown in Figure 4 B.
Finally obtain clarification, transparent solution, as shown in Figure 4 C.
Conclusion: the described environmentally friendly emamectin-benzoate water soluble powder of embodiment 1 preparation
Agent, good water solubility, it is not necessary to by auxiliary agent, just can dissolve rapidly in water, be clarified, transparent molten
Liquid.
Test example 2Tyndall phenomenon is tested
Test sample:
1) the Multifunctional environment friendly emamectin-benzoate water solube powder of embodiment 1 preparation,
Soluble in water, it is configured to the aqueous solution that emamectin-benzoate weight percent concentration is 1%；
2) commercially available 1% emamectin benzoate microemulsion；
Test method:
Will be equipped with in the conical flask of test sample 1 and 2, side by side, the laser that laser pen is launched first passes through test sample 1,
Again by test sample 2, observe in liquid whether laser via occurs.
Result of the test: see Fig. 5.
Fig. 5 shows, laser first passes through the aqueous solution of test sample 1, does not the most occur " light path ", namely
Say that " Tyndall effect " does not occurs substantially；And laser intensity passes through the test sample 2 of same concentrations again after weakening,
Liquid occurs in that significantly " light path ", i.e. create " Tyndall effect ".
Conclusion (of pressure testing):
The emamectin-benzoate water solube powder of embodiment 1 preparation is dissolved in the water, methylamino
Abamectin benzoate dispersity in water, more scattered than traditional microemulsion smaller evenly,
Disperse closer to solution.
Test example 3Multifunctional environment friendly emamectin-benzoate water solube powder indoor are killed
Worm active testing
1. experimental condition:
1.1 for examination target: rice-stem borer (Chilo suppressalis Walker).Gaochun County, Jiangsu Province Oryza sativa L.
Gathering striped rice borer pieces of an egg in rice seedling bed, indoor feeding, 4 day old larva of raising are tested.
1.2 condition of culture: indoor rice seedling is raised.Insectary temperature 28 ± 2 DEG C, relative humidity is 70%
Above, 14h illumination.Potted plant rice seedling is put into, for rice stem borer in the foster worm net cage of 30cm × 30cm × 50cm
Lay eggs.It is sowed in wide mouthed bottle after rice paddy seed two line system accelerating germination, when rice seedling grows up to 5cm～8cm, connects
Enter striped rice borer pieces of an egg or larva raising.The Chilo spp larvae taking 4 ages in days is tested.
1.3 instrument and equipments: shears, brush pen, triangular flask, beaker, graduated cylinder, culture dish, pipet, 3cm × 20cm
Test tube, soaks worm cage, clock and watch.
2 EXPERIMENTAL DESIGN
2.1 test medicine
5% Multifunctional environment friendly emamectin-benzoate water preparation (hereinafter referred to as " 5% methylamino
Abamectin benzoate water preparation "): the Multifunctional environment friendly methylamino Avermectin prepared by embodiment 1
Element benzoate water solube powder adds water formulated；
1% emamectin-benzoate cream, Nanjing HongTaiYang Co., Ltd's product.
2.2 tests process
2.2.1 dosage is arranged:
First carry out pilot study.According to pilot study result, by 5% Multifunctional environment friendly methylamino A Wei
Rhzomorph benzoate aqueous solution is configured to 0.0025mg/L, 0.005mg/L, 0.01mg/L, 0.02mg/L respectively
With five series concentration of 0.04mg/L；1% emamectin-benzoate cream is configured to 0.0025 respectively
Five series concentration of mg/L, 0.005mg/L, 0.01mg/L, 0.02mg/L and 0.04mg/L.
2.2.2 test repetition: each treatment dosage sets 4 repetitions, often repeat with 4 age in days Chilo spp larvaes 15
About Tou.
2.3 processing method
2.3.1 the time is processed: 10 seconds.
2.3.2 soak worm, soak Seedling:
The rice seedling at about the 30 days length of time rice seedlings grow is cut into the rice straw of about 18cm, and root stays a little rice root, cleans and dries in the air
Dry, take out after soaking in medicinal liquid, dry, put in the test tube of 3cm × 20cm, at the bottom of pipe, have little water.
The 4 age in days Chilo spp larvaes raised are put into leaching worm cage, takes out after leaching medicinal liquid, blot the medicine on polypide surface
Liquid, in the careful test tube moving into the rice seedling being placed with respective concentration process, black cloth seals.Shift after off-test
Raise to insectary.
3 test methods
With reference to " People's Republic of China (PRC) agricultural industry criteria NY/T1154.6-2006, farm-chemical indoor determination
Test rule insecticide the 6th part: insecticidal activity test dip method " test.
Control treatment: do blank with the process of the deionized water without medicament.
4 data surveys and statistical method
4.1 control time
Checkout facility result after chemicals treatment 72h.
4.2 data statistic analysis
Comparison mortality rate is more than 20%, and test is reformed, and comparison mortality rate is less than 20%, with Abbott formula school
Respectively process mortality rate, obtain virulence regression equation by DPS data handling system, calculate LC50Value, 95%
Confidence limit, and carry out statistical analysis.
Computational methods:
6 interpretations of result and discussion
As can be seen from Table 2,5% emamectin-benzoate water preparation and 1% Affirm (Merck Co.) benzene
The confession examination concentration of formates cream is identical.Reflect in figure 6,5% emamectin-benzoate water preparation
Toxicity regression line and the toxicity regression line of 1% emamectin-benzoate cream be interleaved each other in one
Rise.As can be seen from Table 3,5% emamectin-benzoate water preparation and 1% Affirm (Merck Co.) benzene
The formates cream LC to 4 age in days Chilo spp larvaes50Be worth close be respectively 0.0048mg/L and
0.0046mg/L；LC90Value is respectively 0.0262mg/L and 0.0268mg/L.Divide by DPS data handling system
Analysis shows 5% emamectin-benzoate water preparation and 1% emamectin-benzoate cream pair
The toxicity of striped rice borer is not significantly different from.
The table 25% emamectin benzoate water preparation determination of activity result to striped rice borer
The table 35% emamectin benzoate water preparation toxicity measure and calculation result to striped rice borer
Note: represent the significant difference reaching 5% level between process with the different English alphabets in string；
The significant difference of not up to 5% level between process is represented with the identical English alphabet in string.
6 conclusion (of pressure testing)s
Result of the test shows, the 5% emamectin-benzoate water preparation room to 4 age in days Chilo spp larvaes
Interior activity is close with 1% emamectin-benzoate cream, with DPS data handling system statistical analysis
Show that 5% emamectin-benzoate water preparation and 1% emamectin-benzoate cream are to two
The virulence changing snout moth's larva is suitable, is not significantly different from.
In a word, the invention provides a kind of Multifunctional environment friendly emamectin-benzoate water-soluble
Property powder, except emamectin-benzoate, other component is all eco-friendly, and water solublity
Good, clarified after being dissolved in water, transparent solution, be there is no any penetrating odor.Indoor insecticidal test proves,
Multifunctional environment friendly emamectin-benzoate water solube powder of the present invention is to striped rice borer
Virulence is suitable with 1% emamectin-benzoate cream.It addition, water solube powder of the present invention
Possibly together with promote plant growing, sterilization, degeneration-resistant, increase emamectin-benzoate stability, change
The composition of kind spray effect etc., when actual Field information, would indicate that more advantage.In sum, originally
Emamectin-benzoate water solube powder described in invention is that usefulness is higher, be more beneficial for ring for one
The novel agrochemical formulations that border protection, low production cost, preparation method are simple and easy to do.
Claims (17)
1. an environmentally friendly emamectin-benzoate water solube powder, it is characterised in that: include first
Amino abamectin benzoate, does not include filler；Raw material consists of:
1-7 weight portion emamectin-benzoate, 1-10 weight portion agent A, 1-6 weight portion is made
Use agent B, 1-5 weight portion functionalizers, 0.1-10 weight portion insecticides adjuvant, 0.01-0.1 weight portion defoamer；
Wherein, described agent A is selected from the compound of structural formula 1,
CH3(CH2)n(OCH2CHR')mOk(CO2)j(SO3)iM
1
Wherein, n=11,13,15, or 17,
R '=H or CH3,
M=0,1,2,3, or 4,
K=0 or 1,
J=0 or 1,
I=0 or 1, and i ≠ j,
M=H, K, Na, or NH4；
Described agent B is selected from the nonionic containing ethylene oxide unit, propylene oxide unit or glucose unit
Type surfactant and/or natural polymeric surface active agent；Described functionalizers selected from have potentiation, sterilization,
Degeneration-resistant, stimulate plant growth, suppress residual hazard, the chemosynthesis material improving the function of agricultural product quality or sky
So product；Described insecticides adjuvant is light stabilizer and drift control agents.
Environmentally friendly emamectin-benzoate water solube powder the most according to claim 1, its
Being characterised by, described raw material consists of:
1-7 weight portion emamectin-benzoate, 2-8 weight portion agent A, 1-6 weight portion is made
Use agent B, 1-5 weight portion functionalizers, 0.1-10 weight portion insecticides adjuvant, 0.01-0.1 weight portion defoamer.
Environmentally friendly emamectin-benzoate water solube powder the most according to claim 1 and 2,
It is characterized in that: described nonionic surfactant is selected from polyethylene glycol oxide, polypropylene oxide, polyethylene
One or more in alcohol and polyvinylpyrrolidone.
Environmentally friendly emamectin-benzoate water solube powder the most according to claim 3, its
It is characterised by: described nonionic surfactant preferably is selected from straight chain fatty polyoxyethylenated alcohol, straight chain fatty
Acid polyoxyethylene ester, straight-chain fatty amine polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, alkane
One or more in alkyl polyglucosides and castor oil polyoxyethylene ether.
Environmentally friendly emamectin-benzoate water solube powder the most according to claim 1 and 2,
It is characterized in that: described natural polymeric surface active agent is selected from water soluble starch derivatives, water-soluble fibre
One or more in element derivant and Chitosan-phospholipid complex.
Environmentally friendly emamectin-benzoate water solube powder the most according to claim 5, its
Be characterised by: described natural polymeric surface active agent selected from dextrin, carboxymethyl starch, carboxymethyl cellulose,
One or more in chitosan, carboxymethyl chitosan and Quaternary Ammonium Salt of Chitosan.
Environmentally friendly emamectin-benzoate water solube powder the most according to claim 1 and 2,
It is characterized in that: described functionalizers is selected from tea saponin, humic acids, Chitosan-phospholipid complex, alginic acid
One or more in salt, hyaluronic acid, Fructus Gleditsiae Abnormalis extract, matrine.
Environmentally friendly emamectin-benzoate water solube powder the most according to claim 1 and 2,
It is characterized in that: described light stabilizer is 0.1-0.4 weight portion；Selected from salicylic acid esters, benzophenone,
One or more in benzotriazole and hindered amine light stabilizer.
Environmentally friendly emamectin-benzoate water solube powder the most according to claim 8, its
It is characterised by: described light stabilizer is water miscible benzophenone light stabilizer.
Environmentally friendly emamectin-benzoate water solube powder the most according to claim 9, its
It is characterised by: described light stabilizer is selected from 2,4-dihydroxy-5-sulfonic group benzophenone, 2,2`, 4,4`-tetrahydroxy
One or more in benzophenone, 2,3,4,4`-tetrahydroxybenzophenone.
11. environmentally friendly emamectin-benzoate water soluble powders according to claim 1 and 2
Agent, it is characterised in that: described drift control agents is 1-3 weight portion, selected from the table that can reduce spray droplet
Surface tension, increases viscoelasticity, improves the deposition of medicine, reduces the water solublity synthetic high polymer of drop bounce-back
Matter and natural high molecular substance.
12. environmentally friendly emamectin-benzoate water solube powders according to claim 11,
It is characterized in that: described drift control agents is described water-soluble natural polymer substance.
13. environmentally friendly emamectin-benzoate water solube powders according to claim 12,
It is characterized in that: described drift control agents is selected from water-soluble cellulose derivative, water solublity guar gum and spreads out
Biology and one or more in water soluble starch and derivant thereof.
14. according to the environmentally friendly emamectin-benzoate water solube powder described in claim or 2,
It is characterized in that: described defoamer is C selected from organic silicon defoamer, carbon atom quantity7-C9Fatty alcohol and phosphorus
One or more in acid tributyl.
Environmentally friendly emamectin-benzoate water solublity according to any one of 15. claim 1 to 14
The preparation method of powder, it is characterised in that: prepared by following method I or II:
Method I: each raw material components mix homogeneously of emamectin-benzoate will be included；
Method II: include, first by soluble in water for described agent A, adding Affirm (Merck Co.) benzoic acid
Salt, other raw material components and water, the concentration expressed in percentage by weight obtaining emamectin-benzoate is 1%-7%
Solution, dehydration, to obtain final product.
Preparation method described in 16. claim 15, it is characterised in that: described method specifically includes following steps:
A. various raw materials are prepared according to formula；
B. described agent A is dissolved in the water of 20-60 weight portion, stirring, makes dissolving, obtain solution A；
C., in addition to defoamer, raw material is included, and other each component of emamectin-benzoate adds
Entering described solution A, addition water makes the concentration expressed in percentage by weight of emamectin-benzoate be 1%-7%,
Stirring, makes dissolving, obtains solution B；
D. defoamer is added solution B, gentle agitation, static, filter, obtain solution C；
E. solution C is dried, to obtain final product.
17. preparation methoies according to claim 16, it is characterised in that: in step e, described solution C is sprayed
Mist is dried.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410051692.2A CN103858862B (en) | 2014-02-14 | 2014-02-14 | A kind of environmentally friendly emamectin-benzoate water solube powder and preparation method thereof |
| BR112016018564-1A BR112016018564B1 (en) | 2014-02-14 | 2015-02-09 | ECOLOGICALLY FAVORABLE EMAMECTIN BENZOATE FORMULATIONS AND METHODS FOR PREPARATION |
| US15/118,825 US10206402B2 (en) | 2014-02-14 | 2015-02-09 | Environmentally-friendly emamectin benzoate preparation and preparation method therefor |
| AU2015218092A AU2015218092B2 (en) | 2014-02-14 | 2015-02-09 | Environmentally-friendly emamectin benzoate preparation and preparation method therefor |
| PCT/CN2015/072545 WO2015120786A1 (en) | 2014-02-14 | 2015-02-09 | Environmentally-friendly emamectin benzoate preparation and preparation method therefor |
| EP15749075.6A EP3106031B1 (en) | 2014-02-14 | 2015-02-09 | Environmentally-friendly emamectin benzoate preparation and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410051692.2A CN103858862B (en) | 2014-02-14 | 2014-02-14 | A kind of environmentally friendly emamectin-benzoate water solube powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103858862A CN103858862A (en) | 2014-06-18 |
| CN103858862B true CN103858862B (en) | 2016-09-21 |
Family
ID=50898327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410051692.2A Active CN103858862B (en) | 2014-02-14 | 2014-02-14 | A kind of environmentally friendly emamectin-benzoate water solube powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103858862B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112016018564B1 (en) * | 2014-02-14 | 2021-08-31 | Nanjing Scienx Biological Technology Co. Ltd | ECOLOGICALLY FAVORABLE EMAMECTIN BENZOATE FORMULATIONS AND METHODS FOR PREPARATION |
| CN104886086A (en) * | 2015-06-12 | 2015-09-09 | 福建省德盛生物工程有限责任公司 | Low-volume spray containing emamectin benzoate |
| CN105028456A (en) * | 2015-06-12 | 2015-11-11 | 福建省德盛生物工程有限责任公司 | Low-volume spray containing emamectin benzoate and dinotefuran |
| CN104920422A (en) * | 2015-06-12 | 2015-09-23 | 福建省德盛生物工程有限责任公司 | Low-volume spray with emamectin benzoate and indoxacarb |
| CN114342946B (en) * | 2021-12-27 | 2023-01-17 | 陕西新指南针化工科技服务有限责任公司 | Emamectin benzoate aqueous solution and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102113505A (en) * | 2010-01-05 | 2011-07-06 | 海南正业中农高科股份有限公司 | Composition containing acetamiprid for controlling brontispa longissima |
| CN102669187A (en) * | 2012-05-25 | 2012-09-19 | 国际竹藤中心 | Botanical herbicide soluble powder and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102475084A (en) * | 2010-11-25 | 2012-05-30 | 上海农乐生物制品股份有限公司 | Methylamino abamectin benzoate water dispersible granules and method for preparing same |
-
2014
- 2014-02-14 CN CN201410051692.2A patent/CN103858862B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102113505A (en) * | 2010-01-05 | 2011-07-06 | 海南正业中农高科股份有限公司 | Composition containing acetamiprid for controlling brontispa longissima |
| CN102669187A (en) * | 2012-05-25 | 2012-09-19 | 国际竹藤中心 | Botanical herbicide soluble powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 5%甲氨基阿维菌素苯甲酸盐可溶粒剂;无;《中国农药信息网（http://www.agrichem.cn/news/2011/12/26/201112261322938332.shtml）》;20111226 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103858862A (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10206402B2 (en) | Environmentally-friendly emamectin benzoate preparation and preparation method therefor | |
| CN103858862B (en) | A kind of environmentally friendly emamectin-benzoate water solube powder and preparation method thereof | |
| CN103858936B (en) | A kind of Multifunctional environment friendly emamectin-benzoate water preparation and preparation method thereof | |
| CN101589722A (en) | Insecticides of a kind of chloride worm benzamide and its production and use | |
| CN104430477A (en) | Pesticide composition containing fluensulfone and neonicotinoid insecticide | |
| CN104488949A (en) | Dinotefuran-containing insecticidal combination | |
| CN103858921B (en) | A kind of environmentally friendly Diacloden aqua and preparation method thereof | |
| CN102960361A (en) | Insecticide composition and application thereof | |
| CN103907643B (en) | A kind of Multifunctional environment friendly Acetamiprid water preparation and preparation method thereof | |
| CN102972430A (en) | Insecticidal composition containing thiamethoxam and acetamiprid | |
| CN103210953B (en) | Insecticide composition, insecticide and application of insecticide | |
| CN105532656B (en) | A kind of environmental-friendly dinotefuran micron-emulsion and preparation method thereof | |
| CN105638650B (en) | A kind of environmental-friendly dinotefuran micron-emulsion of organic solvent-free and preparation method thereof | |
| CN103858922B (en) | A kind of Multifunctional environment friendly Diacloden aqua and preparation method thereof | |
| CN107950541A (en) | A kind of garlic seed coat agent composition and preparation method thereof | |
| CN103858863B (en) | A kind of environmentally friendly Diacloden water solube powder and preparation method thereof | |
| CN109769842A (en) | A kind of insecticide composition containing trifluoro-benzene pyrimidine, rotenoid | |
| CN108208015A (en) | A kind of agricultural chemicals suspension agent and its preparation method and application | |
| CN105532657B (en) | It is a kind of for Herbicidal combinations of monocot crops and application thereof | |
| CN101366387B (en) | Agricultural chemical composition | |
| CN105941423B (en) | A kind of Pesticidal combination containing capillary and cyromazine | |
| CN105104393A (en) | Pesticide composition and application thereof | |
| CN104522041A (en) | Flonicamid and efficient cyhalothrin containing insecticide composition | |
| CN104872147B (en) | Weeding composition containing pentoxazone and mefenacet | |
| CN103858864A (en) | Environmental-friendly acetamiprid water-soluble powder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: Building No. 3 Gaochun Avenue branch Gu Tan Economic Development Zone of Nanjing city of Jiangsu Province in 211300 Applicant after: NANJING SCIENX BIOTECHNOLOGY CO., LTD. Address before: Building No. 3 Gaochun Avenue branch Gu Tan Economic Development Zone of Nanjing city of Jiangsu Province in 211300 Applicant before: NANJING SHANWEI BIOLOGICAL SCIENCE & TECHNOLOGY CO., LTD. |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210112 Address after: Room 2202 and 2205, building A1, 32 Fengzhan Road, Yuhuatai District, Nanjing City, Jiangsu Province, 210012 Patentee after: Nanjing Shansi Ecological Technology Co.,Ltd. Address before: 211300 science and technology innovation building, 3 Gutan Avenue, Gaochun Economic Development Zone, Nanjing, Jiangsu Province Patentee before: NANJING SCIENX BIOTECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right |