CN103907643A - Multifunctional environment-friendly acetamiprid aqua and preparation method thereof - Google Patents
Multifunctional environment-friendly acetamiprid aqua and preparation method thereof Download PDFInfo
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Abstract
The invention provides a multifunctional environment-friendly acetamiprid aqua, comprising, by weight, 1 to 5% of acetamiprid, 1 to 10% of an agent A and 1 to 5% of a functional agent. The agent A is one or more selected from the group consisting of an anionic surfactant containing a sulfonic acid group, an anionic surfactant containing a sulfuric acid group and an anionic surfactant containing a carboxylic group. Preferably, the aqua may further comprise an agent B accounting for 1 to 5% of the total weight of the aqua. The invention also provides a preparation method for the multifunctional environment-friendly acetamiprid aqua. The multifunctional environment-friendly acetamiprid aqua does not contain any organic solvent and/or corrosive solvent, is a uniform and clear solution and has indoor insecticidal activity similar to that of acetamiprid missible oil. Thus, the aqua provided by the invention is obviously better than missible oil and other water-based dosage forms.
Description
Technical field
The invention belongs to pesticides new formulation field, particularly environmentally friendly Acetamiprid aqua of a kind of Multifunction and preparation method thereof.
Background technology
Along with the raising of environmental consciousness, pesticidal preparations is proposed to efficient, eco-friendly requirement.Research discovery, for pesticide original medicine of the same race, the height of pesticidal preparations performance drug effect, depends on its formulation type and dispersity and the size of agricultural chemicals particulate.Scientific common sense is told us, and in the time that other condition is identical, the microparticulate size of pesticide original medicine is less, and its surface area is larger, wider with the contact area of plant leaf blade and insect, and drug effect performance is just more abundant, and the usage amount of agricultural chemicals will correspondingly reduce.
Whether environmental friendliness of a kind of formulations of pesticide, with an organic solvent whether its evaluation criterion had both related to the character of pesticide original medicine itself, also relate in formulation, and whether solvent and the auxiliary agent of use belong to green matter.Although various water baseization pesticidal preparations belong to environmental friendliness formulation generally, the evaluation of environmentally friendly degree should be with reference to above-mentioned standard.In August, 2010, four ministries and commissions of country combine and have put into effect " agricultural chemicals industrial policy ", wherein explicitly point out: " country is by measures such as scientific and technological support, technological transformation, economic policy guiding; support efficient, safety, economy, eco-friendly agricultural chemicals new product development; accelerate substituting and eliminating of high pollution, excessive risk product, promotion breed structure is continued to optimize."; " promote energetically agricultural formulation to efficient, safe future developments such as water baseization, dustlessization, control releases ... strictly control the use of poisonous and harmful solvent and auxiliary agent." in the recent period, Ministry of Industry and Information has put into effect again " pesticide industry " 12 " development plan ", wherein emphasizes: " the strict use of controlling containing the poisonous and harmful solvents such as toluene, dimethylbenzene and auxiliary agent, develops and promotes the formulations such as water baseization ".According to statistics, the xylene solvent that China is used for the manufacture of missible oil formulation is every year just up to 30～400,000 tons.These solvents, after spraying, just evaporate in air, are penetrated in food, soil and groundwater, cause the pollution to ecotope, the infringement to food security and people's health.Therefore, do not use or reduce with an organic solvent as far as possible, choice and operation Green Additives, should become a kind of developing direction and the trend developing and promote the environmental friendliness formulations of pesticide.
In the water baseization formulations of pesticide, only have the pesticide original medicine in aqueous pharmaceutical (aqua) to belong to unimolecule dispersion, size minimum.But the pesticide species that can be prepared into aqua is little, and the pesticide species having easily hydrolysis in water, this has just limited its application.Because most of agricultural chemicals are oil-soluble, what have can only be dissolved in organic solvent, and what have is even difficult to be dissolved in conventional organic solvent, is prepared into water base agent type, conventionally can only be prepared into microemulsion, aqueous emulsion, suspending agent and suspension emulsion.In these four kinds of formulations, the particle size that agricultural chemicals disperses in water increases successively.Microemulsion, aqueous emulsion are to be dispersed in water in the solution droplets mode of organic solvent dissolution pesticide original medicine, the wherein drop size minimum of microemulsion, below 100 nanometers, is less than 1/4th of visible wavelength, thereby system is transparent, belongs to thermodynamic stable system; And the solution droplets size of aqueous emulsion hundreds of nanometer to micron more than, approach or be greater than visible wavelength, system is opaque, and poor stability.Suspending agent is normally suspended in by the effect of macromolcular dispersant the agricultural chemicals particulate that is ground into micron-scale in water, and this system has the tendency that the cohesion of agricultural chemicals crystal grain occurs.Suspension emulsion is the combining form of suspending agent and aqueous emulsion.In these four kinds of formulations, except suspending agent, all contain the organic solvent of 10%-20%, this is reducing their environmental friendliness performance in varying degrees.
Acetamiprid (acetamiprid) is phase late 1980s by the anabasine insecticide of Japanese Cao Da company exploitation.At present, state-owned many companies produce former medicine.Acetamiprid has molecular structure as shown in 2.
Acetamiprid is the replacement kind of Imidacloprid, and Main Function is in the neural joint portion of insect caudacoria, makes insect exaltation, whole body spasm, paralysis and extremely by be combined with acetylcholinergic receptor.That Acetamiprid has in the aqueous solution is stable, interior absorption is strong, consumption is few, quick-acting good, active high, the lasting period long, insecticidal spectrum wide, with conventional pesticide without features such as cross resistances, insect is had and is tagged and stomach poison function, and there is good systemic activity.Acetamiprid is mainly used in preventing and treating Semiptera insect, as aphid, leafhopper, aleyrodid and a red-spotted lizard etc., and thrips, lepidoptera pest, as diamond-back moth, dive fly, Grapholita spp etc., coleopteran pest is as longicorn etc., and thrips order insect is as thrips etc.Beetle order insect is also had to obvious preventive effect, and there is good ovicidal, larvicidal activity.Being 10～15 times of buprofezin to the rice fulgorid medicine virulence of tagging one day after, is 259 times of acephatemet.Suitable crop is oranges and tangerines, cotton, wheat, vegetables paddy rice, fruit tree, tealeaves, tobacco, soybean, melon, peanut, flowers etc.Because Acetamiprid is all different from the insecticidal mechanism of pyrethrins, organic phosphor, carbamate, without cross resistance, thereby can effectively prevent and treat the insect that above-mentioned insecticide is had to resistance with other insecticide, be especially applicable to the control of sucking pest.
Acetamiprid is soluble in acetone, cyclohexanone, methyl alcohol, ethanol, acetonitrile, dimethyl formamide, methyl-sulfoxide, dimethylbenzene equal solvent, only has certain solvability in water, is about 4.2g/L(25 ℃).Its water base agent type mainly contains microemulsion, aqueous emulsion, wetting powder, soluble powder, water dispersible granules etc. at present, does not see so far aqua formulation.
Take Acetamiprid as the situation of the Chinese invention patent of the water base chemical preparation of pesticide original medicine application (microemulsion and aqueous emulsion) as follows:
Publication number is the Chinese invention patent application " a kind of acetamiprid insecticidal aqueous emulsion " of CN1454477A, a kind of aqueous emulsion that contains Acetamiprid is disclosed, by Acetamiprid, surfactant and water composition aqueous emulsion, its composition content (take aqueous emulsion weight as 100%): Acetamiprid 0.2～50%, surfactant 2～50%, water 20%～95%.This aqueous emulsion has used the surfactant up to 50% at most.
Publication number is the Chinese invention patent application " acetamiprid micro emulsion type insecticide " of CN1669435A, a kind of preparation method of acetamiprid micro emulsion agent is disclosed, be made up of former medicine, solvent, emulsifier, water, each weight percentages of components is: Acetamiprid 3～30%, polyphosphoric acids 5～10%, sulfuric acid 6～8%, acetic acid 15～21%, emulsifier 10～15%, water supply 100%.This microemulsion has used the acid up to 26～39%, and wherein the consumption of sulfuric acid is 6～8%.Its preparation has very strong acidity, even if use after dilute with water, growth, the soil pH value of this acid medium to plant can produce destruction.
In the commercialization Acetamiprid agriculture emulsion-type using at home, some has used environmental hormone---the polyoxyethylene nonylphenol ether of state's forbiddings such as European Union.
In addition, market also claims to the further performance of improving Acetamiprid preparation.Therefore, a kind of not containing any organic solvent or aggressive solvent, that various aspects of performance is more superior, the eco-friendly Acetamiprid aqua of Multifunction in the urgent need to developing.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the deficiencies in the prior art, and the new friendly type Acetamiprid of Multifunctional environment aqua is provided.Described aqua has the advantages that be obviously better than acetamiprid EC formulation and other formulation: 1. not containing any organic solvent or aggressive solvent; 2. auxiliary agent is all green matter, not containing environmental hormone; 3. the outward appearance of aqua is colourless uniform solution, and long-term placement stablized, and physical properties meets state specified standards index.And aqua of the present invention has the drug effect of raising, suppresses residual hazard, improves the functions such as agricultural product quality.
A further object of the invention, is to provide the preparation method of the friendly type Acetamiprid of described Multifunctional environment aqua.
In order to realize foregoing invention object, the present invention has adopted following technical scheme:
The friendly type Acetamiprid of a kind of Multifunctional environment aqua, comprises Acetamiprid, functionalizers and water, does not comprise organic solvent and aggressive solvent.
Preferably, the friendly type Acetamiprid of described Multifunctional environment aqua, according to weight percent meter, comprising:
1%-5% Acetamiprid, 1%-10% agent A, 1%-5% functionalizers;
Preferred, the friendly type Acetamiprid of described Multifunctional environment aqua, according to weight percent meter, comprising:
1%-5% Acetamiprid, 2%-8% agent A, 1%-5% functionalizers;
Wherein, described agent A is selected from containing one or more in anionic surfactant, the anionic surfactant of sulfur acid group and the anion surfactant of carboxyl group of sulfonic acid group;
Described functionalizers be selected from there is synergy, sterilization, degeneration-resistant, stimulate plant growth, improve drug effect, suppress residual hazard, improve chemosynthesis material or the natural products of the function of agricultural product quality.
Preferably, described agent A is selected from one or more in straight or branched aliphatic group sulfonic acid and salt, straight or branched aliphatic group ether sulfonic acid and salt thereof, straight or branched aliphatic group sulfuric acid and salt thereof, straight or branched aliphatic group ether sulfuric acid and salt and straight or branched aliphatic group carboxylic acid and salt thereof.
Preferred, described agent A is selected from the compound of structural formula 1
CH
3(CH
2)
n(OCH
2CHR′)
mO
k(CO
2)
j(SO
3)
iM
1
Wherein, n=7-17, preferably n=11,13,15, or 17,
R '=H or CH
3,
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 NH
4.
Therefore, as the preferred embodiment of the present invention, described in water dissociable go out the agent of acid group group be selected from one or more in following compound:
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 sulfuric acid and potassium, sodium or ammonium salt;
IV. dodecyl, myristyl, cetyl and octadecyl sulfuric acid ether and potassium, sodium or ammonium salt;
V. dodecyl, myristyl, cetyl and octadecyl carboxylic acid and potassium, sodium or ammonium salt.
Preferably, the friendly type Acetamiprid of described Multifunctional environment aqua, also comprises the agent B that accounts for total formulation weight amount 1%-5%; Described booster action agent is selected from nonionic surface active agent and/or the high molecular surfactant containing ethylene oxide unit, propylene oxide unit or glucose unit.
Preferably, described nonionic surface active agent is selected from one or more in polyethylene glycol oxide, polypropylene oxide, polyvinyl alcohol and polyvinylpyrrolidone; More excellent, described nonionic surface active agent is selected from straight-chain fatty alcohol APEO, one or more in straight chain fatty acid polyoxyethylene ester, straight-chain fatty amine APEO, sorbitan fatty acid ester APEO, APG and castor oil polyoxyethylene ether;
Preferably, described natural polymeric surface active agent is selected from one or more in water soluble starch derivative, water-soluble cellulose derivative and shitosan and derivative thereof; More excellent, described natural polymeric surface active agent is selected from one or more in dextrin, carboxymethyl starch, carboxymethyl cellulose, shitosan, CMC and Quaternary Ammonium Salt of Chitosan.
Preferably, described functionalizers is selected from one or more in Tea Saponin, humic acid, shitosan and derivative thereof, alginate, hyaluronic acid, Fructus Gleditsiae Abnormalis extract, matrine etc.
Preferably, the friendly type Acetamiprid of above-mentioned Multifunctional environment aqua, also comprises other insecticides adjuvant that accounts for weight of formulation 0.1-10%.
Preferably, described other insecticides adjuvant comprises the drift control agents that accounts for weight of formulation 0.1-4%; Described drift control agents is selected from the surface tension that can reduce spray droplet, increases viscosity, improves the deposition of medicine, reduces water-soluble synthetic high polymer matter and the natural high molecular substance of drop bounce-back; Preferred described water-soluble natural polymer substance; More preferably the one in water-soluble cellulose derivative, water-soluble guar gum and derivative thereof and water soluble starch and derivative thereof is several.
The friendly type Acetamiprid of above-mentioned Multifunctional environment aqua, also comprises the antifreezing agent that accounts for weight of formulation 1%-6% and the defoamer that accounts for weight of formulation 0.01%-0.1%;
Preferably, antifreezing agent of the present invention is selected from one or more in ethylene glycol, propane diols, glycerine, low-molecular-weight polyethylene glycol and sorbierite; Consider one or more in glycerine, ethylene glycol and the propane diols of more preferably easily degrading from environmental friendliness.
Preferably, defoamer of the present invention is selected from silicone defoaming agent, carbon atom quantity is C
7～C
9fatty alcohol and tributyl phosphate in one or more.
As a preferred embodiment of the present invention, the friendly type Acetamiprid of a kind of Multifunctional environment aqua, according to weight percent meter, comprising:
1%-5% Acetamiprid, 1%-10% agent A, 1%-5% agent B, 1%-5% functionalizers, 0.1-4% drift control agents, 1%-6% antifreezing agent, 0.01%-0.1% defoamer, and the water of surplus.
The wherein definition of agent A, agent B, functionalizers, other insecticides adjuvant, antifreezing agent and defoamer and preferably limiting as aforementioned.
The present invention also provides the preparation method of the friendly type Acetamiprid of described Multifunctional environment aqua, comprises that first agent A is dissolved in part water, then adds Acetamiprid, functionalizers and remaining water.
Preferably, described preparation method comprises the steps:
I. prepare various raw materials according to formulation weight proportioning;
II. except Acetamiprid, defoamer, other insecticides adjuvant and water, composition of raw materials is comprised to other raw material of described agent A adds stirred tank, inject part water, stir, make to dissolve, obtain solution A;
III. Acetamiprid is added to described solution A, stir, make to dissolve, obtain solution B;
IV. described other insecticides adjuvant and remaining water are added in described solution B, stir, make to dissolve; Add again defoamer, gentle agitation, static, filter, to obtain final product.
The solvability of Acetamiprid in water is little, is only 4.2g/L(25 ℃).Analyze the chemical constitution of Acetamiprid, have 1 pyridine ring, 2 tertiary amine nitrogen atoms and 1 cyano group in molecule, 4 nitrogen-atoms, to the stack of electronics, have stronger alkalescence.In prior art, generally prepare Acetamiprid aqueous emulsion or microemulsion with poisonous, harmful organic solvent, a large amount of nonionic surface active agent and corrosivity strong acid; But bring the harm to environment.
Agent A of the present invention is the material that a class can improve Acetamiprid solvability and separating degree in water.Inventor finds by research, and some specific compound can function as described above, thereby without by organic solvent, corrosivity strong acid, just can prepare the aqua of Acetamiprid.Inventor has carried out preferably agent A by following experiment.
In 10ml water, add quantitative different types of compound and quantitative Acetamiprid, under room temperature, stir, observe dissolving situation, optimize the material type of agent A.The results are shown in Table 1.
Table 1 agent A screening formula and result
By above-mentioned experiment, described agent A is preferably containing the anionic surfactant of 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 sulfuric acid and salt thereof, straight or branched aliphatic group ether sulfuric acid and salt, straight or branched aliphatic group carboxylic acid and salt thereof.
Most preferred, described agent A is selected from the compound of structural formula 1
CH
3(CH
2)
n(OCH
2CHR′)
mO
k(CO
2)
j(SO
3)
iM
1
Wherein, n=7-17, preferably n=11,13,15, or 17,
R '=H or CH
3,
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 NH
4.
The friendly type Acetamiprid of Multifunctional environment of the present invention aqua can also comprise agent B.So-called agent B, referring to can be to improving the dispersing and dissolving of Acetamiprid in water, improves preparation stability, opposing hard water, reduces the surface tension of preparation dilution and increases the material adding in the plant leaf surface effect of sprawling.It accounts for the 1%-5% of gross weight in preparation.
Kill the effect of insect pest in order to strengthen Acetamiprid aqua, play the effect of plant protection simultaneously, Acetamiprid aqua of the present invention comprises functionalizers.Described functionalizers be selected from there is synergy, sterilization, degeneration-resistant, stimulate plant growth, improve drug effect, suppress residual hazard, improve the material of the functions such as agricultural product quality, comprise chemosynthesis material or natural products.Consider from the environmental friendliness of formulation, preferably natural products, as Tea Saponin, humic acid, shitosan and derivative thereof, alginate, hyaluronic acid, Fructus Gleditsiae Abnormalis extract, matrine etc., can select to add one or more as required.Described functionalizers accounts for the 1%-5% of total formulation weight amount.
Acetamiprid aqua of the present invention is generally used with Sprayable; In order to extend the action time of Acetamiprid aqua of the present invention on crop blade face, improve pulverability, preparation of the present invention also comprises other insecticides adjuvant, for example drift control agents accounts for the 0.1%-10% of total formulation weight amount.
Described drift control agents refers to the surface tension that can reduce spray droplet, increases viscoplasticity, improves the deposition of medicine, reduces the auxiliary agent of drop bounce-back, is selected from synthetic high polymer matter and natural high molecular substance.Consider from the environmental friendliness of formulation, preferentially select water-soluble natural polymer substance, as one or more in water-soluble cellulose derivative, water-soluble guar gum and derivative thereof and water soluble starch and derivative thereof.
In order to meet the preparation requirement of aqueous pesticide solution, in the composition of raw materials of aqua of the present invention, also to comprise antifreezing agent, defoamer.
Antifreezing agent of the present invention refers to that a class improves the material in low-temperature stability and regulation system transparency temperature region, comprises ethylene glycol, propane diols, glycerine, low-molecular-weight polyethylene glycol, sorbierite etc.Consider from environmental friendliness, the preferential easily material of degraded of selecting, as glycerine, ethylene glycol or propane diols.It accounts for the 1%-6% of gross weight in preparation.
Defoamer of the present invention refers to can eliminate foam in the last process of aqua manufacture, be beneficial to the filling material of preparation, is selected from the conventional silicone defoaming agent in this area, carbon atom quantity is C
7～C
9fatty alcohol, tributyl phosphate etc., it accounts for the 0.01-0.1% of gross weight in preparation.
The friendly type Acetamiprid of Multifunctional environment of the present invention aqua, can use the general production equipment of the water baseization formulations of pesticide, under normal temperature condition, carries out, and produces workable.
The friendly type Acetamiprid of Multifunctional environment of the present invention aqua, can be applied to the insects such as crop control Semiptera, thrips, Lepidoptera, coleoptera, thrips order such as vegetables, fruit, tealeaves, paddy rice, corn, cotton.
The friendly type Acetamiprid of Multifunctional environment of the present invention aqua, does not belong to existing microemulsion.Because in the process of the described aqua of preparation invention, do not use any organic solvent.And acetamiprid micro emulsion agent of the prior art, aqueous emulsion are all to have dissolved the system that the organic solvent drop of Acetamiprid is dispersed in water.If the xylene solution of Acetamiprid is distributed in the aqua system of the present invention that does not comprise Acetamiprid, will produce water-oil separating, can not form the system of stable homogeneous.This shows the friendly type Acetamiprid of Multifunctional environment of the present invention aqua, is not traditional microemulsion.
Tyndall phenomenon is the ins and outs of colloid.So-called " Tyndall phenomenon ", refers in the time that Ray Of Light sees through colloid, can observe from the vertical direction of incident light bright " path " occurring colloid, is also Tyndall effect (Tyndall effect).Tyndall effect is exactly scattering of light phenomenon or claims opalescence phenomenon.Colloid can have Tyndall phenomenon, and the purified solution that molecule disperses does not have substantially, can adopt Tyndall phenomenon to distinguish colloid and solution.Microemulsion be by be less than 100nm dissolving the organic solvent drop of agricultural chemicals form in water in disperseing, therefore can be observed obvious Tyndall phenomenon.In the time that a kind of Tyndall phenomenon of liquid system is significantly less than the microemulsion of same concentrations, can think to have formed a kind of aqueous solution or aqueous dispersion.By following experiment, investigate the Tyndall phenomenon of the friendly type Acetamiprid aqua of Multifunctional environment of the present invention and acetamiprid micro emulsion agent of the prior art.
Irradiate the conical flask of 1% the Acetamiprid aqua that is equipped with prepared by the embodiment of the present invention 1 with laser pen respectively and the conical flask of 1% acetamiprid micro emulsion agent (commercially available) is housed, can observe by the light path of solution strong and weak different.Even, by arranged side by side above-mentioned two conical flasks, irradiate laser first by aqua, and then by microemulsion, its result as shown in Figure 2.Fig. 2 shows that the Tyndall phenomenon of multi-functional Acetamiprid aqua of the present invention is obviously weaker than the microemulsion of same concentration.This shows the dispersity of Acetamiprid of the present invention in water, and that disperses than traditional microemulsion is less more even, closer to Solution Dispersion.
The prepared friendly type Acetamiprid of the Multifunctional environment aqua of the present invention is at room temperature placed 2 years, and formulation outward appearance does not change, and is still transparence liquid.
The present invention will be insoluble in the Acetamiprid and preferred agent A composition composition of water, improve its performance with preferred agent B agent simultaneously, the solvability in water of Acetamiprid is improved to 1 more than the order of magnitude, thereby obtained stable Acetamiprid high concentration solution.The existence of functionalizers makes Acetamiprid aqua of the present invention become the environmentally friendly aqua of a kind of Multifunction in addition.After testing, the property indices of the friendly type Acetamiprid of the Multifunctional environment of preparation aqua has reached state specified standards thus:
1. aqua outward appearance is homogeneous transparent shape, and stable storing can any ratio disperse rapidly, dilute in water.
2. in aqua, the active constituent content of Acetamiprid can reach 1%-5%, maintains an equal level with the high-load of current domestic other liquid dosage form.
3. the aqua stability in hard water that preferably contains agent B can be qualified, and muddiness, precipitation do not occur in the hard water of normal concentration, and the northern area large in the water hardness also can use.
4. aqua high-and low-temperature resistance performance is qualified.
Multi-functional Acetamiprid aqua of the present invention has good environmental friendliness performance.The most outstanding feature is, in preparation, do not contain any organic solvent and/aggressive solvent, the auxiliary agent of use is all biodegradable material, and environment is not formed to harm, Acetamiprid can not exist in environment in addition.Therefore, Acetamiprid aqua of the present invention has improved the environmental friendliness performance of pesticidal preparations to greatest extent.
The present invention, by selecting, use water-soluble natural macromolecule as functionalizers, gives the friendly Acetamiprid aqua of novel environmental new function, makes it have the effects such as sterilization, degeneration-resistant, synergy, stimulating growth.Realize this purpose, mainly comprise the functionalizers roles such as Tea Saponin, humic acid and shitosan.Tea Saponin is a kind of natural nonionic surface active agent, has good emulsification, dispersion, foaming, the function such as moistening, can be used as wetting agent, synergist and the spreader-sticker of pesticidal preparations, and has certain desinsection, bactericidal action.Humic acid is the natural polymer organic acid being produced through microbial action by plant and animal residues, wherein fulvic acid molecular weight is little, water-soluble, active high, there is enhancing crop resistance, can be to pesticide slow-release synergy, reduce toxicity, extend drug effect, reduce the effects such as agriculture is residual.Shitosan is the unique alkaline polysaccharide that has in a large number cation of occurring in nature, has disease resistance, safety, trace, efficient feature, can be degeneration-resistant, resist germ and attack, increase production, improve quality of agricultural product.The natural materials that has similar effect with other substitutes functionalizers of the present invention, also in aim of the present invention and spiritual scope.The present invention also adds the auxiliary agent such as drift control agents and spreading agent in Acetamiprid aqua, can extend drug effect, improves pulverability.Finally, the invention provides a kind of environmental friendliness Acetamiprid aqua that integrates several functions.
In addition, Acetamiprid aqua provided by the invention, economic and social benefit is remarkable, has application value.Described multi-functional Acetamiprid aqua, only make water as solvent, compared with the liquid dosage forms such as acetamiprid EC of the prior art, microemulsion, aqueous emulsion, can replace respectively the poisonous and hazardous organic solvent such as dimethylbenzene, toluene or the corrosive acid of the about 20%-90% of mass percent, and environment for use steroids surfactant not.Not only reduce production cost, and can avoid above-mentioned poisonous and harmful substance to environmental emission, significant for protection of the environment and human health, the saving resource energy and low-carbon emission reduction.Therefore,, along with applying of Acetamiprid aqua of the present invention, will produce significant economic benefit and social benefit.
Accompanying drawing explanation
What Fig. 1 showed is the photo of the friendly type Acetamiprid of the Multifunctional environment prepared of embodiment 5 aqua.
What Fig. 2 showed is the photo of the Tyndall phenomenon of test example 1, and wherein the nearly laser pen in left side is the friendly type Acetamiprid of 1% Multifunctional environment aqua prepared by embodiment 1, and right side is commercially available 1% acetamiprid micro emulsion agent away from laser pen.
What Fig. 3 showed is in test example 2, the toxicity regression line of the friendly type Acetamiprid aqua of 3% Multifunctional environment and 5% acetamiprid EC.
Embodiment
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 obtain by commercial channel.
embodiment 1the friendly type Acetamiprid of a kind of 1% Multifunctional environment aqua
Raw material proportioning:
Preparation by the following method:
I. prepare the various raw materials of preparation 1kg target product according to formulation weight proportioning;
II. castor oil polyoxyethylene ether (EL-40), fatty alcohol-polyoxyethylene ether (AEO-09), dodecyl sodium sulfate, Tea Saponin, fulvic acid, CMC and glycerine are joined in stirred tank, inject 2/3 deionized water, under room temperature, stir, make to dissolve, obtain solution A;
III. Acetamiprid is added to described solution A, stir, make to dissolve, obtain solution B;
IV. hydroxyethylcellulose is dissolved in remaining deionized water, this solution is added in solution B, at room temperature stir, make to dissolve; Add again tributyl phosphate, gentle agitation, static, filter, obtain outward appearance clarification, transparent target product.
embodiment 2the friendly type Acetamiprid of a kind of 2% Multifunctional environment aqua
Raw material proportioning:
Adopt preparation method and the step identical with embodiment 1, obtain 1kg outward appearance clarification, transparent password protection product.
embodiment 3the friendly type Acetamiprid of a kind of 3% Multifunctional environment aqua
Raw material proportioning:
Adopt preparation method and the step identical with embodiment 1, obtain 1kg outward appearance clarification, transparent target product.
embodiment 4the friendly type Acetamiprid of a kind of 4% Multifunctional environment aqua
Raw material proportioning:
Adopt preparation method and the step identical with embodiment 1, obtain 1kg outward appearance clarification, transparent target product.
embodiment 5the friendly type Acetamiprid of a kind of 5% Multifunctional environment aqua
Raw material proportioning:
Adopt preparation method and the step identical with embodiment 1, obtain 1kg outward appearance clarification, transparent target product, sample photo as shown in Figure 1.
embodiment 6the friendly type Acetamiprid of a kind of 3% Multifunctional environment aqua
Raw material proportioning:
I. prepare the various raw materials of preparation 1kg target product according to formulation weight proportioning;
II. dodecyl sodium sulfate, sodium ricinoleate, Tea Saponin, fulvic acid, shitosan and glycerine are joined in stirred tank, inject 2/3 deionized water, under room temperature, stir, make to dissolve, obtain solution A;
III. Acetamiprid is added to described solution A, stir, make to dissolve, obtain solution B;
IV. guar gum is dissolved in remaining deionized water, this solution is added in solution B, at room temperature stir, make to dissolve; Add again silicone defoaming agent, gentle agitation, static, filter, obtain outward appearance clarification, transparent target product.
test example 1tyndall effect experiment
The conical flask of the friendly type Acetamiprid of 1% Multifunctional environment aqua prepared by the embodiment of the present invention 1 is housed and the conical flask of commercially available 1% acetamiprid micro emulsion agent is housed arranged side by side, the laser sequencing of laser pen transmitting is by above-mentioned two kinds of liquid.
Result as shown in Figure 2., not there is " light path " in the aqua that laser is first prepared by embodiment 1, that is to say that " Tyndall effect " is very weak substantially; And laser intensity passes through the commercially available microemulsion of same concentrations again after weakening, in liquid, there is significantly " light path ", produce " Tyndall effect ".Acetamiprid aqua prepared by embodiment 1 is described, the dispersity of Acetamiprid in water, that disperses than traditional microemulsion is less more even, closer to Solution Dispersion.
test example 2the friendly type Acetamiprid of the present invention's 3% Multifunctional environment aqua is measured the toxicity of vegetable aphid
1 experimental condition
1.1 for examination target
Black peach aphid Myxus persicae (Sulzer).Test is collected in the wild cabbage vegetable fields of Nanjing Suburb Jiangsu Province Agriculture Science Institute with vegetable aphid, select if indoor 2 age aphid test.
1.2 condition of culture
28 ± 2 ℃ of insectary temperature, relative moisture more than 70%, 14h illumination.
1.3 instrument and equipment
Scissors, writing brush, triangular flask, beaker, graduated cylinder, plastic cup, pipette, clock and watch.
2 experimental scheme
2.1 test medicine
The friendly type Acetamiprid of 3% Multifunctional environment aqua, prepared by embodiment 3;
5% acetamiprid EC, Jiangsu Changlong Chemical Co's product.
2.2 tests are processed
2.2.1 dosage setting
First carry out preliminary experiment.According to preliminary experiment result, the friendly type Acetamiprid of 3% Multifunctional environment aqua is mixed with respectively to 1.25mg/L, 2.5mg/L, 5mg/L, 10mg/L and five series concentration of 20mg/L; 5% acetamiprid EC is mixed with respectively 1.25mg/L, 2.5mg/L, 5mg/L, 10mg/L and five series concentration of 20mg/L.
2.2.2 test repeats
Each treatment dosage is established 4 repetitions, repeat if every to choose neat and consistent 2 age aphid 30-50 head.
2.3 processing method
2.3.1 10 seconds of processing time.
2.3.2 infusion process (soak leaf and soak worm)
Field gathers cabbage leaves with vegetable aphid worm in indoor, if every blade choose neat and consistent 2 age aphid 30-50 head, take out soaked for 10 seconds in the liquid preparing after, blot unnecessary liquid with blotting paper, then put into the plastic cup that diameter is 9cm, seal with black cloth.After off-test, be transferred in insectary and raise.
3 test methods
Test with reference to " the agricultural industry criteria NY/T 1154.6-2006 of the People's Republic of China (PRC), farm-chemical indoor determination test rule insecticide the 6th part: insecticidal activity test dip method ".
Control treatment: do blank with the processing that does not contain the deionized water of medicament.
4 data surveys and statistical method
4.1 control time
Checkout facility result after chemicals treatment 72h.
4.2 data statistic analysis
Contrast lethality is greater than 20%, and test is reformed, and contrast lethality is less than 20%, respectively processes lethality with Abbott formula correction, obtains virulence regression equation by DPS data handling system, calculates LC
50value, 95% confidence limit, and carry out statistical analysis.
Computational methods:
6 interpretations of result and discussion
As can be seen from Table 2, the friendly type Acetamiprid of 3% Multifunctional environment aqua is identical with the confession examination concentration of 5% acetamiprid EC.Be reflected in Fig. 3, together with the toxicity regression line of the friendly type Acetamiprid of 3% Multifunctional environment aqua and the toxicity regression line of 5% acetamiprid EC are interlaced with one another.As can be seen from Table 3, if the friendly type Acetamiprid aqua of 3% Multifunctional environment and 5% acetamiprid EC to 2 age aphid LC
50value is respectively 3.3097mg/L and 3.8390mg/L; LC
90value is respectively 17.7410mg/L and 16.4222mg/L.Show that with the analysis of DPS data handling system the friendly type Acetamiprid aqua of 3% Multifunctional environment and 5% acetamiprid EC do not have significant difference to the toxicity of vegetable aphid.
The determination of activity result of the multi-functional Acetamiprid aqua of table 2 3% to vegetable aphid
The toxicity measure and calculation result of the friendly type Acetamiprid of table 3 3% Multifunctional environment aqua to vegetable aphid
Note: the identical English alphabet in same row represents not reach between processing the significant difference of 5% level;
Different English alphabets in same row represent to reach between processing the significant difference of 5% level.
7 conclusions and recommendations
Result of the test shows, if the friendly type Acetamiprid of 3% Multifunctional environment aqua to 2 age aphid LC
50value is lower than 5% acetamiprid EC, LC
90value is higher than 5% acetamiprid EC.Show that with the statistical analysis of DPS data handling system the friendly type Acetamiprid aqua of 3% Multifunctional environment and 5% acetamiprid EC do not have significant difference between to the virulence of vegetable aphid.
In a word, the invention provides the friendly type Acetamiprid of a kind of Multifunctional environment aqua, experiment showed, that the friendly type Acetamiprid aqua of Multifunctional environment of same concentrations is suitable with the indoor insecticidal effect of acetamiprid EC.But Acetamiprid aqua of the present invention does not contain organic solvent, strong acid etc. to the virulent reagent of environment, and adjuvant used is all environmental protection, and indices all reaches the requirement of country about aqueous pesticide solution.Therefore,, compared to water baseization of the Acetamiprid formulations of pesticide of prior art, aqua of the present invention has larger advantage and promotional value.
Claims (10)
1. the friendly type Acetamiprid of a Multifunctional environment aqua, is characterized in that: comprise Acetamiprid, functionalizers and water, do not comprise organic solvent.
2. the friendly type Acetamiprid of Multifunctional environment according to claim 1 aqua, is characterized in that: according to weight percent meter, comprising:
1%-5% Acetamiprid, 1%-10% agent A, 1%-5% functionalizers;
Preferably, the friendly type Acetamiprid of described Multifunctional environment aqua, according to weight percent meter, comprising:
1%-5% Acetamiprid, 2%-8% agent A, 1%-5% functionalizers;
Wherein, described agent A is selected from containing one or more in anionic surfactant, the anionic surfactant of sulfur acid group and the anion surfactant of carboxyl group of sulfonic acid group;
Described functionalizers be selected from there is synergy, sterilization, degeneration-resistant, stimulate plant growth, improve drug effect, suppress residual hazard, improve chemosynthesis material or the natural products of the function of agricultural product quality.
3. the friendly type Acetamiprid of Multifunctional environment according to claim 2 aqua, is characterized in that: described agent A is selected from one or more in straight or branched aliphatic group sulfonic acid and salt, straight or branched aliphatic group ether sulfonic acid and salt thereof, straight or branched aliphatic group sulfuric acid and salt thereof, straight or branched aliphatic group ether sulfuric acid and salt and straight or branched aliphatic group carboxylic acid and salt thereof.
4. according to the friendly type Acetamiprid of the Multifunctional environment described in claim 2 or 3 aqua, it is characterized in that: described agent A is selected from the compound of structural formula 1
CH
3(CH
2)
n(OCH
2CHR′)
mO
k(CO
2)
j(SO
3)
iM
1
Wherein, n=7-17, preferably n=11,13,15, or 17,
R '=H or CH
3,
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 NH
4.
5. according to the friendly type Acetamiprid of the Multifunctional environment described in claim 1 to 4 any one aqua, it is characterized in that: also comprise the agent B that accounts for total formulation weight amount 1%-5%; Described agent B is selected from nonionic surface active agent and/or the natural polymeric surface active agent containing ethylene oxide unit, propylene oxide unit or glucose unit.
6. the friendly type Acetamiprid of Multifunctional environment according to claim 5 aqua, is characterized in that: described nonionic surface active agent is selected from one or more in polyethylene glycol oxide, polypropylene oxide, polyvinyl alcohol and polyvinylpyrrolidone; Preferably from straight-chain fatty alcohol APEO, one or more in straight chain fatty acid polyoxyethylene ester, straight-chain fatty amine APEO, sorbitan fatty acid ester APEO, APG and castor oil polyoxyethylene ether;
Described natural polymeric surface active agent is selected from one or more in water soluble starch derivative, water-soluble cellulose derivative and shitosan and derivative thereof; Preferably one or more in dextrin, carboxymethyl starch, carboxymethyl cellulose, shitosan, CMC and Quaternary Ammonium Salt of Chitosan.
7. according to the friendly type Acetamiprid of the Multifunctional environment described in claim 1 to 6 any one aqua, it is characterized in that: described functionalizers is selected from one or more in Tea Saponin, humic acid, shitosan and derivative thereof, alginate, hyaluronic acid, Fructus Gleditsiae Abnormalis extract and matrine.
8. according to the friendly type Acetamiprid of the Multifunctional environment described in claim 1 to 7 any one aqua, it is characterized in that: also comprise other insecticides adjuvant that accounts for weight of formulation 0.1-10%;
Preferably, described other insecticides adjuvant comprises the drift control agents that accounts for weight of formulation 0.1-4%; Described drift control agents is selected from the surface tension that can reduce spray droplet, increases viscosity, improves the deposition of medicine, reduces water-soluble synthetic high polymer matter and the natural high molecular substance of drop bounce-back; Preferred described water-soluble natural polymer substance; More preferably the one in water-soluble cellulose derivative, water-soluble guar gum and derivative thereof and water soluble starch and derivative thereof is several.
9. according to the friendly type Acetamiprid of the Multifunctional environment described in claim 1 to 8 any one aqua, it is characterized in that: also comprise the antifreezing agent that accounts for weight of formulation 1%-6% and the defoamer that accounts for weight of formulation 0.01%-0.1%;
Preferably, described antifreezing agent is selected from one or more in ethylene glycol, propane diols, glycerine, low-molecular-weight polyethylene glycol and sorbierite; Preferred, described antifreezing agent is selected from one or more of glycerine, ethylene glycol and propane diols;
Preferably, described defoamer is selected from silicone defoaming agent, carbon atom quantity is C
7-C
9fatty alcohol and tributyl phosphate in one or more.
10. the preparation method of the friendly type Acetamiprid of Multifunctional environment aqua described in claim 1 to 9 any one, is characterized in that: comprise first agent A is dissolved in part water, then add Acetamiprid, functionalizers and remaining water;
Preferably, described preparation method comprises the steps:
I. prepare various raw materials according to formulation weight proportioning;
II. except Acetamiprid, defoamer, other insecticides adjuvant and water, composition of raw materials is comprised to other raw material of described agent A adds stirred tank, inject part water, heat or do not heat, stir, make to dissolve, obtain solution A;
III. Acetamiprid is added to described solution A, stir, make to dissolve, obtain solution B;
IV. described other insecticides adjuvant and remaining water are added in described solution B, stir, make to dissolve; Add again defoamer, gentle agitation, static, filter, to obtain final product.
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| CN103907643B (en) | 2016-08-24 |
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