CN103858936A - Multifunctional environment-friendly emamectin benzoate aqueous solution and preparation method thereof - Google Patents
Multifunctional environment-friendly emamectin benzoate aqueous solution and preparation method thereof Download PDFInfo
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Abstract
The invention provides a multifunctional environment-friendly emamectin benzoate aqueous solution and a preparation method thereof. The aqueous solution comprises the following components by weight percent: 1%-7% of emamectin benzoate, 1%-10% of an agent A, 1%-5% of a functional agent, 1%-6% of an agent B and or 0.1%-10% of other pesticide auxiliaries. The multifunctional aqueous solution does not contain any organic solvents, is uniform and clear in appearance, and is stable after long-term standing. Field tests prove that the multifunctional environment-friendly emamectin benzoate aqueous solution has the fast-acting property comparable to that of market missible oil, and has the pesticide-effect persistence obviously superior to that of the market missible oil; in addition, the growth of plants applied to the aqueous solution can be obviously improved. Therefore, the multifunctional environment-friendly emamectin benzoate aqueous solution is remarkably superior to the missible oil and other water-based forms.
Description
Technical field
The invention belongs to pesticides new formulation field, particularly the friendly type emamectin-benzoate of a kind of new Multifunctional environment aqua and preparation method thereof.
Background technology
Along with the raising of environmental consciousness, pesticidal preparations is proposed to efficient eco-friendly requirement simultaneously.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 ".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) formulation 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.Water base agent type be to be prepared into, microemulsion, aqueous emulsion, suspending agent and suspension emulsion conventionally can only be prepared into.In these four kinds of formulations, the particle size that agricultural chemicals disperses in water increases successively.Microemulsion, aqueous emulsion are that the organic solvent that has dissolved pesticide original medicine is dispersed in water in drop mode, 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 drop 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.
Emamectin-benzoate (being called for short first dimension salt, Emamectin benzoate, EB), structural formula is as shown in 2.The micro-salt of first is from biological antibiotic pesticide avermectin B1a, a kind of super-high-efficient insecticidal/acaricidal agent obtaining through chemical modification.Compared with parent Avermectin B1a, the insecticidal activity of emamectin-benzoate has improved tens times, has super-high-efficient, wide spectrum, closely nontoxic, noresidue, feature that pesticide resistance is little.The test of pesticide effectiveness shows, emamectin-benzoate has the incomparable activity of other agricultural chemicals to a lot of insects, especially to Lepidoptera, diptera super-high-efficient, insect comprises red tape leaf roller, cigarette aphid noctuid, cotton bollworm, maduca sexta, diamond-back moth mythimna separata, beet armyworm, the greedy noctuid in nonirrigated farmland, confused Autographa spp, cabbage looper, imported cabbageworm, cabbage heart snout moth's larva, wild cabbage horizontal stripe snout moth's larva, tomato hawkmoth, colorado potato beetle, Mexico ladybug etc.Emamectin-benzoate antagonism cotton bollworm and diamond-back moth special efficacy also have good insecticidal effect under low-down dosage.Along with the forbidding of high-toxic pesticide, emamectin-benzoate has become the main product of insecticide on market.
Emamectin-benzoate is soluble in the organic solvents such as acetone, methyl alcohol, toluene, dimethylbenzene, but is insoluble in water, and the solvability in water is approximately only 0.024g/L(25 ℃).Therefore its formulation is mainly missible oil, microemulsion, water dispersion granule and soluble granule at present, do not see high concentration water's agent formulation.The missible oil formulation of emamectin-benzoate is used a large amount of poisonous and hazardous toluene, dimethylbenzene equal solvent, is clearly classified as superseded backward formulation by national Ministry of Industry and Information.
In the water base agent type of emamectin-benzoate, the main formulation of current exploitation is microemulsion and aqueous emulsion.Solid dosage forms is mainly water dispersible granules and soluble granule.The active ingredient quality percentage composition from 0.5% to 5% of different dosage form registration is not etc.; Wherein, high-load is 5.7%, and amounting to Affirm (Merck Co.) content is 5.0%.
The situation of the Chinese invention patent of the water base agent type such as microemulsion and aqueous emulsion take emamectin-benzoate as pesticide original medicine application is as follows:
Application number is that 200710009947.9 application for a patent for invention " emamectin benzoate microemulsion and preparation method thereof " discloses a kind of emamectin benzoate microemulsion, formed by former medicine, solvent, cosolvent, emulsifier, water, each weight percentages of components is: emamectin-benzoate 0.5-5%, solvent 5-20%, cosolvent 1-10%, emulsifier 5-30%, synergist 0.1-3%, stabilizing agent 0.1-3%, water supplies 100%.Wherein said solvent is one or more in aromatic solvent, cyclohexanone, dimethyl formamide, acetone.
Application number is 200510012996.9 application for a patent for invention " pest killing micro emulsion that contains Affirm (Merck Co.) ", a kind of pest killing micro emulsion that contains Affirm (Merck Co.) is disclosed, form microemulsion by Affirm (Merck Co.), solvent, emulsifier, stabilizing agent, antifreezing agent and water, its composition content (take microemulsion weight as 100%): Affirm (Merck Co.) 0.2-10%, solvent 10-20%, emulsifier 8%-15%, stabilizing agent 1-3%, antifreezing agent 2-3%, all the other are made up of water.Described solvent is selected from methyl alcohol, ethanol or cyclohexanone.
The patent No. is that the patent of invention " a kind of emamectin-benzoate aqueous emulsion " of ZL200910111224.9 discloses a kind of emamectin-benzoate aqueous emulsion.Be made up of emamectin-benzoate, solvent, co-emulsifier, emulsifier, thickener, antifreezing agent, defoamer and water, the percentage by weight that each raw material accounts for aqueous emulsion is: emamectin-benzoate 0.5-10%, solvent 2%-10%, emulsifier 2%-10%, co-emulsifier 0.15%-5%, thickener 0.05%-5%, antifreezing agent 0.2%-5%, defoamer 0.05%-0.8%, moisturizing to 100%.Wherein said solvent is dimethylbenzene.
The patent No. is the patent of invention " emamectin-benzoate aqueous emulsion and preparation method thereof " of ZL200610023384.4, and a kind of emamectin-benzoate aqueous emulsion and preparation method thereof is provided.It is raw material that described aqueous emulsion adopts the material of following component and weight content: emamectin-benzoate 0.1%-20%, solvent 1%-10%, emulsifier 1%-10%, thickener 0.1%-5%, antifreezing agent 0.5%-5%, defoamer 0.1%-1%, moisturizing to 100%.Wherein solvent is selected from dimethylbenzene and/or toluene.
In foregoing invention patent, no matter be microemulsion or aqueous emulsion, in preparation, all to use the organic solvents such as poisonous and hazardous methyl alcohol, toluene, dimethylbenzene or its mixture.Its preparation principle is all first emamectin-benzoate to be dissolved in to described organic solvent, and recycling surfactant, by emulsification, is distributed in water it.Although the amount of the organic solvent that microemulsion or aqueous emulsion use obviously reduces than missible oil formulation, quality percentage composition is still at 10%-20%.That is to say, produce 1 ton of emamectin benzoate microemulsion or aqueous emulsion, need the xylene solvent using to be about 100-200kg.In the time that the production scale of these formulations is larger, the quantity of the organic solvent of use also can not be ignored.
In addition, market also claims to the further performance of improving emamectin-benzoate preparation.Therefore, a kind of not containing any organic solvent, that various aspects of performance is more superior, the eco-friendly emamectin-benzoate 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 emamectin-benzoate of Multifunctional environment aqua is provided.Described aqua is not containing any organic solvent, and outward appearance is the uniform solution of clarification, and long-term placement is stable, and has the advantages that be obviously better than emamectin-benzoate missible oil formulation and other water base agent formulation: 1. not containing any organic solvent; 2. auxiliary agent is all green matter; 3. the physical properties of aqua meets state specified standards index.And there is better photostability, wetability and functional, and not only can extend the lasting period of desinsection, reduce spraying times, reduce pesticide dosage, but also there is the drug effect of raising, suppress residual hazard, improve the functions such as agricultural product quality.
A further object of the invention, is to provide the preparation method of the friendly type emamectin-benzoate of described Multifunctional environment aqua.
In order to realize foregoing invention object, the present invention has adopted following technical scheme:
The friendly type emamectin-benzoate of a kind of Multifunctional environment aqua, comprises emamectin-benzoate, functionalizers and water, does not comprise organic solvent.
Preferably, the friendly type emamectin-benzoate of described Multifunctional environment aqua, according to weight percent meter, comprising:
1%-7% emamectin-benzoate, 1%-10% agent A, 1%-5% functionalizers.
Preferred, the friendly type emamectin-benzoate of described Multifunctional environment aqua, according to weight percent meter, comprising:
1%-7% emamectin-benzoate, 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 refer to 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 emamectin-benzoate of described Multifunctional environment aqua, also comprises the agent B that accounts for total formulation weight amount 1%-6%; 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.
Preferably, described nonionic surface active agent is selected from one or more in polyethylene glycol oxide, polypropylene oxide, polyvinyl alcohol and polyvinylpyrrolidone; More 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;
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 preferably 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 emamectin-benzoate of above-mentioned Multifunctional environment aqua, also comprises other insecticides adjuvant that accounts for weight of formulation 0.1-10%;
Preferred, described other insecticides adjuvant comprises light stabilizer and/or drift control agents.
Wherein, described light stabilizer accounts for the 0.1-0.4% of total formulation weight amount; Be selected from one or more in salicylate class, benzophenone, benzotriazole and hindered amine light stabilizer; Preferably benzophenone light stabilizer; More preferably from 2,4-dihydroxy-5-sulfonic group benzophenone, 2,2`4,4`-tetrahydroxybenzophenone, 2,3,4, one or more in 4`-tetrahydroxybenzophenone;
Described drift control agents accounts for the 1%-3% of total formulation weight amount; Be selected from the surface tension that can reduce spray droplet, increase viscosity, improve the deposition of medicine, reduce 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 emamectin-benzoate 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, 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.
As a preferred embodiment of the present invention, the friendly type emamectin-benzoate of a kind of Multifunctional environment aqua, according to weight percent meter, comprising:
1%-7% emamectin-benzoate, 1%-10% agent A, 1%-6% agent B, 1%-5% functionalizers, 1%-6% antifreezing agent, 0.01%-0.1% defoamer, other insecticides adjuvant of 0.1-10%, and the water of surplus.
Another object of the present invention, is to provide the preparation method of the friendly type emamectin-benzoate of described Multifunctional environment aqua, comprises first agent A is dissolved in part water, then add emamectin-benzoate and remaining water.
Preferably, described preparation method comprises the steps:
I. prepare various raw materials according to formulation weight proportioning;
II. except emamectin-benzoate, defoamer, outside other insecticides adjuvant and water, comprises that by formula other raw material of described agent A adds stirred tank, injects part water, stirs, and makes to dissolve, and obtains solution A;
III. emamectin-benzoate 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.
Emamectin-benzoate is in the chemical constitution of antibiotic Avermectin B1a, has introduced this characteristic group of methylamino and has made it and benzoic acid salify.The solvability of emamectin-benzoate in water is very little, is only 0.024g/L.Prior art is all first emamectin-benzoate to be dissolved in organic solvent, is then prepared into aqueous emulsion or microemulsion.
Agent A of the present invention is the material that a class can improve emamectin-benzoate solvability and separating degree in water.Inventor finds by research, and some specific compound can function as described above, thereby without by organic solvent, just can prepare the aqua of emamectin-benzoate.Therefore, inventor has carried out preferably agent A by following experiment.
In 10ml water, add quantitative different types of compound and quantitative emamectin-benzoate, under room temperature, stir, observe dissolving situation, optimize 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 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 test, 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 emamectin-benzoate of Multifunctional environment of the present invention aqua can also comprise agent B.So-called agent B, referring to can be to improving the dispersiveness of emamectin-benzoate 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%-6% of gross weight in preparation.
Kill the effect of insect pest in order to strengthen emamectin-benzoate aqua, play the effect of plant protection simultaneously, emamectin-benzoate aqua of the present invention comprises functionalizers.Described functionalizers refer to a class have 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.
In order further to improve the performance of emamectin-benzoate aqua of the present invention, aqua of the present invention also comprises other insecticides adjuvant, accounts for the 0.1%-10% of total formulation weight amount.Preparation of the present invention is generally used with Sprayable; In order to extend the action time of emamectin-benzoate aqua of the present invention on crop blade face, improve pulverability, other insecticides adjuvant of the present invention comprises light stabilizer and/or drift control agents.
Described light stabilizer refers to and can reduce the material that emamectin-benzoate decomposes very soon under solar radiation, comprises the light stabilizers such as salicylate class, benzophenone, benzotriazole, hindered amines.Consider from environmental friendliness angle, preferably can be applicable to the light stabilizer of the benzophenone of cosmetics.Consider from the feature of formulation of the present invention, preferably benzophenone light stabilizer, concrete, preferably from 2,4-dihydroxy-5-sulfonic group benzophenone, 2,2`, one or more in 4,4`-tetrahydroxybenzophenone and 2,3,4,4`-tetrahydroxybenzophenone.Described light stabilizer accounts for the 0.1%-0.4% of total formulation weight amount.
Described drift control agents refers to the surface tension that can reduce spray droplet, increases viscosity, 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.Described drift control agents accounts for the 1%-3% of total formulation weight amount.
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 the material that can eliminate foam in the last process of aqua manufacture, 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 emamectin-benzoate 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 emamectin-benzoate of Multifunctional environment of the present invention aqua, can be applied to the insects such as crop control Lepidoptera, diptera, Homoptera, coleoptera such as vegetables, fruit, tealeaves, paddy rice, corn, cotton.
The friendly type emamectin-benzoate of Multifunctional environment of the present invention aqua, should not belong to existing microemulsion.Because in the process of the described aqua of preparation invention, do not use any organic solvent.And emamectin benzoate microemulsion of the prior art, aqueous emulsion are all to have dissolved the system that the solution droplets of emamectin-benzoate organic solvent is disperseed in water.If the xylene solution of emamectin-benzoate is distributed in the aqua system of the present invention that does not comprise emamectin-benzoate, will produce water-oil separating, can not form the system of stable homogeneous.This shows the friendly type emamectin-benzoate 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, therefore can adopt Tyndall phenomenon to distinguish colloid and solution.Microemulsion is in water, to form in being disperseed by the organic solution drop that is dissolved with pesticide original medicine that is less than 100nm, 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 emamectin-benzoate aqua of Multifunctional environment of the present invention and emamectin benzoate microemulsion of the prior art.
Referring to Fig. 1, the Tyndall phenomenon of the friendly type emamectin-benzoate of known Multifunctional environment of the present invention aqua is obviously weaker than the microemulsion of same concentration.This shows the dispersity of emamectin-benzoate of the present invention in water, and that disperses than traditional microemulsion is less more even, closer to Solution Dispersion.
The prepared friendly emamectin-benzoate aqua of Multifunctional environment 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 emamectin-benzoate and preferred agent A composition composition of water, the solvability in water of emamectin-benzoate is improved to two orders of magnitude, obtained stable emamectin-benzoate high concentration solution.Can also improve its performance with preferred agent B in addition.Thereby provide on this basis a kind of Multifunction environmental friendliness emamectin-benzoate aqua.After testing, the property indices of the friendly type emamectin-benzoate 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 first dimension salt can reach 1-7%, fair or higher with the high-load of current domestic other liquid dosage form.
3. aqua stability in hard water can be qualified, and muddiness, precipitation do not occur in the hard water of normal concentration.
4. aqua high-and low-temperature resistance performance is qualified.
Emamectin-benzoate aqua of the present invention has good environmental friendliness performance.The most outstanding feature is, do not contain any organic solvent in preparation, and the auxiliary agent of use is all biodegradable material, and environment is not formed to harm, emamectin-benzoate basic noresidue in environment in addition.Therefore, emamectin-benzoate aqua of the present invention has improved the environmental friendliness performance of pesticidal preparations to greatest extent.
The present invention is by selecting, use water-soluble chemical synthetic or natural products, preferred water soluble natural product is as functionalizers, gives the friendly emamectin-benzoate 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, to pesticide slow-release synergy, reduce toxicity, extend drug effect, effectively 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 light stabilizer and drift control agents in emamectin-benzoate aqua, can extend drug effect, improves pulverability.Finally, the invention provides a kind of environmentally friendly emamectin-benzoate aqua that integrates several functions.
In addition, the friendly type emamectin-benzoate of Multifunctional environment provided by the invention aqua, economic and social benefit is remarkable, has application value.Described emamectin-benzoate aqua, only make water as solvent, compared with the liquid dosage forms such as emamectin-benzoate missible oil of the prior art, microemulsion, aqueous emulsion, can replace respectively the poisonous and hazardous organic solvent such as dimethylbenzene, toluene of the about 15%-85% of mass percent.Not only reduce production cost, and can avoid these poisonous and hazardous organic solvents to environmental emission, significant for protection of the environment, the saving resource energy and low-carbon emission reduction.Therefore,, along with applying of the friendly type emamectin-benzoate of Multifunctional environment of the present invention aqua, will produce significant economic benefit and social benefit.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is elaborated.
The Tyndall phenomenon photo of what the photo of Fig. 1 showed the is friendly type emamectin-benzoate aqua of Multifunctional environment of the present invention and commercially available emamectin benzoate microemulsion; Wherein: in the conical flask of left side is the friendly type emamectin-benzoate of 1% Multifunctional environment aqua prepared by the embodiment of the present invention 1, and in the conical flask of right side is that 1% first is tieed up salt microemulsion
The photo of the friendly type emamectin-benzoate of the Multifunctional environment aqua of embodiment 1,3 and 5 preparations that the photo of Fig. 2 shows.Respectively the friendly type emamectin-benzoate of the Multifunctional environment aqua of embodiment 1,3 and 5 preparations from left to right.
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 emamectin-benzoate of a kind of 1% Multifunctional environment aqua
Raw material proportioning:
Preparation by the following method:
I. according to formulation weight proportioning, prepare the various raw materials of the multi-functional aqua of preparation 1kg;
II. respectively 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, stir, make to dissolve, obtain solution A;
III. emamectin-benzoate 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 to solution B, then add 2,2`, 4,4`-tetrahydroxybenzophenone, at room temperature stirs, and makes it to dissolve, and adds tributyl phosphate, stirs, static, froth breaking.Obtain target product.
The friendly type emamectin-benzoate of the 1% Multifunctional environment aqua of above-mentioned preparation, appearance transparent, clarification, referring to Fig. 2.
embodiment 2the friendly type emamectin-benzoate of a kind of 2% Multifunctional environment aqua
Raw material proportioning:
Adopt preparation method and the step identical with embodiment 1, obtain the target product that 1kg outward appearance is transparence.
embodiment 3the friendly type emamectin-benzoate of a kind of 3% Multifunctional environment aqua
Raw material proportioning:
Adopt preparation method and the step similar to embodiment 1, obtain the target product that 10kg outward appearance is transparence, referring to Fig. 2.
embodiment 4the friendly type emamectin-benzoate of a kind of 4% Multifunctional environment aqua
Raw material proportioning:
Adopt preparation method and the step identical with embodiment 1, obtain the target product that 1kg outward appearance is transparence.
embodiment 5the friendly type emamectin-benzoate of a kind of 5% Multifunctional environment aqua
Raw material proportioning:
Adopt preparation method and the step identical with embodiment 1, obtain the target product that 1kg outward appearance is transparence, referring to Fig. 2.
embodiment 6a kind of 7% Multifunctional environment close friend's emamectin-benzoate aqua
Raw material proportioning:
Adopt preparation method and the step similar to embodiment 1, obtain 1000kg target product.
embodiment 7a kind of 1% Multifunctional environment close friend's emamectin-benzoate aqua raw material proportioning:
Adopt preparation method and the step similar to embodiment 1, obtain 1000kg target product.
embodiment 8a kind of 3% eco-friendly emamectin-benzoate aqua
Raw material proportioning:
Adopt preparation method and the step similar to embodiment 1, obtain 1000kg target product.
test example 1the Tyndall phenomenon of the friendly type emamectin-benzoate of Multifunctional environment of the present invention aqua
The conical flask of 1% the friendly type emamectin-benzoate of the Multifunctional environment aqua that is equipped with prepared by the embodiment of the present invention 1 and that the conical flask of 1% emamectin benzoate microemulsion (Shandong × × Chemical Co., Ltd. produces) is housed is arranged side by side, the laser of laser pen transmitting is successively by above-mentioned two kinds of liquid.
Result as shown in Figure 1., 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 ".Emamectin-benzoate aqua prepared by embodiment 1 is described, the dispersity of emamectin-benzoate in water, that disperses than traditional microemulsion is less more even, closer to Solution Dispersion.
test example 2the test of pesticide effectiveness of the friendly type emamectin-benzoate of Multifunctional environment of the present invention aqua
Test name: the friendly type emamectin-benzoate of 3% Multifunctional environment aqua control vegetables diamond-back moth trial crops: wild cabbage
Controlling object: diamond-back moth (Plutella xylostella L.)
The friendly type emamectin-benzoate of 3% Multifunctional environment aqua prepared by test medicine: embodiment 3, arranges three dosage groups, and described 3% environmentally friendly emamectin-benzoate aqua dilutes respectively
2000,1500 and 1000 times;
Contrast medicament: commercially available 1% emamectin-benzoate missible oil
Application method and water consumption: spraying, 900 liters/hectare.Contain and send out phase dispenser at diamond-back moth low instar larvae.
Result of the test: in table 2.
Table 2 test of pesticide effectiveness result
Evaluating drug effect:
Result of the test shows, after medicine 1 day, three dosage of the environmentally friendly emamectin-benzoate aqua of test medicine 3% process to wild cabbage diamond-back moth preventive effect be respectively 18.21%, 32.03% and 52.67%, three dosage process preventive effect significant difference.It is suitable with the preventive effect (29.73%) that contrasts 500 times of processing of medicament 1% emamectin-benzoate missible oil dilution that middle dosage is processed.After medicine 7 days, the preventive effect of each dosage processing of test medicine was 42.87%-83.49%, and three dosage are processed preventive effect significant differences.It is suitable with the preventive effect (42.81%) that contrasts medicament 1% emamectin-benzoate missible oil that low dosage is processed preventive effect; Middle dosage is processed the preventive effect of preventive effect 51.66% higher than Isodose missible oil.
In addition, the cabbage leaves hypertrophy of three of multi-functional aqua dosage processed group, moist.After finish 120 day vegetative period, the output average specific 1% emamectin-benzoate missible oil processed group of above-mentioned three processed group increases by 5.2%.
Conclusion (of pressure testing):
The quick-acting of the friendly type emamectin-benzoate of Multifunctional environment of the present invention aqua is suitable with commercially available missible oil effect, but drug effect continuation is obviously better than commercially available missible oil.Adopt the friendly type aqua of Multifunctional environment of the present invention can effectively improve the control efficiency to insect pest, reduce Application, frequency, and then reduce total consumption of emamectin-benzoate.And missible oil is owing to having comprised organic solvent, smell is pungent, and aqua of the present invention is without any penetrating odor.In addition, the friendly type aqua of Multifunctional environment of the present invention can obviously promote to be executed the growth of plant.In sum, emamectin-benzoate aqua usefulness of the present invention is higher, be conducive to reduce production costs, and is more conducive to environmental protection; Compared with existing cream preparation, there is significant advantage.
Claims (10)
1. the friendly type emamectin-benzoate of a Multifunctional environment aqua, is characterized in that: comprise emamectin-benzoate, functionalizers and water, do not comprise organic solvent.
2. the friendly type emamectin-benzoate of Multifunctional environment according to claim 1 aqua, according to weight percent meter, comprising:
1%-7% emamectin-benzoate, 1%-10% agent A, 1%-5% functionalizers;
Preferably, the friendly type emamectin-benzoate of described Multifunctional environment aqua, according to weight percent meter, comprising:
1%-7% emamectin-benzoate, 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 refer to 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 emamectin-benzoate 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 emamectin-benzoate 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 emamectin-benzoate 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%-6%; 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 emamectin-benzoate 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 emamectin-benzoate 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, matrine etc.
8. according to the friendly type emamectin-benzoate 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 light stabilizer and/or drift control agents;
Wherein, described light stabilizer accounts for the 0.1-0.4% of total formulation weight amount; Be selected from one or more in salicylate class, benzophenone, benzotriazole and hindered amine light stabilizer; Preferably benzophenone light stabilizer; More preferably from 2,4-dihydroxy-5-sulfonic group benzophenone, 2,2`4,4`-tetrahydroxybenzophenone, 2,3,4, one or more in 4`-tetrahydroxybenzophenone;
Described drift control agents accounts for the 1%-3% of total formulation weight amount; Be selected from the surface tension that can reduce spray droplet, increase viscosity, improve the deposition of medicine, reduce 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 emamectin-benzoate 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 emamectin-benzoate of Multifunctional environment aqua described in claim 1 to 9 any one, it is characterized in that: comprise first described agent A is dissolved in part water, then add emamectin-benzoate and remaining water;
Preferably, described preparation method comprises the steps:
I. prepare various raw materials according to formulation weight proportioning;
II. except emamectin-benzoate, outside defoamer and other insecticides adjuvant, formula is comprised to other raw material of described agent A adds stirred tank, inject part water, stir, make to dissolve, obtain solution A;
III. emamectin-benzoate 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410052228.5A CN103858936B (en) | 2014-02-14 | 2014-02-14 | A kind of Multifunctional environment friendly emamectin-benzoate water preparation and preparation method thereof |
| US15/118,825 US10206402B2 (en) | 2014-02-14 | 2015-02-09 | Environmentally-friendly emamectin benzoate preparation and preparation method therefor |
| BR112016018564-1A BR112016018564B1 (en) | 2014-02-14 | 2015-02-09 | ECOLOGICALLY FAVORABLE EMAMECTIN BENZOATE FORMULATIONS AND METHODS FOR PREPARATION |
| EP15749075.6A EP3106031B1 (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 |
| AU2015218092A AU2015218092B2 (en) | 2014-02-14 | 2015-02-09 | Environmentally-friendly emamectin benzoate preparation and preparation method therefor |
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