CN103858936B - A kind of Multifunctional environment friendly emamectin-benzoate water preparation and preparation method thereof - Google Patents
A kind of Multifunctional environment friendly emamectin-benzoate water preparation and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of new Multifunctional environment friendly emamectin-benzoate water preparation of providing, according to weight percent meter, including: 1%-7% emamectin-benzoate, 1%-10% agent A, 1%-5% functionalizers；1%-6% other insecticides adjuvant of agent B and/or 0.1%-10% can also be included.Multi-functional water preparation of the present invention is without any organic solvent, and outward appearance is the solution of uniformly clarification, and long-term placement is stablized.Field test proves, Multifunctional environment friendly emamectin-benzoate water preparation quick-acting of the present invention is suitable with commercially available cream effect, but drug effect persistence is significantly stronger than commercially available cream；And can be obviously promoted by the growth executing plant.Therefore, preparation of the present invention is substantially better than emulsifiable concentrate and other water base agent type.
Description
Technical field
The invention belongs to pesticides new formulation field, particularly to a kind of new Multifunctional environment friendly emamectin-benzoate water preparation and preparation method thereof.
Background technology
Along with the raising of environmental consciousness, efficiently eco-friendly requirement simultaneously is proposed pesticidal preparations.Research finds, for pesticide original medicine of the same race, pesticidal preparations plays the height of drug effect, depends on its types of formulation and the dispersity of pesticide microgranule and size.Scientific common sense teaches that, when other condition is identical, the microgranule dispersion size of pesticide original medicine is more little, and its surface area is more big, more wide with the contact area of plant leaf blade and insect, and drug effect plays more abundant, and the consumption that makes of pesticide will reduce accordingly.
A kind of formulations of pesticide whether environmental friendliness, its evaluation criterion had both related to the character of pesticide original medicine itself, is directed in dosage form and whether uses organic solvent, and whether the solvent of use and auxiliary agent belong to green matter.Although various water baseization pesticidal preparations pertain generally to environmental friendliness dosage form, but the evaluation of environmentally friendly degree should refer to above-mentioned standard.In August, 2010, four ministries and commissions of country combine appearance " pesticide industrial policy ", wherein explicitly point out: " country is by the science and technology measure such as supports, technological transformation, economic policy guiding; support efficiently, safety, economy, the development of eco-friendly pesticide new product; accelerating high pollution, the replacement of excessive risk product and eliminate, promotion breed structure is continued to optimize."；" agricultural dosage form is promoted to develop to efficient, safe directions such as water baseization, dustlessization, control releases energetically ... the strict use controlling 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: " strictly controlling the use containing the poisonous and harmful solvent such as toluene, dimethylbenzene and auxiliary agent, develop and promote the dosage forms such as water baseization ".Therefore, do not use or reduce use organic solvent as far as possible, select and use Green Additives, exploitation should be become and promote a kind of developing direction and the trend of the environmental friendliness formulations of pesticide.
In the water baseization formulations of pesticide, only the pesticide original medicine in aqueous pharmaceutical (water preparation) dosage form belongs to monomolecular dispersion, and size is minimum.But the pesticide species that can prepare into water preparation is little, and the pesticide species having easily is hydrolyzed in water, which limits its application.Because most of pesticide are oil-soluble, what have can only be dissolved in organic solvent, and being even difficult to of having is dissolved in conventional organic solvent.It is prepared into water base agent type, is typically only capable to prepare into microemulsion, aqueous emulsion, suspending agent and suspension emulsion.In these four dosage form, pesticide scattered particle size in water increases successively.Microemulsion, aqueous emulsion are that the organic solvent having dissolved pesticide original medicine is dispersed in water with drop form, wherein the drop size of microemulsion is minimum, below 100 nanometers, less than 1/4th of visible wavelength, thus system is transparent, belong to thermodynamic stable system；And the drop size of aqueous emulsion is more than hundreds of nanometer to micron, close or larger than visible wavelength, system is opaque, and poor stability.The pesticide microgranule being ground into micron-scale is usually suspended in water by the effect of macromolcular dispersant by suspending agent, and this system has the tendency that the cohesion of pesticide crystal grain occurs.Suspension emulsion is then the combining form of suspending agent and aqueous emulsion.In these four dosage form, except suspending agent, all containing the organic solvent of 10%-20%, this is reducing their environmental friendliness performance in varying degrees.
Emamectin-benzoate (is called for short emamectin benzoate, Emamectinbenzoate, EB), and structural formula is as indicated with 2.The micro-salt of first is from biological antibiotic pesticide avermectin B1a, through a kind of ultra high efficiency insecticidal/acaricidal agent that chemical modification obtains.Compared with parent Avermectin B1a, the insecticidal activity of emamectin-benzoate improves tens times, has ultra high efficiency, wide spectrum, closely nontoxic, noresidue, feature that Drug resistance is little.The test of pesticide effectiveness shows, a lot of insects are had the activity that other pesticide is incomparable by emamectin-benzoate, especially to Lepidoptera, Diptera ultra high efficiency, insect includes red tape leaf roller, cigarette aphid noctuid, bollworm, maduca sexta, diamondback moth mythimna separata, beet armyworm, nonirrigated farmland greedy noctuid, confused Autographa spp, cabbage looper, cabbage butterfly, Brassica campestris L. ssp.chinensis snout moth's larva, Caulis et Folium Brassicae capitatae horizontal stripe snout moth's larva, Fructus Lycopersici esculenti hawkmoth, colorado potato bug, Mexico ladybug etc..Emamectin-benzoate antagonism bollworm and diamondback moth specially good effect, also have good insecticidal effect under low-down dosage.Along with the disabling 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, methanol, toluene, dimethylbenzene, but is insoluble in water, and the dissolubility in water is about only 0.024g/L(25 DEG C).Therefore its dosage form is presently mainly cream, microemulsion, water dispersion granule and soluble granule, do not see high concentration water's agent dosage form.The cream dosage form of emamectin-benzoate uses a large amount of poisonous and hazardous toluene, dimethylbenzene equal solvent, is clearly classified as superseded backward dosage form by Ministry of Industry and Information of country.
In the water base agent type of emamectin-benzoate, the main dosage form of current exploitation is microemulsion and aqueous emulsion.Solid dosage forms is mainly water dispersible granules and soluble granule.The effective ingredient weight/mass percentage composition of different dosage form registration is from 0.5% to 5% not etc.；Wherein, most 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 with emamectin-benzoate for pesticide original medicine application is as follows:
Application number be 200710009947.9 application for a patent for invention " emamectin benzoate microemulsion and preparation method thereof " disclose a kind of emamectin benzoate microemulsion, it is made up of former medicine, solvent, cosolvent, emulsifying agent, water, each weight percentages of components is: emamectin-benzoate 0.5-5%, solvent 5-20%, cosolvent 1-10%, emulsifying agent 5-30%, synergist 0.1-3%, stabilizer 0.1-3%, water supplies 100%.Wherein said solvent is one or more in aromatic solvent, Ketohexamethylene, dimethylformamide, acetone.
Application number is the application for a patent for invention " pest killing micro emulsion containing Affirm (Merck Co.) " of 200510012996.9, disclose a kind of pest killing micro emulsion containing Affirm (Merck Co.), microemulsion is formed, its composition content (with microemulsion weight for 100%): Affirm (Merck Co.) 0.2-10%, solvent 10-20%, emulsifying agent 8%-15%, stabilizer 1-3%, antifreezing agent 2-3%, all the other are made up of water by Affirm (Merck Co.), solvent, emulsifying agent, stabilizer, antifreezing agent and water.Described solvent selected from methanol, ethanol or Ketohexamethylene.
The patent of invention " a kind of emamectin-benzoate aqueous emulsion " that the patent No. is ZL200910111224.9 discloses a kind of emamectin-benzoate aqueous emulsion.Being made up of emamectin-benzoate, solvent, co-emulsifier, emulsifying agent, thickening agent, antifreezing agent, defoamer and water, each raw material accounts for the percentage by weight of aqueous emulsion and is: emamectin-benzoate 0.5-10%, solvent 2%-10%, emulsifying agent 2%-10%, co-emulsifier 0.15%-5%, thickening agent 0.05%-5%, antifreezing agent 0.2%-5%, defoamer 0.05%-0.8%, moisturizing are 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, it is provided that a kind of emamectin-benzoate aqueous emulsion and preparation method thereof.Described aqueous emulsion adopts the material of following component and weight content to be raw material: emamectin-benzoate 0.1%-20%, solvent 1%-10%, emulsifying agent 1%-10%, thickening agent 0.1%-5%, antifreezing agent 0.5%-5%, defoamer 0.1%-1%, moisturizing is to 100%.Wherein solvent is selected from dimethylbenzene and/or toluene.
In foregoing invention patent, no matter it is microemulsion or aqueous emulsion, preparation will use the organic solvents such as poisonous and hazardous methanol, toluene, dimethylbenzene or its mixture.Its preparation principle is all that emamectin-benzoate is first dissolved in described organic solvent, and recycling surfactant passes through emulsification so that it is be distributed in water.Although the amount of the organic solvent that microemulsion or aqueous emulsion use significantly reduces than cream dosage form, but weight/mass percentage composition is still at 10%-20%.It is to say, produce 1 ton of emamectin benzoate microemulsion or aqueous emulsion, it is necessary to the xylene solvent of use is about 100-200kg.When the production scale of these dosage forms is bigger, the quantity of the organic solvent of use also can not be ignored.
It addition, the performance improving emamectin-benzoate preparation further is also claimed by market.Therefore, in the urgent need to develop a kind of without any organic solvent, various aspects of performance is more superior, the eco-friendly emamectin-benzoate water preparation of Multifunction.
Summary of the invention
The primary and foremost purpose of the present invention is in that to overcome the deficiencies in the prior art, it is provided that new Multifunctional environment friendly emamectin-benzoate water preparation.Described water preparation is without any organic solvent, and outward appearance is for clarifying uniform solution, and long-term placement is stablized, and has the advantages that to be substantially better than emamectin-benzoate cream dosage form and other water base agent dosage form: 1. without any organic solvent；2. auxiliary agent is all green matter；3. the physical properties of water preparation meets state specified standards index.And there is better light stability, wettability and functional, not only can extend the lasting period of parasite killing, reduce spraying times, reduce pesticide dosage, but also there is raising drug effect, suppress residual hazard, improve the functions such as agricultural product quality.
A further object of the invention, is in that the preparation method providing described Multifunctional environment friendly emamectin-benzoate water preparation.
In order to realize foregoing invention purpose, present invention employs following technical scheme:
A kind of Multifunctional environment friendly emamectin-benzoate water preparation, including emamectin-benzoate, functionalizers and water, does not include organic solvent.
Preferably, described Multifunctional environment friendly emamectin-benzoate water preparation, according to weight percent meter, including:
1%-7% emamectin-benzoate, 1%-10% agent A, 1%-5% functionalizers.
It is furthermore preferred that described Multifunctional environment friendly emamectin-benzoate water preparation, according to weight percent meter, including:
1%-7% emamectin-benzoate, 2%-8% agent A, 1%-5% functionalizers.
Wherein, one or more in the anionic surfactant containing sulfonic acid group, the anionic surfactant of sulfur acid group and the anion surfactant of carboxyl group of described agent A；
Described functionalizers refer to have potentiation, sterilization, degeneration-resistant, stimulate plant growth, improve drug effect, suppress residual hazard, improve chemosynthesis material or the natural product 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, straight or branched aliphatic group sulphuric acid and salt, straight or branched aliphatic group ether sulphuric acid and salt thereof and straight or branched aliphatic group carboxylic acid and salt thereof.
It is furthermore preferred that described agent A is selected from the compound of structural formula 1,
CH3(CH2)n(OCH2CHR′)mOk(CO2)j(SO3)iM
1
Wherein, n=7-17, it is preferable that n=11,13,15, or 17,
R '=H or CH3,
M=0,1,2,3, or 4,
K=0 or 1,
J=0 or 1,
I=0 or 1, and i ≠ j,
M=H, K, Na, or NH4。
Accordingly, as the preferred embodiment of the present invention, described in water dissociable go out sulfonate groups one or more in the following compound of agent:
I. dodecyl, myristyl, cetyl and octadecyl sulfonic acid and potassium, sodium or ammonium salt;
II. dodecyl, myristyl, cetyl and octadecyl sulfonic acid ether and potassium, sodium or ammonium salt;
III. dodecyl, myristyl, cetyl and octadecyl sulphuric acid and potassium, sodium or ammonium salt;
IV. dodecyl, myristyl, cetyl and octadecyl sulphuric acid ether and potassium, sodium or ammonium salt；
V. dodecyl, myristyl, cetyl and octadecyl carboxylic acid and potassium, sodium or ammonium salt.
Preferably, described Multifunctional environment friendly emamectin-benzoate water preparation, also include the agent B accounting for total formulation weight amount 1%-6%;Described agent B is selected from the nonionic surfactant containing ethylene oxide unit, propylene oxide unit or glucose unit and/or natural polymeric surface active agent.
Preferably, one or more in polyethylene glycol oxide, polypropylene oxide, polyvinyl alcohol and polyvinylpyrrolidone of described nonionic surfactant；More preferably from straight chain fatty polyoxyethylenated alcohol, one or more in straight chain fatty acid polyoxyethylene ester, straight-chain fatty amine polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, APG and castor oil polyoxyethylene ether；
Preferably, one or more in water soluble starch derivatives, water-soluble cellulose derivative and Chitosan-phospholipid complex of described natural polymeric surface active agent；More preferably from one or more in dextrin, carboxymethyl starch, carboxymethyl cellulose, chitosan, carboxymethyl chitosan and Quaternary Ammonium Salt of Chitosan.
Preferably, one or more in tea saponin, humic acids, Chitosan-phospholipid complex, alginate, hyaluronic acid, Fructus Gleditsiae Abnormalis extract, matrine etc. of described functionalizers.
Preferably, above-mentioned Multifunctional environment friendly emamectin-benzoate water preparation, also include other insecticides adjuvant accounting for weight of formulation 0.1-10%；
It is furthermore preferred that other insecticides adjuvant described includes light stabilizer and/or drift control agents.
Wherein, described light stabilizer accounts for the 0.1-0.4% of total formulation weight amount；One or more in salicylic acid esters, benzophenone, benzotriazole and hindered amine light stabilizer；Preferred benzophenone light stabilizer；More preferably from one or more in 2,4-dihydroxy-5-sulfonic group benzophenone, 2,2`4,4`-tetrahydroxybenzophenone, 2,3,4,4`-tetrahydroxybenzophenone；
Described drift control agents accounts for the 1%-3% of total formulation weight amount；Selected from the surface tension that can reduce spray droplet, increase viscosity, improve the deposition of medicine, reduce water solublity synthetic high polymer matter and the natural high molecular substance of drop bounce-back；Preferred described water-soluble natural polymer substance；Several more preferably from the one in water-soluble cellulose derivative, water solublity guar gum and derivant thereof and water soluble starch and derivant thereof.
Above-mentioned Multifunctional environment friendly emamectin-benzoate water preparation, also includes accounting for the antifreezing agent of weight of formulation 1%-6% and accounting for the defoamer of weight of formulation 0.01%-0.1%；
Preferably, one or more in ethylene glycol, propylene glycol, glycerol, low-molecular-weight Polyethylene Glycol and sorbitol of described antifreezing agent；It is furthermore preferred that described antifreezing agent is selected from one or more of glycerol, ethylene glycol and propylene glycol；
Preferably, described defoamer is C selected from organic silicon defoamer, carbon atom quantity7～C9Fatty alcohol and tributyl phosphate in one or more.
As a preferred embodiment of the present invention, a kind of Multifunctional environment friendly emamectin-benzoate water preparation, according to weight percent meter, including:
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 in that the preparation method providing described Multifunctional environment friendly emamectin-benzoate water preparation, including being first dissolved in part water by agent A, adds emamectin-benzoate and remaining water.
Preferably, described preparation method comprises the steps:
I. various raw materials are prepared according to formulation weight proportioning；
II. except emamectin-benzoate, defoamer, outside other insecticides adjuvant and water, other raw material that formula includes described agent A adds stirred tank, injects part water, stirring, makes dissolving, obtain solution A；
III. emamectin-benzoate is added described solution A, stirring, make dissolving, obtain solution B；
IV. other insecticides adjuvant described and remaining water are added in described solution B, stirring, make dissolving；Add defoamer, gentle agitation, static, filter, to obtain final product.
Emamectin-benzoate is in the chemical constitution of antibiotics Avermectin B1a, introduces this characteristic group of methylamino and so as to becomes salt with benzoic acid.Emamectin-benzoate dissolubility in water is only small, is only 0.024g/L.Prior art is all first be dissolved in organic solvent by emamectin-benzoate, then prepares into aqueous emulsion or microemulsion.
Agent A of the present invention, is that a class can improve emamectin-benzoate material of dissolubility and separating degree in water.Inventor finds by studying, and some specific compound can function as described above, from without by organic solvent, it is possible to prepare the water preparation of emamectin-benzoate.Therefore, agent A has been undertaken preferably by inventor by following experiment.
10ml water adds quantitative different types of compound and quantitative emamectin-benzoate, stirs under room temperature, observe dissolving situation, it is preferable that go out the material type of agent A.Result is in Table 1.
Table 1 agent screening formula and result
By above-mentioned experiment, described agent A is preferably the anion surfactant of the anionic surfactant containing sulfonic acid group, the anionic surfactant of sulfur acid group and carboxyl group.
By further test, it has been found that described agent A is more preferably from straight or branched aliphatic group sulfonic acid and salt, straight or branched aliphatic group sulfonic acid ether and salt, straight or branched aliphatic group sulphuric acid and salt, straight or branched aliphatic group ether sulphuric 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
CH3(CH2)n(OCH2CHR′)mOk(CO2)j(SO3)iM
1
Wherein, n=7-17, it is preferable that n=11,13,15, or 17,
R '=H or CH3,
M=0,1,2,3, or 4,
K=0 or 1,
J=0 or 1,
I=0 or 1, and i ≠ j,
M=H, K, Na, or NH4。
Multifunctional environment friendly emamectin-benzoate water preparation of the present invention can also include agent B.So-called agent B, refers to improving emamectin-benzoate dispersibility in water, improves preparation stability, opposing hard water, reduces the surface tension of inhibitor dilutions and increase the material added in the plant leaf surface effect of sprawling.It accounts for the 1%-6% of gross weight in the formulation.
Killing the effect of insect pest in order to strengthen emamectin-benzoate water preparation, simultaneously work as the effect of plant protection, emamectin-benzoate water preparation of the present invention includes functionalizers.Described functionalizers refer to a class have potentiation, sterilization, degeneration-resistant, stimulate plant growth, improve drug effect, suppress residual hazard, improve the material of the functions such as agricultural product quality, including chemosynthesis material or natural product.Consider from the environmental friendliness of dosage form, it is preferable that natural product, such as tea saponin, humic acids, Chitosan-phospholipid complex, alginate, hyaluronic acid, Fructus Gleditsiae Abnormalis extract, matrine etc., may be optionally added one or more as required.Described functionalizers accounts for the 1%-5% of total formulation weight amount.
In order to improve the performance of emamectin-benzoate water preparation of the present invention further, water preparation of the present invention also includes 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 emamectin-benzoate water preparation of the present invention action time on crop blade face, improving pulverability, other insecticides adjuvant of the present invention includes light stabilizer and/or drift control agents.
Described light stabilizer refers to reduce the material that emamectin-benzoate quickly decomposes under sunlight irradiates, the light stabilizer such as including salicylic acid esters, benzophenone, benzotriazole, hindered amines.Consider from environmental friendliness angle, it is preferable that can be applicable to the light stabilizer of the benzophenone of cosmetics.Consider from the feature of dosage form of the present invention, it is preferable that benzophenone light stabilizer, concrete, it is preferable that from 2,4-dihydroxy-5-sulfonic group benzophenone, 2,2`, 4,4`-tetrahydroxybenzophenone and one or more in 2,3,4,4`-tetrahydroxybenzophenones.Described light stabilizer accounts for the 0.1%-0.4% of total formulation weight amount.
Described drift control agents refers to reduce the surface tension of spray droplet, increases viscosity, improves the deposition of medicine, reduces the auxiliary agent of drop bounce-back, selected from synthetic high polymer matter and natural high molecular substance.Consider from the environmental friendliness of dosage form, prioritizing selection water-soluble natural polymer substance, one or more in water-soluble cellulose derivative, water solublity guar gum and derivant thereof and water soluble starch and derivant thereof.Described drift control agents accounts for the 1%-3% of total formulation weight amount.
In order to meet the formulation requirements of aqueous pesticide solution, the composition of raw materials of water preparation of the present invention also to include 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, including ethylene glycol, propylene glycol, glycerol, low-molecular-weight Polyethylene Glycol, sorbitol etc..Considering from environmental friendliness, the material that prioritizing selection is degradable, such as glycerol, ethylene glycol or propylene glycol.It accounts for the 1%-6% of gross weight in the formulation.
Defoamer of the present invention refers to eliminate the material of foam in the last process of water preparation manufacture, is C selected from organic silicon defoamer commonly used in the art, carbon atom quantity7～C9Fatty alcohol, tributyl phosphate etc., it accounts for the 0.01-0.1% of gross weight in the formulation.
Multifunctional environment friendly emamectin-benzoate water preparation of the present invention, can use the general production equipment of the water baseization formulations of pesticide, carry out, produce workable under normal temperature condition.
Multifunctional environment friendly emamectin-benzoate water preparation of the present invention, it is possible to be applied to the insects such as crop preventing and treating Lepidoptera, Diptera, Homoptera, coleoptera such as veterinary antibiotics, Folium Camelliae sinensis, Oryza sativa L., Semen Maydis, Cotton Gossypii.
Multifunctional environment friendly emamectin-benzoate water preparation of the present invention, should not belong to existing microemulsion.Because inventing in the process of described water preparation in preparation, do not use any organic solvent.And emamectin benzoate microemulsion of the prior art, aqueous emulsion, it is all the solution droplets having dissolved emamectin-benzoate organic solvent scattered system in water.If being distributed to by the xylene solution of emamectin-benzoate in the water preparation system of the present invention not including emamectin-benzoate, oil-water separation will be produced, it is impossible to form the system of stable homogeneous.This shows Multifunctional environment friendly emamectin-benzoate water preparation of the present invention, is not traditional microemulsion.
Tyndall phenomenon is the ins and outs of colloid.So-called " Tyndall phenomenon ", refers to when Ray Of Light is through colloid, from the vertical direction of incident illumination it is observed that bright " path " occurred colloid, is also Tyndall effect (Tyndalleffect).Tyndall effect is exactly scattering of light phenomenon or claims opalescence phenomenon.Colloid can have Tyndall phenomenon, and the purified solution of molecular dispersion is substantially free of, and Tyndall phenomenon therefore can be adopted to distinguish colloid and solution.Microemulsion is to be formed in water by less than being dissolved with in the organic solution droplet distribution of pesticide original medicine of 100nm, it will thus be seen that arrive obvious Tyndall phenomenon.When the Tyndall phenomenon of a kind of liquid system is significantly less than the microemulsion of same concentrations, it is believed that be define a kind of aqueous solution or aqueous dispersion.By following experiment, investigate the Tyndall phenomenon of Multifunctional environment friendly emamectin-benzoate water preparation of the present invention and emamectin benzoate microemulsion of the prior art.
Referring to Fig. 1, it is known that the Tyndall phenomenon of Multifunctional environment friendly emamectin-benzoate water preparation of the present invention is markedly less than the microemulsion of same concentration.This shows the emamectin-benzoate of present invention dispersity in water, more scattered than traditional microemulsion less evenly, disperse closer to solution.
Multifunctional environment close friend's emamectin-benzoate water preparation prepared by the present invention is at room temperature placed 2 years, and dosage form outward appearance does not change, and is still transparence liquid.
The emamectin-benzoate being insoluble in water is grouped compound with preferred agent A by the present invention, the dissolubility in water of emamectin-benzoate is improve two orders of magnitude, it is thus achieved that stable emamectin-benzoate high concentration solution.It can in addition contain improve its performance with preferred agent B.Thus providing a kind of Multifunction environmental friendliness emamectin-benzoate water preparation on this basis.After testing, the property indices of the Multifunctional environment friendly emamectin-benzoate water preparation thus prepared has reached state specified standards:
1. water preparation outward appearance is homogeneous transparent shape, stable storing, it is possible to any ratio is dispersion rapidly, dilution in water.
2. in water preparation, the active constituent content of emamectin benzoate can reach 1-7%, maintains an equal level or higher with the high-load of other liquid dosage form domestic at present.
3. water preparation stability in hard water can be qualified, and muddiness, precipitation do not occur in the hard water of normal concentration.
4. water preparation high-and low-temperature resistance performance is qualified.
Emamectin-benzoate water preparation of the present invention has excellent environmental friendliness performance.The most prominent being characterized by, not containing any organic solvent in preparation, the auxiliary agent of use is all biodegradable material, and environment does not constitute harm, in addition emamectin-benzoate basic noresidue in the environment.Therefore, the emamectin-benzoate water preparation of the present invention improves the environmental friendliness performance of pesticidal preparations to greatest extent.
The present invention is by selecting, use water-soluble chemical synthetic or natural product, preferred water-soluble natural product, as functionalizers, gives the function that novel environmental close friend's emamectin-benzoate water preparation is new so that it is have the effects such as sterilization, degeneration-resistant, potentiation, stimulating growth.Realize this purpose, mainly include the functionalizers roles such as tea saponin, humic acids and chitosan.Tea saponin is a kind of natural nonionic surfactant, has good emulsifying, dispersion, foaming, the function such as moistening, as the wetting agent of pesticidal preparations, synergist and spreader-sticker, and can have certain parasite killing, bactericidal action.Humic acids is the natural polymer organic acid produced through microbial action by plant and animal residues, wherein fulvic acid molecular weight is little, is dissolved in water, and activity is high, there is enhancing crop resistance, to pesticide slow-release potentiation, reduce toxicity, extend drug effect, the effect such as effectively to reduce agriculture residual.Chitosan is the alkaline polysaccharide that uniquely there is cation in nature in a large number, has disease resistance, safety, trace, efficient feature, it is possible to degeneration-resistant, resist pathogenic bacteria and attack, increase production, improve quality of agricultural product.Functionalizers of the present invention is substituted, also in the objective of the present invention and scope with the natural materials that other has similar effect.The present invention also adds the auxiliary agent such as light stabilizer and drift control agents in emamectin-benzoate water preparation, can extend drug effect, improve pulverability.Finally, the invention provides a kind of environmentally friendly emamectin-benzoate water preparation integrating several functions.
It addition, Multifunctional environment friendly emamectin-benzoate water preparation provided by the invention, economic and social benefit is notable, great application value.Described emamectin-benzoate water preparation, only use water as solvent, compared with the liquid dosage forms such as emamectin-benzoate cream of the prior art, microemulsion, aqueous emulsion, mass percent can be replaced respectively and be about the poisonous and hazardous organic solvents such as the dimethylbenzene of 15%-85%, toluene.Not only reduce production cost, and these poisonous and hazardous organic solvents can be avoided to environmental emission, significant for protection environment, saving energy resource and low-carbon emission reduction.Therefore, along with the popularization and application of the Multifunctional environment friendly emamectin-benzoate water preparation of the present invention, significant economic benefit and social benefit will be produced.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is elaborated.
The photo of Fig. 1 is shown that the Tyndall phenomenon photo of Multifunctional environment friendly emamectin-benzoate water preparation of the present invention and commercially available emamectin benzoate microemulsion；Wherein: in the conical flask of left side is 1% Multifunctional environment friendly emamectin-benzoate water preparation of the embodiment of the present invention 1 preparation, and in the conical flask of right side is 1% emamectin benzoate microemulsion
The photo of the Multifunctional environment friendly emamectin-benzoate water preparation of embodiment 1,3 and 5 preparation that the photo of Fig. 2 shows.It is the Multifunctional environment friendly emamectin-benzoate water preparation of embodiment 1,3 and 5 preparation from left to right respectively.
Detailed description of the invention
Below, by preferred embodiment, the present invention is described in detail.But the present invention is not restricted to following embodiment.
Various raw materials used in embodiment all can be by what commercial channel obtained.
Embodiment 1A kind of 1% Multifunctional environment friendly emamectin-benzoate water preparation
Proportioning raw materials:
It is prepared via a method which:
I. according to formulation weight proportioning, prepare to prepare the various raw materials of the multi-functional water preparation of 1kg；
II. respectively castor oil polyoxyethylene ether (EL-40), fatty alcohol-polyoxyethylene ether (AEO-09), dodecyl sodium sulfate, tea saponin, fulvic acid, carboxymethyl chitosan and glycerol are joined in stirred tank, inject the deionized water of 2/3, stirring, makes dissolving, obtains solution A；
III. emamectin-benzoate is added described solution A, stirring, make dissolving, obtain solution B；
IV. hydroxyethyl cellulose is dissolved in remaining deionized water, this solution is added solution B, adds 2,2`, 4,4`-tetrahydroxybenzophenones, at room temperature stir, so as to dissolve, add tributyl phosphate, stir, static, froth breaking.Obtain target product.
1% Multifunctional environment friendly emamectin-benzoate water preparation of above-mentioned preparation, appearance transparent, clarification, referring to Fig. 2.
Embodiment 2A kind of 2% Multifunctional environment friendly emamectin-benzoate water preparation
Proportioning raw materials:
Adopt the preparation method identical with embodiment 1 and step, obtain the target product of the transparent shape of 1kg outward appearance.
Embodiment 3A kind of 3% Multifunctional environment friendly emamectin-benzoate water preparation
Proportioning raw materials:
Adopt the preparation method similar to embodiment 1 and step, obtain the target product of the transparent shape of 10kg outward appearance, referring to Fig. 2.
Embodiment 4A kind of 4% Multifunctional environment friendly emamectin-benzoate water preparation
Proportioning raw materials:
Adopt the preparation method identical with embodiment 1 and step, obtain the target product of the transparent shape of 1kg outward appearance.
Embodiment 5A kind of 5% Multifunctional environment friendly emamectin-benzoate water preparation
Proportioning raw materials:
Adopt the preparation method identical with embodiment 1 and step, obtain the target product of the transparent shape of 1kg outward appearance, referring to Fig. 2.
Embodiment 6The emamectin-benzoate water preparation that a kind of 7% Multifunctional environment is friendly
Proportioning raw materials:
Adopt the preparation method similar to embodiment 1 and step, obtain 1000kg target product.
Embodiment 7The emamectin-benzoate water preparation proportioning raw materials that a kind of 1% Multifunctional environment is friendly:
Adopt the preparation method similar to embodiment 1 and step, obtain 1000kg target product.
Embodiment 8A kind of 3% eco-friendly emamectin-benzoate water preparation
Proportioning raw materials:
Adopt the preparation method similar to embodiment 1 and step, obtain 1000kg target product.
Test example 1The Tyndall phenomenon of Multifunctional environment friendly emamectin-benzoate water preparation of the present invention
Arranged side by side equipped with the conical flask of Multifunctional environment friendly emamectin-benzoate water preparation of 1% of the embodiment of the present invention 1 preparation and conical flask equipped with the emamectin benzoate microemulsion (productions of Shandong ×× Chemical Co., Ltd.) of 1%, the laser that laser pen is launched successively passes through above two liquid.
Result is as shown in Figure 1.Laser first passes through the water preparation of embodiment 1 preparation, is substantially free of appearance " light path ", say, that " Tyndall effect " is very weak；And laser intensity weaken after again through the commercially available microemulsion of same concentrations, liquid occurs in that significantly " light path ", namely creates " Tyndall effect ".Emamectin-benzoate water preparation prepared by embodiment 1 is described, emamectin-benzoate dispersity in water, more scattered than traditional microemulsion less evenly, disperse closer to solution.
Test example 2The test of pesticide effectiveness of Multifunctional environment friendly emamectin-benzoate water preparation of the present invention
Test name: 3% Multifunctional environment friendly emamectin-benzoate water preparation preventing and treating vegetable diamondback moth trial crops: Caulis et Folium Brassicae capitatae
Controlling object: diamondback moth (PlutellaxylostellaL.)
Test medicine: 3% Multifunctional environment friendly emamectin-benzoate water preparation of embodiment 3 preparation, arranges three dosage groups, and described 3% environmentally friendly emamectin-benzoate water preparation dilutes respectively
2000,1500 and 1000 times；
Comparison medicament: commercially available 1% emamectin-benzoate cream
Application method and water consumption: spraying, 900 liters/hectare.Contain at diamondback moth low instar larvae and send out phase dispenser.
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, and three dosage of the environmentally friendly emamectin-benzoate water preparation of test medicine 3% process Caulis et Folium Brassicae capitatae diamondback moth preventive effect respectively 18.21%, 32.03% and 52.67%, and three dosage process preventive effect significant differences.Middle dosage processes and compares 500 times of preventive effects (29.73%) processed of medicament 1% emamectin-benzoate cream dilution quite.After medicine 7 days, the preventive effect that each dosage of test medicine processes was 42.87%-83.49%, and three dosage process preventive effect significant differences.It is suitable with the preventive effect (42.81%) compareing medicament 1% emamectin-benzoate cream that low dosage processes preventive effect；Middle dosage processes the preventive effect 51.66% preventive effect higher than Isodose cream.
It addition, the cabbage leaves of the three of multi-functional water preparation dosage process groups is loose, moist.After within 120 days, trophophase terminates, the yield average specific 1% emamectin-benzoate cream process group increase by 5.2% of above three process group.
Conclusion (of pressure testing):
The quick-acting of Multifunctional environment friendly emamectin-benzoate water preparation of the present invention is suitable with commercially available cream effect, but drug effect persistence is significantly stronger than commercially available cream.Adopt Multifunctional environment friendly water preparation of the present invention can be effectively improved the prevention effect to insect pest, reduce Application, frequency, and then reduce total consumption of emamectin-benzoate.And cream is owing to containing organic solvent, abnormal smells from the patient is pungent, and water preparation of the present invention does not have any penetrating odor.It addition, Multifunctional environment friendly water preparation of the present invention can be obviously promoted by the growth executing plant.In sum, emamectin-benzoate water preparation usefulness of the present invention is higher, advantageously reduce production cost, is more beneficial for environmental conservation；Compared with existing cream preparation, there is significant advantage.
Claims (15)
1. a Multifunctional environment friendly emamectin-benzoate water preparation, it is characterised in that: include emamectin-benzoate, functionalizers and water, do not include organic solvent；According to weight percent meter, consist of:
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；
Described agent A is selected from one or more in dodecyl sodium sulfate, lauryl sulphate acid, myristyl sulfate, sodium tetradecyl sulfate, ammonium tetradecyl sulfate, myristyl ether sodium sulfate, cetyl ether sulphuric acid, potassium oleate, sodium ricinoleate；
Described agent B is selected from the nonionic surfactant containing ethylene oxide unit, propylene oxide unit or glucose unit and/or natural polymeric surface active agent；
Described functionalizers refer to have potentiation, sterilization, degeneration-resistant, stimulate plant growth, improve drug effect, suppress residual hazard, improve chemosynthesis material or the natural product of the function of agricultural product quality.
2. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 1, it is characterised in that the percentage by weight of agent A is 2%-8%.
3. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 1, it is characterised in that: one or more in polyethylene glycol oxide and polypropylene oxide of described nonionic surfactant；
One or more in water soluble starch derivatives, water-soluble cellulose derivative and Chitosan-phospholipid complex of described natural polymeric surface active agent.
4. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 3, it is characterized in that: described nonionic surfactant is selected from straight chain fatty polyoxyethylenated alcohol, one or more in straight chain fatty acid polyoxyethylene ester, straight-chain fatty amine polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, APG and castor oil polyoxyethylene ether.
5. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 3, it is characterised in that: one or more in dextrin, carboxymethyl starch, carboxymethyl cellulose, chitosan, carboxymethyl chitosan and Quaternary Ammonium Salt of Chitosan of described natural polymeric surface active agent.
6. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 1, it is characterised in that: one or more in tea saponin, humic acids, Chitosan-phospholipid complex, alginate, hyaluronic acid, Fructus Gleditsiae Abnormalis extract, matrine etc. of described functionalizers.
7. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 1, it is characterised in that: other insecticides adjuvant described includes light stabilizer and/or drift control agents；
Wherein, described light stabilizer accounts for the 0.1-0.4% of total formulation weight amount；One or more in salicylic acid esters, benzophenone, benzotriazole and hindered amine light stabilizer；
Described drift control agents accounts for the 1%-3% of total formulation weight amount；Selected from the surface tension that can reduce spray droplet, increase viscosity, improve the deposition of medicine, reduce water solublity synthetic high polymer matter and the natural high molecular substance of drop bounce-back.
8. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 7, it is characterised in that: described light stabilizer is selected from benzophenone light stabilizer.
9. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 8, it is characterized in that: described light stabilizer is selected from 2,4-dihydroxy-5-sulfonic group benzophenone, 2,2`4,4`-tetrahydroxybenzophenone, 2, one or more in 3,4,4`-tetrahydroxybenzophenones.
10. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 7, it is characterised in that: described drift control agents one in water-soluble cellulose derivative, water solublity guar gum and derivant thereof and water soluble starch and derivant thereof is several.
11. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 1, it is characterised in that: one or more in ethylene glycol, propylene glycol, glycerol, low-molecular-weight Polyethylene Glycol and sorbitol of described antifreezing agent.
12. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 11, it is characterised in that: described antifreezing agent is selected from one or more of glycerol, ethylene glycol and propylene glycol.
13. Multifunctional environment friendly emamectin-benzoate water preparation according to claim 1, it is characterised in that: described defoamer is C selected from organic silicon defoamer, carbon atom quantity7～C9Fatty alcohol and tributyl phosphate in one or more.
14. the preparation method of Multifunctional environment friendly emamectin-benzoate water preparation described in any one of claim 1 to 13, it is characterized in that: include first being dissolved in part water by described agent A, add emamectin-benzoate and remaining water.
15. preparation method according to claim 14, it is characterised in that described preparation method comprises the steps:
I. various raw materials are prepared according to formulation weight proportioning；
II. except emamectin-benzoate, outside defoamer and other insecticides adjuvant, other raw material that formula includes described agent A adds stirred tank, injects part water, stirring, makes dissolving, obtain solution A；
III. emamectin-benzoate is added described solution A, stirring, make dissolving, obtain solution B；
IV. other insecticides adjuvant described and remaining water are added in described solution B, stirring, make dissolving；Add defoamer, gentle agitation, static, filter, to obtain final product.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410052228.5A CN103858936B (en) | 2014-02-14 | 2014-02-14 | A kind of Multifunctional environment friendly emamectin-benzoate water preparation and preparation method thereof |
| EP15749075.6A EP3106031B1 (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 |
| PCT/CN2015/072545 WO2015120786A1 (en) | 2014-02-14 | 2015-02-09 | Environmentally-friendly emamectin benzoate preparation and preparation method therefor |
| US15/118,825 US10206402B2 (en) | 2014-02-14 | 2015-02-09 | Environmentally-friendly emamectin benzoate preparation and preparation method therefor |
| AU2015218092A AU2015218092B2 (en) | 2014-02-14 | 2015-02-09 | Environmentally-friendly emamectin benzoate preparation and preparation method therefor |
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| AU2015218092B2 (en) * | 2014-02-14 | 2017-09-21 | Nanjing Scienx Biological Technology Co., Ltd. | Environmentally-friendly emamectin benzoate preparation and preparation method therefor |
| CN103858861B (en) * | 2014-02-14 | 2016-05-04 | 南京善思生物科技有限公司 | A kind of environmentally friendly emamectin-benzoate aqua and preparation method thereof |
| CN109336451B (en) * | 2018-11-12 | 2021-03-26 | 武汉市浩盛特种建材有限责任公司 | Low-alkali high-strength large-porosity plant-growing concrete admixture |
| CN111011368A (en) * | 2019-11-11 | 2020-04-17 | 南京华洲药业有限公司 | Composite insecticidal and acaricidal nano-water agent containing efficient cyhalothrin and emamectin benzoate and application thereof |
| CN110973154A (en) * | 2019-11-13 | 2020-04-10 | 南京华洲药业有限公司 | Composite insecticidal and acaricidal nano water agent containing fenpropathrin and emamectin benzoate and application thereof |
| CN114342946B (en) * | 2021-12-27 | 2023-01-17 | 陕西新指南针化工科技服务有限责任公司 | Emamectin benzoate aqueous solution and preparation method thereof |
| CN115191430B (en) * | 2022-06-02 | 2023-07-07 | 中国科学院化学研究所 | Application of biomass-based surfactant system as auxiliary agent in improving effective utilization rate of pesticide |
| CN116491516A (en) * | 2023-03-02 | 2023-07-28 | 河北威远生物化工有限公司 | Emamectin benzoate B 2a Application of salt compound thereof in preparation of medicine for promoting plant growth |
| CN116253626B (en) * | 2023-03-10 | 2023-09-01 | 中国农业科学院农业环境与可持续发展研究所 | Alcohol ether compound and application thereof in water-based nano pesticide preparation |
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