Difenoconazole propiconazole suspension emulsion and preparation method thereof
Technical field
The present invention relates to a kind of biocide preparation of broad spectrum activity, relate in particular to a kind of Difenoconazole propiconazole suspension emulsion and preparation method thereof.
Background
Difenoconazole belongs to interior absorption sterilization, tool protection and therapeutic action.Fungicidal spectrum is wide, and blade face or seed treatment can improve output and the guaranteed quality of crop.To Ascomycetes, Basidiomycetes and comprise Alternaria, Ascochyta, the mould genus of tail spore, Colletotrichum, ball Cuo Pseudomonas, Phoma, Ramularia, Septoria, Venturia partly know disease, Erysiphaceae, Uredinales and some are planted and are passed pathogen lasting protection and therapeutic action are arranged.
Propiconazole is a kind of interior absorption triazole bactericidal agent with protection and therapeutic action; can be absorbed by root, stem, leaf portion; and can be soon in the plant strain body on conduction; the control sac fungi; the disease that basidiomycetes and imperfect fungus cause; particularly to take-all, powdery mildew, rust, root rot, water rice bakanae disease, sigatoka have the better prevention effect.
The Difenoconazole list agent of domestic market sale at present is based on missible oil EC and water dispersible granules WDG; Single agent of propiconazole is based on missible oil EC, and the complex preparation of Difenoconazole and propiconazole is based on missible oil EC, this quasi-tradition preparation (as missible oil) in a large number with an organic solvent with surfactant, not only wasted valuable resource, simultaneously also severe contamination environment for use.
Summary of the invention
The present invention is in order to overcome the problem that prior art exists, and a kind of Difenoconazole propiconazole suspension emulsion that provides and preparation method thereof, by Difenoconazole, two kinds of pesticide activity components of propiconazole are re-dubbed a kind of be the stable suspension emulsion of medium with water, economize on resources, improve control efficiency and environmental purpose thereby reach.
To achieve these goals, Difenoconazole propiconazole suspension emulsion, be characterized in, the component that mainly contains following percentage by weight: Difenoconazole 10~20%, propiconazole 10~20%, wetting dispersing agent 2~6%, solvent 5~15%, emulsifier 2~10%, thickener 2~10%, adjuvant 0~10%, water surplus, supplying total weight percent is 100%.
Above-mentioned Difenoconazole propiconazole suspension emulsion, wherein, described wetting dispersing agent is selected naphthalenesulfonic acid-formaldehyde condensate for use, triphenyl vinyl phenol polyethenoxy ether class and derivative eater, fatty alcohol polyethenoxy ether class, the alkylphenol polyoxyethylene class, macromolecule EO-PO block copolymer, lignosulfonates, alkylphenol-polyethenoxy formaldehyde condensation products sulphate, alkylphenol polyoxyethylene formaldehyde condensation products sulphate phosphate, styrene phenol formaldehyde resin polyoxyethylene ether phosphate salt, styryl phenol polyethenoxy polyethenoxy ether, the alkyl naphthalene formaldehyde condensate sulfonates, macromolecule is dredged a dress copolymer of type, being used in combination more than two kinds or three kinds in the polymerization of carboxylic acid salt.
Above-mentioned Difenoconazole propiconazole suspension emulsion, wherein, described solvent is selected from a kind of in toluene, dimethylbenzene, aliphatic solvent oil, cyclohexanone, methylated vegetable oil, mineral oil, aromatic solvent naphtha, N-Methyl pyrrolidone, carrene, methyl-sulfoxide, the benzinum.
Above-mentioned Difenoconazole propiconazole suspension emulsion, wherein, described emulsifier is selected macromolecule EO-PO block copolymer for use, Nonyl pheno (NP series), alkylphenol-polyethenoxy polyethers and sulphate thereof or phosphoric acid fat, fatty alcohol-polyoxyethylene ether (AEO series), the polyoxyethylene nonylphenol ether phosphate, alkylphenol polyoxyethylene formaldehyde condensation products sulphate phosphate, styrene phenol formaldehyde resin polyoxyethylene ether phosphate salt, styryl phenol polyethenoxy polyethenoxy ether, this dish SPAN series, one or more kinds of being used in combination in the soil temperature TWEEN series.
Above-mentioned Difenoconazole propiconazole suspension emulsion, wherein, described thickener is selected from the one or more kinds of combinations in xanthans, cellulose ether and derivative thereof, polyethylene glycol, PVAC polyvinylalcohol, aluminium-magnesium silicate, bentonite, kaolin, diatomite, white carbon, polyvinyl alcohol, gelatin, the gum Arabic.
Above-mentioned Difenoconazole propiconazole suspension emulsion, wherein, described adjuvant is selected from one or more the combination in antifreeze, PH conditioning agent, sterilization antiseptic, the defoamer; Wherein:
Described antifreeze is selected from a kind of in ethylene glycol, propane diols, glycerine, PEG400, isopropyl alcohol, the urea; It accounts for 0~10% of total weight percent;
Described PH acid-base modifier is selected from a kind of among glacial acetic acid, hydrochloric acid, citric acid, ammoniacal liquor, monoethanolamine, triethanolamine, the NaOH; Institute's expense is adjusted in the stability range for the pH value with final products;
A kind of its that described sterilization antiseptic is selected from formaldehyde, potassium sorbate, Sodium Benzoate, formaldehyde, the isothiazolinone accounts for 0.1~0.5% of total weight percent;
Described defoamer is selected from a kind of in silicon defoamer, polyethers defoamer, higher alcohols, tributyl phosphate, the polysiloxane defoamers, and it accounts for 0.5~2% of total weight percent.
Above-mentioned Difenoconazole propiconazole suspension emulsion, wherein, described water is deionized water or distilled water.
The preparation method of Difenoconazole propiconazole suspension emulsion is characterized in, according to above-mentioned described raw material components and ratio, may further comprise the steps:
Step 1: in deionized water, add wetting dispersing agent, silicone defoaming agent mixing and stirring, after dropping into difenoconazole technical material then and being uniformly dispersed, carry out the serialization sand milling by horizontal sand mill, the sand milling temperature is controlled at below 40 ℃, granularity stops sand milling after reaching claimed range, obtains the suspending agent of Difenoconazole;
Step 2: propiconazole is dissolved in the solvent, obtains oil phase after stirring; The difenoconazole suspending agent that emulsifier, step 1 are prepared joins to stir evenly in the deionization and obtains water; The oil phase that configures is poured into aqueous phase and open the high speed homogenizing, form stable suspension emulsion;
Step 3: in the Difenoconazole propiconazole suspension emulsion for preparing, open and stir, add antifreeze, thickener, bactericide then, stir, promptly make Difenoconazole propiconazole suspension emulsion finished product.
The preparation method of Difenoconazole propiconazole suspension emulsion is characterized in, according to above-mentioned described raw material components and ratio, may further comprise the steps:
Step 1: in deionized water, add wetting dispersing agent, silicone defoaming agent mixing and stirring, after dropping into difenoconazole technical material then and being uniformly dispersed, carry out the serialization sand milling by horizontal sand mill, the sand milling temperature is controlled at below 40 ℃, granularity stops sand milling after reaching claimed range, obtains the suspending agent of Difenoconazole;
Step 2: propiconazole is dissolved in the solvent, obtains oil phase after stirring; Emulsifier joined to stir evenly in the deionization obtain water; The oil phase that configures to going into aqueous phase and open the high speed homogenizing, is formed propiconazole emusion in water, treat that the propiconazole emusion in water granularity reaches requirement after, add the difenoconazole suspending agent that step 1 prepares then, stir, obtain suspension emulsion;
Step 3: in the Difenoconazole propiconazole suspension emulsion for preparing, open and stir, add antifreeze, thickener, bactericide then, stir, promptly make Difenoconazole propiconazole suspension emulsion finished product.
The preparation method of above-mentioned Difenoconazole propiconazole suspension emulsion, wherein, it is average grain diameter 0.5 μ m~1.5 μ m that the described aqueous emulsion granularity of step 2 reaches requirement.
The preparation method of above-mentioned Difenoconazole propiconazole suspension emulsion, wherein, it is average grain diameter 1 μ m~5 μ m that the described suspending agent granularity of step 1 reaches requirement.
Because the present invention has adopted above technical scheme, the technique effect of its generation is tangible:
1, suspension emulsion of the present invention is combined in two pesticide activity components in the same formulation, and the biological control effect can be complementary, prevents and treats pedigree thereby enlarged; Can avoid single agent bucket to mix the problem of immiscible property during use, improve agricultural production efficiency;
2, the present invention is continuous media with water, to the producer and user's safety, environment is had environmental-protection function; Making water is that continuous media also can effectively reduce excitant and the toxicity to skin and eyes;
3, the present invention does not use or reduces the usage amount of organic solvent (as: toluene, xylene), has avoided inflammable, explosive in the production and the poisoning problem; Packing, storage and freight are reduced, save production cost.
Embodiment
The present invention is with Difenoconazole and two kinds of active ingredients of propiconazole, add relevant wetting dispersing agent, solvent, emulsifier, thickener, adjuvant, by the formulations of pesticide compounded technology of water baseization, preparing with water is the environment-friendly type preparation Difenoconazole propiconazole suspension emulsion SE of medium.Difenoconazole and propiconazole belong to the interior absorption triazole bactericidal agent with protection and treatment, wherein:
The Difenoconazole physicochemical property: the benzene product are colorless solid, 76 ℃ of fusing points, 220 ℃/4Pa of boiling point, vapour pressure 120nPa (20 ℃).Dissolubility (20 ℃): water 3.3 mg/litre are soluble in organic solvent.≤ 300 ℃ stable, and mobility is little in soil, slowly degraded.
The propiconazole physicochemical property: former medicine outward appearance is faint yellow sticking silk fabric liquid, 180 ℃ of boiling points (13.3Pa), vapour pressure (20 ℃) 0.133mPa, index of refraction 1.5468, proportion (20 ℃) 1.27g/cm3.Solvability is 110mg/L in water, is soluble in organic solvent.Stable below 320 ℃, more stable to light, hydrolysis is not obvious.More stable in acid, alkaline medium, corroding metal not.
Difenoconazole propiconazole suspension emulsion of the present invention, the component that mainly contains following percentage by weight: Difenoconazole 10~20%, propiconazole 10~20%, wetting dispersing agent 2~6%, solvent 5~15%, emulsifier 2~10%, thickener 2~10%, adjuvant 0~10%, water surplus, supplying total weight percent is 100%.
Be distributed in the whole system because suspension emulsion Central Plains pharmaceutically active ingredient is the form of emulsion particle, can use the former medicine of some dissolution with solvents solids or dilute the former medicine of full-bodied liquid.There is the phenomenon of oiling dissolving on the part solia particle surface that can cause solid dispersed phase in the suspension emulsion under these solvent actions, and causes the problem of Ostwald ripening (promptly generate crystallization and crystal is grown up), finally causes the instability of suspension emulsion.The present invention effectively avoids the appearance of above-mentioned phenomenon by screening suitable wetting dispersing agent.Wetting dispersing agent of the present invention is selected naphthalenesulfonic acid-formaldehyde condensate for use, triphenyl vinyl phenol polyethenoxy ether class and derivative eater, fatty alcohol polyethenoxy ether class, the alkylphenol polyoxyethylene class, macromolecule EO-PO block copolymer, lignosulfonates, alkylphenol-polyethenoxy formaldehyde condensation products sulphate, alkylphenol polyoxyethylene formaldehyde condensation products sulphate phosphate, styrene phenol formaldehyde resin polyoxyethylene ether phosphate salt, styryl phenol polyethenoxy polyethenoxy ether, the alkyl naphthalene formaldehyde condensate sulfonates, macromolecule is dredged a dress copolymer of type, being used in combination more than two kinds or three kinds in the polymerization of carboxylic acid salt.
Because in the suspension emulsion, the former medicine of propiconazole exists in the whole suspension system with the form of emulsion particle, is the high viscosity liquid shape under this former medicine normal temperature, so will screen a kind of thinner (solvent), be used for effectively reducing the viscosity of propiconazole, prepare more stable emulsion system.And this thinner (solvent) is answered water insoluble or micro-solvability is arranged in water.The propiconazole emulsion particle that makes should be stable under the temperature of production and product duration of storage, can not have crystallization to separate out.Thinner (solvent) has high flash-point simultaneously, the safety during with the assurance preparation.Solvent of the present invention is selected from a kind of in toluene, dimethylbenzene, aliphatic solvent oil, cyclohexanone, methylated vegetable oil, mineral oil, aromatic solvent naphtha, N-Methyl pyrrolidone, carrene, methyl-sulfoxide, the benzinum, can reach stable effect.
Because suspension emulsion is disperse phase (comprising: a solia particle and emulsion particle) stable and uniform to be dispersed in water is among the medium of continuous phase, because emulsion dispersion belongs to unsettled system on thermodynamics, cause coacervation or emulsion attached collection breakdown of emulsion on solid dispersed phase of system easily.So the emulsifier of the present invention's screening can effectively be avoided this point, obtains stable suspension emulsion.Emulsifier of the present invention is selected macromolecule EO-PO block copolymer for use, Nonyl pheno (NP series), alkylphenol-polyethenoxy polyethers and sulphate thereof or phosphoric acid fat, fatty alcohol-polyoxyethylene ether (AEO series), the polyoxyethylene nonylphenol ether phosphate, alkylphenol polyoxyethylene formaldehyde condensation products sulphate phosphate, styrene phenol formaldehyde resin polyoxyethylene ether phosphate salt, styryl phenol polyethenoxy polyethenoxy ether, this dish SPAN series, one or more kinds of being used in combination in the soil temperature TWEEN series.
Thickener of the present invention is selected from the one or more kinds of combinations in xanthans, cellulose ether and derivative thereof, polyethylene glycol, PVAC polyvinylalcohol, aluminium-magnesium silicate, bentonite, kaolin, diatomite, white carbon, polyvinyl alcohol, gelatin, the gum Arabic.
Described adjuvant is selected from one or more the combination in antifreeze, PH conditioning agent, sterilization antiseptic, the defoamer; Wherein: described antifreeze is selected from a kind of in ethylene glycol, propane diols, glycerine, PEG400, isopropyl alcohol, the urea; It accounts for 0~10% of total weight percent; Described PH acid-base modifier is selected from a kind of among glacial acetic acid, hydrochloric acid, citric acid, ammoniacal liquor, monoethanolamine, triethanolamine, the NaOH; Institute's expense is adjusted in the stability range for the pH value with final products; A kind of its that described sterilization antiseptic is selected from formaldehyde, potassium sorbate, Sodium Benzoate, formaldehyde, the isothiazolinone accounts for 0.1~0.5% of total weight percent; Described defoamer is selected from a kind of in silicon defoamer, polyethers defoamer, higher alcohols, tributyl phosphate, the polysiloxane defoamers, and it accounts for 0.5~2% of total weight percent.
Described water is deionized water or distilled water.
The present invention has adopted a kind of low cost, is convenient to the preparation method and the process route of the suspension emulsion of suitability for industrialized production.Because in the suspension emulsion of the present invention, the former medicine of Difenoconazole exists in the whole suspension system with the form of solia particle, this former medicine belongs to the former medicine of low melting point (76 ℃ of fusing points), the general method of pulverizing has dry pulverization process and waterproof pulverization, the way that the former medicinal powder of the solid that adopts among the present invention is broken, select the broken difenoconazole technical material of wet method hypothermia grait abrasive dust, obtain the suspension system of solia particle, the emulsion system with propiconazole is deployed into suspension emulsion then.
Now further describe the technology of the present invention in order better to illustrate by following instantiation.Described embodiment only is exemplary, is not in order to limit the present invention.The technical staff in the technical field of the invention without departing from the spirit and scope of the present invention, can be used for a variety of modifications and variations.Therefore, protection scope of the present invention is with being as the criterion that claims were defined.
Embodiment one:
The first step: with 25g deionized water and Nekal BX 1.0g (the wetting dispersing agent product of BASF AG's Negel), MD-T 3.0g (the dispersant product of the Nantong Lian Nong EO/PO of company block copolymer), silicone defoaming agent 0.5g mixing and stirring, after the difenoconazole technical material that drops into 10g then is uniformly dispersed, carry out the serialization sand milling by horizontal sand mill, the sand milling temperature is controlled at below 40 ℃, granularity stops sand milling (actual measurement average grain diameter 1.5 μ m) after reaching claimed range, obtains the suspending agent SC of Difenoconazole.
Second step: the propiconazole of 10g is dissolved in the esterification soybean oil of 5g (commercial material), obtains oil phase after stirring; Stir evenly (water) in the deionization with Pluronic PE6800 (emulsifier production of the PO-EO of BASF AG block copolymer), the 28.4g of 2.0g; The oil phase that configures to going into water and opening the high speed homogenizing, is formed stable O/W emulsion, and granularity stops the aqueous emulsion EW that homogenizing (actual measurement average grain diameter 0.5 μ m~1.5 μ m) obtains propiconazole after reaching claimed range.
The 3rd step: in the difenoconazole suspending agent SC 39.5g for preparing, add the propiconazole emusion in water EW 45.4g for preparing, open to stir simultaneously (keeping 200 changes/min), add then ethylene glycol 5.0g, 10g xanthans (2%) aqueous solution, the triumphant loose 0.1g of bactericide (isothiazolinone compounds), stir, the average granula 1.43 μ m of final products promptly make 20% Difenoconazole propiconazole suspension emulsion SE.
Embodiment two,
The first step: with 24g deionized water and Igepal BC/100 1.0g (the wetting dispersing agent product of Rhodia), dispersant MD 3.0g (Nantong Lian Nong company alkylphenol-polyethenoxy polyethers phosphoric acid lipid product), silicone defoaming agent 1g mixing and stirring, after the difenoconazole technical material that drops into 15g then is uniformly dispersed, carry out the serialization sand milling by horizontal sand mill, the sand milling temperature is controlled at below 40 ℃, granularity stops sand milling (actual measurement average grain diameter 4.56 μ m) after reaching claimed range, obtains the suspending agent SC of Difenoconazole.
Second step: the propiconazole of 15g is dissolved in the aliphatic solvent oil of 8g (commercial material), obtains oil phase after stirring; The emulsifier LS (Nantong Lian Nong company polyoxyethylene polyethers product) of 3.0g, the 43g difenoconazole suspending agent SC for preparing are joined in the deionization of 20.3g and stir evenly (water); The oil phase that configures to going into water and opening the high speed homogenizing, is formed stable suspension emulsion SE.
The 3rd step: in the Difenoconazole propiconazole suspension emulsion SE for preparing, open to stir (keeping 180 changes/min), xanthans (2%) aqueous solution, PVAC polyvinylalcohol 0.5g, the bactericide Sodium Benzoate 0.2g that add propane diols 2.0g, 7.0g then stir, and promptly make 30% Difenoconazole propiconazole suspension emulsion SE (the average granula 2.39 μ m of final products).
Embodiment three,
The first step: with 30g deionized water and Cresplus 1209 1.0g (the nonionic wetting dispersing agent product of standing grain major company), Atlox 4913 3.0g (polycarboxylate salt dispersant's agent product of standing grain major company), silicone defoaming agent 1g mixing and stirring, after the difenoconazole technical material that drops into 20g then is uniformly dispersed, carry out the serialization sand milling by horizontal sand mill, the sand milling temperature is controlled at below 40 ℃, granularity stops sand milling (actual measurement average grain diameter 3.8 μ m) after reaching claimed range, obtains the suspending agent SC of Difenoconazole.
Second step: the propiconazole of 20g is dissolved among the EXXSOL D80 of 8g (Exxon Mobil Corporation's aliphatic solvent oil), obtains oil phase after stirring; The emulsifier Atlox 4912 (the block high polymer product of standing grain major company) of 4.0g, the 54.5g difenoconazole suspending agent SC for preparing are joined in the deionization of 10g and stir evenly (water); The oil phase that configures to going into water and opening the high speed homogenizing, is formed stable suspension emulsion SE.
The 3rd step: in the Difenoconazole propiconazole suspension emulsion SE for preparing, open to stir (keeping 180 changes/min), xanthans (2%) aqueous solution, PVAC polyvinylalcohol 1.0g, the triumphant loose 0.1g of bactericide that add 3.0g then stir, and promptly make 40% Difenoconazole propiconazole suspension emulsion SE (the average granula 3.05 μ m of final products).
The key technical indexes of the present invention such as following table: