CN102511475B - Composite emulsion stabilizer for preparing stable pesticide emulsion in water - Google Patents
Composite emulsion stabilizer for preparing stable pesticide emulsion in water Download PDFInfo
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- CN102511475B CN102511475B CN2011104076538A CN201110407653A CN102511475B CN 102511475 B CN102511475 B CN 102511475B CN 2011104076538 A CN2011104076538 A CN 2011104076538A CN 201110407653 A CN201110407653 A CN 201110407653A CN 102511475 B CN102511475 B CN 102511475B
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Abstract
The invention discloses a composite emulsion stabilizer for preparing a stable pesticide emulsion in water, belonging to the field of colloid and interface chemistry. The composite emulsion stabilizer comprises unmodified nano silica particles and an amphiphilic compound, wherein the amphiphilic compound is a cationic surfactant or cation/nonionic mixed surfactant. The composite emulsion stabilizer is suitable for liquid or solid technical materials which are insoluable or poorly soluble in water and can keep chemical stabilization when being dispersed in aqueous mediums. The emulsion in water contains 5-70 % of the technical materials and no larger than 3 % of emulsion stabilizer, thus the cost is relatively low. Because of the good synergistic effect between the nano silica and the amphiphilic compound, the prepared pesticide emulsion in water has hyperstability, and can be stored more than two years at normal temperature without demulsification. The application of the composite emulsion stabilizer can change missible oil into the emulsion in water, thus the amount of organic solvents is greatly reduced, and the resource waste and environmental pollution are reduced.
Description
Technical field
The present invention relates to a kind of mixed emulsifying stabilizer and application thereof for the preparation of stablizing pesticide emulsion in water, relate generally to farm chemical emulgent and pesticide emulsion in water, belong to the Colloid and interface chemistry field.
Background technology
As everyone knows, using agricultural chemicals is important measures that guarantee agricultural foison.But because pesticide original medicine is scarcely water-soluble, in China, mostly be made into missible oil and use, will consume hundreds of thousands ton organic solvent for this reason every year, not only waste resource, and cause serious environmental pollution.One of method that solves is exploitation aqueous pesticide preparation, as former medicine made to oil-in-water (O/W) type microemulsion or emulsion, is called microemulsion and aqueous emulsion.Yet the micro-emulsion formulation technical sophistication, dosage of surfactant is large, cost is high, be difficult to promote, although and low with the stable aqueous emulsion cost of conventional surfactants, owing to being thermodynamic unstable system, be difficult to long term storage.
It is found that in recent years having surface-active nano particle can be adsorbed in oil/water termination stable emulsion, and because the adsorption free energy of nano particle can be than large thousands of times of heat energy (kT), its absorption in oil/water termination is almost irreversible, with it, as emulsion prepared by emulsifier, therefore has superstability.This makes the overstable pesticide emulsion in water of preparation become technically possibility.
Yet most of commodity nano particles be not often too hydrophilic be exactly oleophylic too, substantially do not have surface-active, separately stable emulsion.Making them obtain one of surface-active method is surface modification, and for example nanometer silicon dioxide particle, after the modification of surface silicon alkanisation, can make its hydrophily significantly reduce, and lipophile significantly increases, thereby becomes surfactant granules, can stable emulsion.But the surface modification cost is large, often cause the cost of emulsifier to rise at double, and the surface-active of particle immobilizes.The present invention utilize nanometer silicon dioxide particle with micro-cationic surfactant, to occur to interact in aqueous medium and original position (
In situ) surface activation, become surfactant granules, not only cost is low, and the surface-active of particle is adjustable.Due to the existence of surfactant, while making the aqueous emulsion dilution use, plant surface is had to good wetability, thereby solved satisfactorily the Related Technical Issues of long term storage and the use of aqueous emulsion simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of emulsifier or stabilizing agent of efficient, pervasive emulsion, for the preparation of overstable pesticide emulsion in water.
Technical scheme of the present invention: a kind of mixed emulsifying stabilizer for the preparation of stablizing pesticide emulsion in water, by with unmodified nanometer silicon dioxide particle and parents' compound is composite forms.Silica dioxide granule by the in-situ surface activate, obtains good surface-active by Liquidity limit parents compound in aqueous medium.
The primary particle diameter of nanometer silicon dioxide particle used is 5～200 nm, without any surface modification, adds concentration and counts 0.1% ~ 3% with the water weight of emulsion.Parents' compound used is the binary mixture of single cationic surface active agent or cationic surface active agent and nonionic surface active agent.The lipophilic group of these surfactants is straight or branched, saturated or unsaturated, the alkyl that contains or do not contain benzene ring structure, and chain length is C
8~ C
18.Hydrophilic group is partly cationic as quaternary ammonium salt, pyridine type ammonium salt, imidazoline type ammonium salt etc.; Nonionic such as polyoxyethylene, polyalcohol, alkylolamides type etc.The working concentration of parents' compound is counted 1*10 with the water volume of emulsion
-7Mol/L～0.05mol/L.
This emulsion stabilizer is applicable to prepare pesticide emulsion in water.Applicable agricultural chemicals comprises insoluble or is slightly soluble in water, is dispersed in aqueous medium and can keeps chemically stable liquid state or solid-state former medicine.Liquid former medicine such as benthiocarb, EPTC, esprocarb etc., the percentage by volume in aqueous emulsion is 5% ~ 70%; Solid-state former medicine such as chlopyrifos, triallate, dimepiperate, Imidacloprid, Diacloden, clothianidin, MTI-446, thiacloprid, beta-cypermethrin, spiral shell mite esters etc., be dissolved in suitable organic solvent, and in aqueous emulsion, the percentage by volume of organic facies is 5% ~ 70%.Applicable organic solvent is alkanes such as hexane and thiacyclohexane etc., aromatic hydrocarbons such as toluene, dimethylbenzene etc., fatty acid ester such as ethyl acetate, fatty acid methyl ester, fatty-acid ethyl ester etc., and C
5~ C
10Aliphatic alcohols etc.Water for the preparation of emulsion can be deionized water, running water or from the natural water of rivers and lakes well.Can contain ethylene glycol and other alcohols antifreezing agent, mass concentration 1% ~ 5%.
Applying the concrete grammar that this emulsion stabilizer prepares overstable pesticide emulsion in water is, parents' compound is water-soluble, be scattered in parents' compound water solution nanometer silicon dioxide particle is ultrasonic again, then add organic facies, by ultrasonic dispersion or high-shear emulsifying, make oil/water two-phase emulsification.
Beneficial effect of the present invention: the invention provides a kind of emulsion stabilizer of pesticide emulsion in water of general type, be applicable in theory that all are insoluble or be slightly soluble in water, be scattered in aqueous medium and can keep the former medicine of chemically stable liquid state maybe can be dissolved in organic solvent, be scattered in aqueous medium and can keep chemically stable solid-state former medicine.This makes and missible oil is transformed into to aqueous emulsion becomes technically possibility, thereby can significantly reduce consumption and the environmental pollution of organic solvent.Emulsion stabilizer consumption of the present invention is low, and efficiency is high, also helps the overall cost that reduces pesticidal preparations.
The accompanying drawing explanation
Fig. 1. the outward appearance photo under benthiocarb aqueous emulsion normal temperature after one week of preparation.Benthiocarb/water volume ratio 1:1, nanometer SiO
2Mass fraction (with respect to water) 2%, surfactant and concentration thereof (with respect to water) are from left to right: without (0), CTAB (3*10
-4Mol/L), CTAB (3*10
-4Mol/L)-TX-10 (1*10
-4Mol/L).
Fig. 2. the hot outward appearance photo that stores up benthiocarb aqueous emulsion after month under 54 ° of C, the same Fig. 1 of relevant parameter.
Fig. 3. the microphoto of benthiocarb aqueous emulsion.A, B and C are the microphoto after one week of preparation under normal temperature, the same Fig. 1 of relevant parameter.D, E and F are the microphoto of heat storage after one month, the same Fig. 2 of relevant parameter.
Fig. 4. under high performance aqueous emulsion of cypermethrin normal temperature, place the outward appearance photo in a week.Beta-cypermethrin toluene solution (mass ratio 6:10)/water volume ratio=1:1; From left to right: nanometer SiO
2Mass fraction (with respect to water) 1%, 1%, 1%, 2%, 3%, 1%, 1%, 2%, 2%, 2%; CTAB concentration 0,1*10
-4Mol/L, 3*10
-4Mol/L, 3*10
-4Mol/L, 3*10
-4Mol/L, 6*10
-4Mol/L, 1*10
-3Mol/L, 3*10
-4Mol/L, 3*10
-4Mol/L, 3*10
-4Mol/L; TX-10 concentration 0,0,0,0,0,0,0,1*10
-4Mol/L, 1*10
-3Mol/L, 1*10
-2Mol/L.
Fig. 5. the outward appearance photo of heat storage after one month under 54 ° of C of high performance aqueous emulsion of cypermethrin.The same Fig. 4 of relevant parameter.
Fig. 6. the microphoto under high performance aqueous emulsion of cypermethrin normal temperature after one week of storage.Beta-cypermethrin toluene solution (mass ratio 6:10)/water volume ratio=1:1; From A to G, nanometer SiO
2Mass fraction (with respect to water) 1%, 1%, 1%, 2%, 3%, 1%, 2%; CTAB concentration 0,1*10
-4Mol/L, 1*10
-4Mol/L, 3*10
-4Mol/L, 3*10
-4Mol/L, 1*10
-3Mol/L, 3*10
-4Mol/L; TX-10 concentration 0,0,0,0,0,0,1*10
-4Mol/L.
The microphoto of heat storage after one month under 54 ° of C of Fig. 7 high performance aqueous emulsion of cypermethrin.The same Fig. 6 of relevant parameter.
Embodiment
Embodiment 1, the benthiocarb aqueous emulsion
Benthiocarb, English name thiobencarb, have another name called benthiocarb, weed eradication pellet, Benthiocarb etc.Low to people, animal and birds toxicity.Be widely used in water paddy and wheat class, soybean, peanut, corn, vegetable fields and orchard etc. as weed killer herbicide.
Benthiocarb is insoluble in water, but is soluble in organic solvent, therefore mostly makes at present 50% or 80% missible oil and uses.Obviously this need to consume a large amount of organic solvents, causes environmental pollution and waste.As the former medicine of a kind of liquid state, apply emulsion stabilizer of the present invention, can make overstable aqueous emulsion and without using any organic solvent.
In the cylindricality bottle of a series of high 6.5cm, diameter 2.5cm, first take proper amount of nano SiO
2Particle is (without the grand magnificent chemical industry of Sillim's ancient cooking vessel Co., Ltd product, trade mark HL200, SiO
2Content>99.8%, specific surface area 200 ± 20m
2/ g, primary particle diameter 7 ~ 60 nm), add 7 mL aqueous surfactant solutions, surfactant is cationic softex kw (CTAB, purity>99%, Chemical Reagent Co., Ltd., Sinopharm Group's product), and concentration is 3*10
-4Mol/L, or the mixture of CTAB and non-ionic surface active isooctylphenol polyoxyethylene (10) ether (TX-10, content>99%, Chemical Reagent Co., Ltd., Sinopharm Group's product), wherein CTAB concentration is 3*10
-4Mol/L, TX-10 concentration is 1*10
-4Mol/L, with FS-250 ultrasonic crusher (ultrasonic instrument Co., Ltd is analysed in the Shanghai life) ultrasonic dispersion 2min under 50W power.Add subsequently 7 mL benthiocarbs (Jiangsu Aolunda Science and Technology Industry Co.,Ltd's product), with XHF-D high-shear emulsion machine (NingBo XinZhi Biology Science Co., Ltd) emulsification 1.5 min under the speed of 3500 rpm, obtain overstable oil-in-water (O/W) type emulsion.
Fig. 1 places the outward appearance photo in a week under emulsion normal temperature.(1.16g/mL) is larger than water for benthiocarb density, and is in lower floor after water mixing layering.The emulsion that obtains as seen from Figure 1 is very stable, and after the week, upper strata does not have water to separate out, and lower floor does not have oil phase to separate out.These emulsion are put into to the insulating box of 54 ° of C and were placed one month, outward appearance as shown in Figure 2, SiO wherein
2Particle has a small amount of water to separate out in stable emulsion upper strata separately, and adds the emulsion of parents' compound all not have oil phase or water to separate out, and namely keeps stable.Draw appropriate emulsion and under constantly stirring, use standard hard water (0.304g CaCl
2+ 0.139g MgCl
25H
2O is dissolved in 1L water) dilute 200 times, the dispersiveness of emulsion in hard water is all relatively good, but SiO
2Separately stable emulsion dilution of particle, there are a small amount of oil bloom to separate out after standing, and do not have oil bloom to separate out after adding the emulsion dilution of parents' compound.Fig. 3 is the microphoto of emulsion, and wherein A, B and C are the microphoto after one week of placement under normal temperature, and D, E and F are the microphoto of heat storage after one month under 54 ° of C, and heat more as can be known is stored up emulsion droplet size after month does not have marked change.Drop is even, and diameter is no more than 30mm.Further investigate and show, under this kind emulsion normal temperature, store breakdown of emulsion did not occur more than 2 years, namely prepared emulsion has superstability.
Embodiment 2, high performance aqueous emulsion of cypermethrin
Beta-cypermethrin is a kind of pyrethroid insecticides, and biologically active is high, has and tags and stomach poison function, and insecticidal spectrum is wide, the speed of knocking down is fast, is applicable to prevent and treat insect and the sanitary insect pest on the various plants such as cotton, vegetables, fruit tree, tea tree, forest.Beta-cypermethrin is solid-state former medicine, and the solvability in water extremely low (<100mg/L, 25C) is usually made 45% missible oil and used.The present invention is dissolved in toluene by it, as oil phase, makes aqueous emulsion, can greatly reduce the consumption of organic solvent and emulsifier.
By beta-cypermethrin (production of Yangzhou, Jiangsu insecticide factory) with mass ratio 6 (solute): 10 (solvents) are dissolved in toluene, as oil phase.Nanometer SiO
2Particle is ultrasonic to be dispersed in water or aqueous surfactant solution as water.Surfactant is CTAB, or the mixture of CTAB and TX-10, and the concentration of CTAB is 1*10
-4Mol/L to 1*10
-3Mol/L, the concentration of TX-10 is 1*10
-4Mol/L to 1*10
-2Mol/L.In the cylindricality bottle of high 6.5cm, diameter 2.5cm by 7 mL SiO
2Particle dispersion (containing 2% ethylene glycol) mixes with 7 mL oil phases, with XHF-D high-shear emulsion machine emulsification 1.5min under the speed of 3500 rpm.When CTAB concentration reaches 1*10
-4Mol/L and when above, obtain overstable oil-in-water (O/W) type emulsion.
Fig. 4 places the outward appearance photo in a week under high performance aqueous emulsion of cypermethrin normal temperature.As can be seen from the figure, while there is no CTAB, emulsion has water to separate out, add CTAB after emulsion very stable.Under 25 ° of C, emulsion is diluted to 200 times with standard hard water under constantly stirring, emulsion all can be uniformly dispersed, nanometer SiO
2The standing rear water surface of the independent stable emulsion dilution of particle has a small amount of oil bloom to separate out, but nanometer SiO
2The standing rear water surface of emulsion dilution of particle/surfactant jointly stabilizing is separated out without oil bloom.Fig. 5 is the outward appearance photo of emulsion after heat under 54 ° of C is stored up January, and visual appearance does not have to change substantially, and namely emulsion keeps stable, especially with SiO
2The emulsion liquid of/CTAB/TX-10 stabilized with mixture is best.Fig. 6 and Fig. 7 are respectively the microphotos of placing under emulsion normal temperature after heat storage under a week and 54 ° of C January, and before and after visible heat storage, emulsion liquid pearl diameter is substantially constant, and liquid pearl size is even, diameter at 10mm between 30 mm.To fixing nanometer SiO
2Concentration, the stability of emulsion rises with the increase of CTAB concentration, and liquid pearl diameter increases along with CTAB concentration and reduces.Granule density is also influential to the liquid pearl diameter of emulsion.Visible from outward appearance, mobility, microphoto etc., with granule density 2%, CTAB concentration 3 * 10
-4Mol/L is good, and emulsion stability and mobility are better, the outward appearance uniform and smooth.Particle and CTAB excessive concentration can cause the viscosity of emulsion to increase, until become gel, outward appearance is coarse.After adding TX-10, can make liquid pearl diameter more even, reach below 10mm, and the outward appearance of emulsion be finer and smoother.Under this kind emulsion normal temperature, store breakdown of emulsion did not occur more than 2 years.
Claims (1)
1. the application of a mixed emulsifying stabilizer, is characterized in that for the preparation of high performance aqueous emulsion of cypermethrin; Beta-cypermethrin is dissolved in solvent toluene with mass ratio 6:10, as oil phase; Nanometer SiO
2Particle is ultrasonic to be dispersed in aqueous surfactant solution as water; Surfactant is the mixture of softex kw CTAB and secondary octyl phenol polyethenoxy 10 ether TX-10, and the concentration of CTAB is 3 * 10
-4Mol/L, the concentration of TX-10 is 1 * 10
-4Mol/L; 7 mL are contained to 2% ethylene glycol, granule density in the cylindricality bottle of high 6.5cm, diameter 2.5cm and are 2% SiO
2The water of particle mixes with 7 mL oil phases, with XHF-D high-shear emulsion machine emulsification 1.5min under the speed of 3500 rpm, obtains overstable oil-in-water O/W type emulsion.
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| CN2011104076538A CN102511475B (en) | 2011-12-09 | 2011-12-09 | Composite emulsion stabilizer for preparing stable pesticide emulsion in water |
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| CN102511475B true CN102511475B (en) | 2013-11-20 |
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| US20160316744A1 (en) * | 2013-12-19 | 2016-11-03 | Dow Global Technologies Llc | Additive package compositions for pesticide suspension concentrate formulations |
| CN108383201A (en) * | 2018-03-14 | 2018-08-10 | 江南大学 | A kind of fast emulsion breaking of oil-in-water emulsion and again antihunt means |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376029A (en) * | 1999-09-10 | 2002-10-23 | 孟山都技术有限责任公司 | Stable concentrated pesticidal suspension |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376029A (en) * | 1999-09-10 | 2002-10-23 | 孟山都技术有限责任公司 | Stable concentrated pesticidal suspension |
Non-Patent Citations (4)
| Title |
|---|
| Bernard P. Binks，等.Synergistic Stabilization of Emulsions by a Mixture of Surface-Active Nanoparticles and Surfactant.《Langmuir》.2007,1098-1106. * |
| 杨礼礼.纳米SiO2/表面活性剂相互作用研究.《中国优秀硕士学位论文全文数据库》.2009, |
| 纳米SiO2/表面活性剂相互作用研究;杨礼礼;《中国优秀硕士学位论文全文数据库》;20090315;参见第13、45-48页，图5-2至图5-4 * |
| 陈钊,等.纳米SiO2与阳离子表面活性剂的相互作用及其诱导的正辛烷-水乳状液的双重相转变.《高等学校化学学报》.2010, * |
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