CN100417324C - Compsn. of agricultural pesticide and preparation method - Google Patents

Compsn. of agricultural pesticide and preparation method Download PDF

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CN100417324C
CN100417324C CNB2004100433131A CN200410043313A CN100417324C CN 100417324 C CN100417324 C CN 100417324C CN B2004100433131 A CNB2004100433131 A CN B2004100433131A CN 200410043313 A CN200410043313 A CN 200410043313A CN 100417324 C CN100417324 C CN 100417324C
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hollow porous
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nano particle
porous sio
pesticide
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CN1695446A (en
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陈建峰
文利雄
李珠柱
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The present invention relates to pesticide composition with the function of controllable release and a preparation method thereof. The composition which comprises active pesticide components and hollowed porous SiO2 nanometer particles can be made into different dosage forms, such as aqueous agents, emulsion, powder, dry suspension agents, etc. The nanometer particles can be in different forms, such as the cubical form, the fusiform, the petaling form, the acicular form, the spherical form, the fiber form, etc. The hollowed porous SiO2 particles whose particle diameter range is from 5 to 500 nm are hollowed and porous, and have thin walls that are composed of SiO2 particles and pore canals that are basically arranged vertically in radial direction, and the size of each pore canal is adjustable.

Description

A kind of composition pesticide and preparation method thereof
Invention field
The present invention relates to a kind of nano pesticide controlled release agent and preparation method thereof; Specifically, the present invention relates to a kind of composition pesticide, it comprises pesticide activity component and hollow porous SiO 2Particle.
Background technology
Agricultural chemicals must form the preparation of certain form by certain process, can use, and the quality of formulation directly influences the effect and the application of agricultural chemicals.If short agricultural chemicals is stored in a kind of formulation in the life-span, the control agricultural chemicals is by necessary dosage, and in the specific time, arriving sustainedly and stably needs the place, to keep enough longevities of residure and to make full use of agricultural chemicals.This agricultural chemicals of controlling by effective dose, is arrived the technology that needs the place in the time of necessity, be referred to as control release technic.Claim that said preparation is the sustained release preparation.Thereby the pesticide action-controlling slow release method has been subjected to paying close attention to widely.
As far back as 1940, U.S.'s microcapsule formulations that begins one's study.What at first microencapsulation of pesticide is introduced to the market is the Pennwalt company of the U.S..The Penncap-M microcapsule formulations of U.S. Pennwalt company in 1974 moves towards practicability with typical case's representative of sustained release agent, and it makes the fugitive parathion-methyl of high poison significantly reduce toxicity, and has prolonged residual effect.The said firm has released microencapsulation basudin, microencapsulation permethrin, weed killer herbicide trefanocide etc. subsequently again.Controlled-release material mainly concentrates on the research as the capsule leather material such as starch derivatives such as starch, starch xanthate, Phospholipids.At present, a large amount of Insecticides (tech) ﹠ Herbicides (tech), bactericide such as dichlorodiphenyl trichloroethane, pyrethrins, chlormequat etc. are by various wall material microencapsulations.Kind surplus the commercial microencapsulation of pesticide 50 in 1994.
In recent years, the microencapsulation for various agricultural chemicals has proposed different suggestions.For example, US-A-5160530 (Griffin company) discloses a kind of technology (as trefanocide) of pesticide capsuleization, is earlier with the active ingredient fusion, then with film forming polymer for example polyvinyl alcohol (PVA) mix.The emulsified together and atomized drying of these materials then.US-A-4244836 (Hoechst company) discloses a kind of similar pesticide capsule method, the i.e. dispersion liquid of atomized drying active ingredient and polyvinyl alcohol.US-A-4936901 (Monsanto company) discloses encapsulated another method, and at this, the microcapsules that contain effective composition are that the reaction by interfacial polycondensation reaction-isocyanates and polyamine makes.Then, the microcapsules with the interfacial polymerization of gained carry out atomized drying.
The controlled-release material base-material of the pesticide slow-releasing agent that these are traditional mostly is macromolecular compound.Commonly used have two classes, and the first kind is a natural polymer as methylcellulose, ethyl cellulose, CMC, hydroxypropyl cellulose, starch and starch derivatives thereof, bark, lignosulfonates, gum Arabic, gelatin, shellac, some protein, wax class, natural rubber etc.Another kind of is synthetic macromolecular compound as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene, polypropylene, polyvinyl chloride, the inclined to one side ethene of polychlorostyrene, polystyrene, polyacrylonitrile, polyacrylic acid and derivative thereof, haloflex, propylene is a polyester, polyethers, polyester, polyurethanes, polyureas, polyvinyl acetate, poly-hydroxyethyl ethylene glycol, ethylene-vinyl acetate copolymer, polybutadiene, poly-isoprene, neoprene, dichloroprene, poly(silicon aether), SBR styrene butadiene rubbers, silicon rubber, butyl rubber, nitrile rubber, the ethylene propylene diene polymer, PLA, polyethylene glycol acid, lactic acid-glycolic acid copolymer etc.
Traditional pesticide slow-releasing agent has the deficiency that it is difficult to overcome.When synthesized polymer material, can produce environment and pollute; Most of synthesized polymer material is not biodegradable; Particle is big, and more than micron order, so when dispenser, skewness comes off easily, contaminated environment can not reach the purpose of protecting environment; Sustained release agent participates in drug response, influences the drug effect performance.The pesticide activity component poor permeability remains in active ingredient a large amount of decomposition wastes because of environmental factors such as light, air cause on blade face.
In the inorganic additive that existing agricultural chemicals uses, mainly adopt atlapulgite, imvite, kaolin, diatomite, in addition, the stone flour of also useful perlite, float stone, talcum and fly ash micro-sphere etc. use as agricultural chemicals.(patent publication No. CN 1072311A, CN 1109269A).But all these inorganic additives, because of the deficiency of himself, when using as pesticides additive agent, evenly distributivity is poor, forms agglomerate easily, influences drug effect, so not ideal enough.Poor as diatomite adsorption, hardness is big slightly; Bentonitic hardness is low; The adsorptivity of loess is poor, hardness is little, suspension difference etc.And the main purpose that these inorganic additives use is as pesticide dispersing agent and adsorbent usefulness, can not satisfy user's slowly-releasing requirement.
As mentioned above, the deficiency that the conventional art Chinese traditional medicine exists causes very big harm for the user and the producer, for the use of medicine great limitation is arranged.
Therefore, need more effective composition pesticide with slow releasing function in the prior art, its slow-release time length, pesticide activity component and slow-release material does not react.Therefore, one of purpose of the present invention provides a kind of new composition pesticide; Further purpose of the present invention provides a kind of preparation method of composition pesticide.
Summary of the invention
The inventor is through deep discovering, with pesticide activity component and hollow porous SiO 2Thereby nano particle is in conjunction with making hollow porous SiO 2Nano particle carrying agricultural chemicals active component can provide the good slow release performance, and does not influence the effect of pesticide activity component.
According to a first aspect of the invention, provide a kind of composition pesticide, comprise one or more pesticide activity components and hollow porous SiO 2Nano particle; Wherein said hollow porous SiO 2The wall of nano particle has the duct of basic arranged radially; And wherein said hollow porous SiO 2Nano particle is loaded with to the described agricultural chemicals of small part.
According to a second aspect of the invention, provide a kind of preparation method who prepares composition pesticide; It comprises the steps:
A) pesticide activity component is dissolved in obtains a solution in organic solvent or the water;
B) with hollow porous SiO 2Nano particle in vacuum drying chamber under the condition of 90～600 ℃ of temperature, vacuum 0.01～0.1Mpa, activating 1～24 hour;
C) with the hollow porous SiO that obtains in the step b) 2Nano particle mixes with a) solution and soaked 0.5 hour～3 months;
D) randomly add additive and can obtain product emulsion;
E) maybe will be through soaking the hollow porous SiO of pesticide activity component 2The nano particle drying obtains solid product or is scattered in the water under high-speed stirred, forms aqua product.
Description of drawings
Fig. 1 is the used hollow ball shape nano SiO 2 particle HRTEM photo of the present invention.
Fig. 2 is the used spherical hollow porous silicon dioxide nano particle SEM photo of the present invention.
Fig. 3 is the used spherical hollow porous silicon dioxide nano granule partial HRTEM photo of the present invention of Fig. 1.
Fig. 4 is the used tubular hollow porous nano SiO 2 particle TEM photo of the present invention.
Fig. 5 is the local HRTEM photo of the used tubular hollow porous nano SiO 2 particle of Fig. 4 the present invention.
Fig. 6 is the used tubular hollow porous nano SiO 2 particle SEM photo of Fig. 4 the present invention.
Fig. 7 is one of used spherical hollow porous silicon dioxide nano particle pore size distribution curve of the present invention of Fig. 1.
Fig. 8 is one of used spherical hollow porous silicon dioxide nano particle adsorption isothermal curve of the present invention of Fig. 1.
Fig. 9 prepares the calcium carbonate TEM photo (overweight force method is synthetic) of the used inorganic template calcium carbonate of hollow porous SiO 2 mesoporous materials.
Figure 10 is a tubular SiO 2 mesoporous materials adsorption isothermal curve among the present invention of Fig. 4.
Figure 11 is the growth pattern of mesoporous film on matrix.
The synthetic route of the hollow mesoporous material of Figure 11-1 expression.
Figure 12 is the schematic diagram of one of composition pesticide preparation method of the present invention-immersion process.
Figure 13 is one of composition pesticide preparation method of the present invention-high pressure method schematic diagram.
Figure 14 is the used spherical hollow porous nano SiO of the present invention 2One of TEM of particle.
Figure 15 is the present invention spherical hollow nanoporous SiO 2The absorption of particle and desorption isotherm.
Figure 16 is another hollow porous nanometer SiO 2The pore size distribution of particle.
Figure 17 is the schematic diagram (controlled release carrier after the embedding Avermectin) of avermectin nanometer controlled release agent.
Figure 18 is hollow porous nanometer SiO 2The thermogravimetric curve of carrier (PHSN) and avermectin nanometer controlled release (Av-PHSN).
The hollow porous nanometer SiO of Figure 19 2The infrared spectrum of carrier, Avermectin and avermectin nanometer controlled release agent
Figure 20 is the comparison of the former medicine of Avermectin, avermectin nanometer controlled release agent stripping curve.
Figure 21 is different pH value (under the acid condition) avermectin nanometer controlled release agent (Av-PHSN) controlled release behavior.
Figure 22 is different pH value (under the alkali condition) avermectin nanometer controlled release agent (Av-PHSN) controlled release behavior.
Figure 23 is avermectin nanometer controlled release agent (Av-PHSN) controlled release behavior under the different temperatures.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in detail.
According to a first aspect of the invention, provide a kind of composition pesticide, comprise one or more pesticide activity components and hollow porous SiO 2Nano particle; Wherein said hollow porous SiO 2Nano particle has basically wall thickness uniformly, and the wall of described particle has the duct of basic arranged radially; And wherein said hollow porous SiO 2Nano particle is loaded with to the described agricultural chemicals of small part.
The hollow porous SiO that the present invention is used 2Nano particle also can be referred to as hollow SiO 2Mesoporous material.According to the definition of IUPAC (IUPAC), duct (window) size is a micro porous molecular sieve less than the molecular sieve of 2.0nm; Molecular sieve between 2.0-50nm is a mesopore molecular sieve.The scientist of Mobil in 1992 is for synthetic new era of opening the molecular sieve science of M41S (MCM-41, MCM-48, MCM-50) series silica-based (silica-based) mesopore molecular sieve, referring to Beck J.S, Vartuli J C, Roth W J., A new family of mesoporous molecular sieves prepared with liquidtemplate, J.Am.Chem.Soc., 1992,114:10834-10843.
At present, the bodies such as many application need films of mesoporous material preparation.Existing bibliographical information the mesoporous material of some preparation special forms: it is supporter that Yang in 1996 etc. prepare with the mica surface, the continuous mesoporous SiO of the parallel oriented growth with mica surface in its duct 2Film, referring to Yang H, Kuperman A, Coombs N., Suzan Mamlche-Afara ﹠amp; Geoffrey A.Ozin, Syntheisof oriented film of mesoporous silica on mica, Nature, 1996,379:703-705.Mesoporous SiO 2Fiber and diameter are several millimeters mesoporous SiO 2Bead and at the SiO of the atresia of 420nm 2The ball non-directional grow a layer thickness be the mesoporous film of 75nm referring to Whittingham M S, Current Opinionin Solid State; Mater.Sci., 1996,1,227.Because its duct is parallel to supporting body surface, causes inside diffusional resistance big.
Hollow porous SiO 2The preparation of nano particle is described in detail in the applicant's Chinese patent application formerly: in 02160383.9, be incorporated herein by reference in full at this this patent specification.
Specifically, the hollow porous SiO of the present invention 2The preparation method of nano particle comprises the steps:
(1) to being selected from calcium carbonate, in the inorganic template agent suspension of magnesium carbonate or barium carbonate, adds the surfactant of formation 1.5～30%, add organic solvent such as the ethanol or the methyl alcohol etc. of some again.
(2) under alkali condition, mixture adding silicon source to step (1) comprises organic esters of silicon acis such as ethyl orthosilicate or inorganic silicon such as sodium silicate, six square arrays that its hydrolysate or polymer deposition form to surfactant, be coated on around the rod-shaped micelle of surfactant formation, constitute mesoporous wall.
(3) suspension that step (2) is obtained filters, roasting,
(4) acid is molten, filters, and drying promptly obtains described product.
Composition pesticide according to a first aspect of the invention, wherein said hollow porous SiO 2The particle diameter of nano particle is 5～500 nanometers, preferred 40～150 nanometers, more preferably 50～100 nanometers.This depends on the size of the particle diameter of the inorganic template for preparing mesoporous material.
Composition pesticide according to a first aspect of the invention, wherein said hollow porous SiO 2Nano particle is spherical, needle-like, cube, spindle, petal, sheet, fibrous.This depends on the shape of the inorganic template for preparing mesoporous material.
About spindle calcium carbonate, day the disclosure specially permit flat 5-238730, a day disclosure and specially permit that clear 59-26927, a day disclosure specially permit flat 1-301510, a day disclosure is speciallyyed permit and carried out description among the flat 2-243513, wherein described by in conventional stirred tank or bubble tower, prepared calcium carbonate with required form by adding crystal control agent.
For for example needle-like calcium carbonate, at US 5,164, described in 172 a kind ofly under the situation that has needle-like calcium carbonate crystal seed and phosphoric acid, by carbonizatin method, obtained needle-like calcium carbonate by calcium hydroxide suspension.Relevant preparation various thinner, form is more complete, the CaCO of easier control 3A large amount of patented technologies occurred, for example a day disclosure is speciallyyed permit clear 59-223225, a day disclosure is speciallyyed permit clear 62-278123.
Beijing University of Chemical Technology has developed a kind of method for preparing calcium carbonate superfine powder under the rotating bed super gravity condition, for example be described in the method in Chinese patent ZL95105343.4, Chinese invention patent application 00100355.0 and the Chinese invention patent application 00129696.5, the present invention introduces these patents or patent application as a reference.
The synthesis technique that is used for the calcium carbonate of different shape of the present invention can be referring to Chinese patent application 01145312.5 and 02105389.9, by the rotating speed of control revolving bed and the nucleation and growth of other process conditions such as initial reactant concentration, temperature, pH value and corresponding crystal control agent control calcium carbonate, can accurately control the composite character of carburizing reagent, synthetic calcium carbonate with narrow particle size distribution, different-shape.
In Chinese patent application 01145312.5, under the hypergravity condition, for example in the supergravity reactor, utilize carbonizatin method, by slaked lime and carbonic acid gas are reacted, and preparation comprises the calcium carbonate of various concrete forms, for example spindle, petal, fiber shape, sheet, needle-like, spherical calcium carbonate.In Chinese patent application 02105389.9, provide a kind of microwhisker like calcium carbonate.All above-mentioned documents are incorporated herein by reference.
At above-mentioned hollow porous SiO 2Nano particle the preparation method in, the concentration of used inorganic template agent suspension is 1.5～25% (percetages by weight).Be preferably 5～10%.
At above-mentioned hollow porous SiO 2Nano particle the preparation method in, the concentration of used organic formwork agent is 1.5～20% (in the weight of mixture).
At above-mentioned hollow porous SiO 2Nano particle the preparation method in, used surfactant can prepare the used any surfactant of mesoporous material for this area, see Journal of Inorganic Materials, 1999,14 (3): 333-342 report, as have the surfactant of parents' group, be preferably quaternary surfactant, more preferably cetyl trimethyl ammonium halide, more preferably softex kw.
At above-mentioned hollow porous SiO 2Nano particle the preparation method in, used surfactant concentrations is wide variation very, can be the concentration that forms spherical micelle or rod-shaped micelle, as 1.5-20%, be preferably 1.8-10%, more preferably 2.0～5% (in the weight of suspension).The ratio 1～20 of inorganic template agent and surfactant, preferred 2～10, more preferably 3～5.The silicon source is (with SiO 2The weight meter) with inorganic template agent ratio 0.05～300, preferred 0.1～10, more preferably 0.15～5.
At above-mentioned hollow porous SiO 2Nano particle the preparation method in, the pH value can be controlled at 8-14; Be preferably 10-14, more preferably 12-14.The material that is used to regulate pH comprises sodium hydroxide, potassium hydroxide, lithium hydroxide, urea, carbonic hydroammonium, ammoniacal liquor and ammonium chloride etc.10～200 degrees centigrade of reaction temperatures are preferably 25～150 degrees centigrade, and the reaction time is 10 minutes～36 hours, and roasting time is 0.2～100 hour.
According to above-mentioned hollow porous SiO 2Nano particle the preparation method, be that the calcium carbonate of 40-50nm is inorganic template with the particle diameter, prepared spherical hollow porous SiO 2Nano particle (SiO 2Nano mesoporous balls), its particle diameter is 60nm, and specific surface area aBET is 1016.72m 2/ g, the average pore size on the ball wall is 3.94nm, pore volume 1.002cm 3/ g.
According to above-mentioned hollow porous SiO 2Nano particle the preparation method, be 200-300nm with the diameter, draw ratio is that about 5 aciculiform calcium carbonate is inorganic template, CTAB concentration 2% has prepared the hollow porous SiO of tubulose 2Nano particle (meso-porous hollow pipe), the about 40nm of its wall thickness.a BJHBe 565.9m 2/ g, pore volume 0.6218cm 3/ g, the wall average pore size is 4.39nm.
Adopt Japanese JEM-2010F field emission high-resolution transmission electron microscope (Aceleration:200kv), resolution is that 1.5nm and FEG-SEM high resolution scanning Electronic Speculum (Resolution 1.5nm) have been carried out electronic microscope photos to thin-shell type nano mesoporous balls of the present invention, and the result as Figure 1-3.
From Fig. 1 and 2 as can be seen, spherical hollow porous SiO 2The particle diameter of nano particle (nano mesoporous balls) is approximately about 60nm, although adopt ultrasonic to disperse before the sample preparation in ethanolic solution, it is serious to reunite, and more can see damaged hollow ball from the SEM photo, further proves the existence of hollow-core construction.Fig. 3 is the local electromicroscopic photograph of nano mesoporous balls, therefrom as can be seen, by self assembly, exists really to have mesoporous that six sides arrange.Figure 14 also provides another TEM of the used hollow porous nano SiO 2 particle of the present invention.
Adopt SIEMENS D5005D type X-ray diffractometer (100mA, wavelength X=0.15406nm, step-length is 0.02 ° for Cu target, 40kv) that the silica nanometer hollow ball has been carried out low-angle mensuration, 100 crystal faces, 2 θ=2.4 °, mesoporous aperture D=3.58nm.
The ASAP2010 type that adopts U.S. Micromeritics instrument corporation production is to spherical hollow porous SiO of the present invention 2The pore-size distribution of nano particle (nanometer mesoporous hollow sphere) characterizes, as shown in Figure 7.
Fig. 7 is spherical hollow porous SiO 2The pore-size distribution of nano particle (nano mesoporous balls), as can be seen from the figure, its pore-size distribution is narrow.According to the BET method, record condition 1016.72m 2/ g, Vg=1cm 3/ g, so average pore size D is 4V g/ a=3.94nm, the bigger 0.36nm of aperture D=3.58nm that this and XRD calculate, this may be that reason owing to two aspects causes, the first, the aperture of calculated value is an ideal situation, has the situation of some unordered phase, causes underestimating of mesoporous size; The second, this may be because the pore volume of being measured except that mesoporous volume, also comprises the duct volume of forming between shell meso-porous nano ball, makes that therefore the average pore size that adopts the BET method to measure is more bigger than the aperture of calculating with XRD.The average pore size that adopts the BJH method to obtain is 4.3nm.Than more bigger with the BET method.
Figure 16 also provides the pore size distribution of another kind of spherical hollow porous silica particle.
Fig. 8 is when temperature is 77.39K, the spherical hollow porous SiO that the present invention is used 2The adsorption isotherm of nano particle (thin-shell type nano mesoporous balls) absorption nitrogen is at the low P/P of relative pressure 0≤ 0.1 o'clock, along with the raising of relative pressure, adsorbing capacity increased sharply; Work as P/P 0〉=0.1 o'clock, isothermal absorption was milder; Work as P/P 0Between 0.2～0.3, adsorbing capacity occur one less more prominent, this is because nitrogen in mesoporous capillary condensation effect, but P/P do not occur 0In the unexpected phenomenon that increases of 0.3～0.4 adsorbing capacity.The difference that therefore, may cause adsorption isotherm; Work as P/P 0Curve becomes smooth after 〉=0.3; Work as P/P 0→ 1 o'clock, the whole condensations of nitrogen.
Adopt Japanese JEM-2010F field emission high-resolution transmission electron microscope (Aceleration:200kv), resolution is 1.5nm and FEG-SEM high resolution scanning Electronic Speculum (Resolution 1.5nm) the hollow porous SiO to tubulose of the present invention 2Nano particle (meso-porous hollow pipe) has carried out measurement result as shown in Figure 4.
As can see from Figure 4, the hollow porous SiO of prepared tubulose 2The internal diameter of nano particle (hollow pipe) is approximately 200-300nm, and wall thickness is about 40nm.The draw ratio of this hollow pipe depends on the draw ratio diameter of inorganic template aciculiform calcium carbonate, and the calcium carbonate draw ratio that this experiment is adopted is about 5.Fig. 5 be the meso-porous hollow tubular axis to the high resolution electron microscopy photo, can see that therefrom the radial direction at pipe has many regular orderly stripeds of wheel shape that are, Here it is mesopore orbit.From Fig. 6 hollow pipe top as can be seen, described tubular material is hollow material.
The ASAP2010 type determining adsorption instrument that adopts U.S. Micromeritics instrument corporation to produce has been measured the hollow porous SiO of tubulose of the present invention 2The nitrogen adsorption characteristic of nano particle (meso-porous hollow pipe) is seen shown in Figure 10.
As can be seen from Figure 10, as relative pressure P/P 0When low, the nitrogen adsorption amount improves rapidly with the increase of relative pressure, works as P/P 0Between 0.2～0.3, adsorbing capacity occur one less more prominent, this be since nitrogen in mesoporous capillary condensation effect.Smooth increase appears after this, when reduced pressure near 1 the time, the whole condensations of nitrogen.Hysteresis loop occurs in absorption and desorption process, this is owing to capillarity causes.
Figure 15 provides the present invention used spherical hollow porous SiO 2The nitrogen adsorption characteristic of nano particle.
Mesoporous film has following three kinds of modes in the growth of matrix:
Bibliographical information Figure 11 (b), (c) two kinds of growth patterns are considered from minimum energy principle with regard to it, carry out than being easier to, and first kind of growth pattern (a) is difficult to and is a kind of growth pattern of wishing most to obtain, see K.R.Kloetstra, H.W.Zandbergen, J.C.Jansen, H.van Bekkum, MicroporousMater.1996,6:287-293.The mesoporous film of existing bibliographical information is by b basically, two kinds of growth patterns of c carry out, as document Yang P, Zhao D, Margolese D I, Generalized synthesis of largepore mesop-orous metal oxides with semicrystalline frameworks, Nature, 1998,396:152-155 mixes the acidic aqueous solution of ethyl orthosilicate (TEOS) with chloro-hexadecane base trimethyl ammonium, then on the fresh mica surface that dissociates in 80 ℃ of following nucleating growths, obtained oriented growth, the duct is parallel to the continuous mesoporous SiO of mica surface 2Film.
From forming the duct form of tubulose mesoporous material, the mesopore orbit that this experiment is synthesized is seen Fig. 5 perpendicular to inorganic template agent calcium carbonate surface, and the length with two strands of CTMAB is the same basically by the diameter of XRD and mesopore orbit, so SiO 2In any case with the surfactant effect, regardless of process, final result is SiO 2Be coated on the outside of CTMAB micella, constitute six side's phases by self-organizing then, otherwise just can not appear in all mesoporous material preparation process, utilize high-temperature roasting or chemical method to remove organic surface active agent, left space constitutes mesopore orbit, use for reference liquid crystal templated mechanism, therefore mesoporous SiO 2Forming its possible growth mechanism of mesoporous film at template agent calcium carbonate is:
(1) surface of the calcium carbonate in the calcium carbonate suspension is because particle is little, the surface can be high, absorption surface activating agent CTMAB, and CTMAB is at the calcium carbonate surface enrichment, thereby make the CTMAB concentration ratio liquid phase main body concentration height of calcium carbonate surface, reach second CMC (cmc2).
(2) surfactant CTMAB micella is by complicated synergies such as weak and non-covalent bond less directionality such as Coulomb force, hydrogen bond, sterically hindered and Van der Waals power and weak ionic bond or ion strengths, make micella the vertical and calcium carbonate surface of axial direction, and, form six square arrays by self assembly according to minimum energy principle.
(3) silicon source such as ethyl orthosilicate (TEOS) hydrolysis under alkali condition, the silicic acid oligomer of generation polygamy position is filled into around the micella of six square arrays, carries out polymerization and deposition, constitutes the skeleton thickness of MCM-41.
(4) organic formwork agent be surfactant (as CTMAB) through 550 ℃ of calcination process of temperature, make it be decomposed into gas and overflow, calcium carbonate becomes CaCl through dissolving with hydrochloric acid 2And CO 2Diffuse out from mesopore orbit, constitute mesoporous material with hollow shape.
Above-mentioned mechanism can be carried out proper explanations to experimental phenomena, and the synthetic route of hollow mesoporous material can Figure 11-1 expression.
Hollow porous SiO 2 mesoporous materials pore size of the present invention is adjustable, wall thickness is adjustable, particle size is adjustable or the like, mesoporous material has regulatable nanoscale regular pore canal, can be used as " the miniature controlled release carrier " of nano particle, be the controlled release of medicine, open up new approach, increase new formulation.Novel pesticide action-controlling carrier-hollow porous SiO 2Nanosphere is a kind of inert carrier, and to people and animals' nonhazardous, specific surface is big, and its adsorptivity is strong; There are silica group and silanol group, and the hollow form structure is arranged; Suspension is good, and hardness is moderate, and light specific gravity has very low deactivation energy, has high macroporosity, is good soil conditioner, is the novel carriers of agricultural chemicals.
Specifically, the invention provides and a kind ofly prepare a kind of composition pesticide as controlled release carrier material with hollow porous silica: the nano pesticide controlled release agent, by mass percentage, it contains pesticide original medicine: 0.01～90.0%, hollow porous SiO 2Sill: 0.01～99.5%, solvent: 0.01～10.0%, cosolvent: 0.01～10.0%, additive: 0.01～15.0%, organic solvent or water: surplus.
Additive in the composition pesticide of the present invention is pesticides additive agent commonly used, and it comprises emulsifier, dispersant, preservative, protecting colloid.The amount of the additive in the composition pesticide of the present invention is pesticides additive agent amount commonly used.
Solvent is an arene, as benzene,toluene,xylene, ethylbenzene etc.; Solvent also can be the ester class, as methyl formate, Ethyl formate, butyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate etc.
Cosolvent is an alcohols, as methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, n-octyl alcohol, n-butanol, isobutanol, ethylene glycol, polyethylene glycol, propane diols etc.
The emulsifier that is fit to is nonionic emulsifier and anion emulsifier; Nonionic emulsifier can be used tween, this dish, polyoxyethylene nonylphenol ether; Anion emulsifier is selected dodecyl phenenyl sulfate, neopelex, calcium dodecyl benzene sulfonate etc. for use.The dispersant that is fit to is the copolymer of poly-methyl acrylate, low molecular weight phenylethylene-maleate.The protecting colloid that is fit to is many materials commonly used, can be preferably: materials such as polyvinyl alcohol, Sodium Polyacrylate, methylcellulose, carboxymethyl cellulose, pectate, gelatin, gum Arabic, PEO.
In the composition pesticide of the present invention, also can contain other auxiliary agent, auxiliary agent is one or more in preservative, defoamer and the antifreezing agent, and its content is expressed as 0.01～10.0% of total composition with mass percent.The preservative that is fit to is commonly used in the polymer emulsion, as penta sodium pentachlorophenate, adjacent chloro-m-cresol, daconil M etc.The defoamer that is fit to is the product that can conveniently use, as silane derivative dimethyl silicone polymer class, tributyl phosphate, poly propane diols etc.The antifreezing agent that is fit to has ethylene glycol, glycerine, propane diols, 2-Butoxyethyl acetate, urea, sucrose etc.
The average grain diameter of the particle of disperse phase is 50～100 nanometers, is not more than 150 nanometers.
In a kind of preferred scheme; composition pesticide of the present invention comprises continuous phase and disperse phase; wherein continuous phase comprises that water, additive such as emulsifier, dispersant, protecting colloid and auxiliary agent are preservative, defoamer and antifreezing agent, and preferred ingredients is top those materials of mentioning.Water can also comprise a spot of dispersed phase component in addition.Disperse phase is described hollow porous SiO 2Nano particle, it is loaded with the part pesticide activity component.The amount of disperse phase is 1.0～50.0% weight of composition by weight, the concentration of each material following (by weight) in the disperse phase:
Hollow porous SiO 2Controlled release carrier: 0.01～99.5%;
Pesticide original medicine 0.01～90.0%;
Additive is generally 0.01～35.0%, is preferably 5.0～20.0%;
Organic solvent or water: surplus.
Composition pesticide according to a first aspect of the invention, wherein said hollow porous SiO 2The thickness of nano particle wall is 5～100 nanometers, is preferably 8～20 nanometers, more preferably 10～15 nanometers.
Composition pesticide according to a first aspect of the invention, wherein said hollow porous SiO 2The average pore size in the duct on the nano particle wall is the 1-50 nanometer, is preferably the 2-40 nanometer, is preferably the 1-10 nanometer.
Agricultural chemicals used among the present invention is also without particular limitation, the water-soluble or organic solvent of its energy, thus enter hollow porous SiO 2The passage of nano particle and hollow position.Agricultural chemicals commonly used is as follows:
A, insecticide, for example
Sumithion (fenitrothion), chemical name: O, O-dimethyl-O-(4-nitro-3-tolyl) thiophosphate;
Fenthion (fenthion), chemical name: O, O-dimethyl-O-(4-methyl mercapto-3-tolyl) thiophosphate;
Diazinon (diazinon), chemical name: O, O-diethyl-O-(2-isopropyl-4-methylpyrimidine-6-methyl) thiophosphate;
Pyridaphethione (pyridaphenthion), chemical name: O, O-diethyl-O-(2,3-dihydro-3-oxidation-2-phenyl-6-pyridazinyl) thiophosphate;
Hostathion (triazophos), chemical name: O, O-diethyl-O-1,2,4-triazole-3-base thiophosphate;
Cynock (cyanophos), chemical name: O, O-dimethyl-O-(right-piperazine base phenyl) thiophosphate;
Parathion (parathion), chemical name: O, O-diethyl-O-(4-nitrobenzophenone) thiophosphate;
Parathion-methyl (parathion-methyl), chemical name: O, O-dimethyl-O-(4-nitrobenzophenone) thiophosphate;
Ethion (ethion), chemical name: O, O, O ', O '-tetraethyl-S, S '-methylene-two (phosphorodithioate);
Nuvacron (monocrotophos), chemical name: O, O-dimethyl-O-[1-methyl-2-(methylamino formyl)] vinyl phosphate;
Phosphamidon (phosphamidon), chemical name: O, O-dimethyl-O-[2-chloro-2-(diethylamino formyl-1-methyl)] vinyl phosphate;
MDYL, chemical name: O, O-diethyl-O-2-methoxyl group-6-methylpyrimidine base-4-base thiophosphate;
Acephatemet (methamidophos), chemical name: O, S-dimethyl amido thiophosphate;
Sulfotep (sulfotep), chemical name: O, O, O ', O '-tetraethyl dithiopyrophosphate;
Phenthoate dimephenthoate cidial (phenthoate), chemical name: O, O-dimethyl-S-(α-ethoxy carbonyl benzyl) phosphorodithioate;
Phosalone (phosalone), chemical name: O, O-diethyl-S-[(6-chloro-2-oxygen benzoxazoles quinoline-3-yl) methyl] phosphorodithioate;
Quinalphos (quinalphos), chemical name: O, O-diethyl-O-(quinoxaline-2-yl) thiophosphate;
Chlorophos (trichlorphon), chemical name: O, O-dimethyl-(2,2,2-three chloro-1-hydroxyethyls) phosphonate ester;
Dichlorvos (dichlorvos), chemical name: O, O-dimethyl-O-(2, the 2-dichloro) vinyl phosphate;
Phoxim (phoxim), chemical name: O, O-diethyl-O-alpha-cyano benzene fork amido thiophosphate;
Chlopyrifos (chlorpyrifos), chemical name: O, O-diethyl-O-(3,5, the 6-trichloro-2-pyridyl) thiophosphate;
Rogor (dimethoate), chemical name: O, O-dimethyl-S-(N-methyl amido formyl methyl) phosphorodithioate;
Omethoate (omethoate), chemical name: O, O-dimethyl-S-(N-methylamino formyl methyl) thiophosphate;
Malathion (malathion), chemical name: O, O-dimethyl-S-[1,2-two (ethoxy carbonyl) ethyl] phosphorodithioate;
Phosmet (phosmet), chemical name: O, O-dimethyl-S-(phthalimide ylmethyl) phosphorodithioate;
Orthene (acephate), chemical name: O, S-dimethyl acetyl group thio-phosphamide ester;
Methidathion (methidathion), chemical name: S-2,3-dihydro-5-methoxyl group-2-oxo-1,3,4-sulphur two pyrolles-3 ylmethyls-O, O-Methyl disulfide substituted phosphate;
Thimet (phorate), chemical name: O, O-diethyl-S-(ethylmercapto group methyl) phosphorodithioate;
Phosfolan_methyl, chemical name: 2-dimethoxy phosphinylidyne imino group 1,3-dithiolane;
Isofenphos methyl (isofenphos-methyl), chemical name: O-methyl-O-(2-isopropoxy carbonyl) phenyl-N-isopropylthio phosphoramidate;
Fonofos (fonofos), chemical name: O, O-diethyl-S-phenyl phosphorodithioate;
Ethoprop (ethoprop or ethoprophos), chemical name: O-ethyl-S, S-dipropyl phosphorodithioate;
Toyodan (prothiofos), chemical name: O-(2,4 dichloro benzene base)-O-ethyl-S-n-pro-pyl phosphorodithioate;
Profenofos (protenofos), chemical name: O-(4-bromo-2-chlorphenyl)-O-ethyl-S-propyl group-thiophosphate;
Pyraclofos (pyraclofos), chemical name: (RS)-[O-1-(4 chlorphenyl) pyrazoles-4-yl]-O-ethyl S-propyl dithiocarbamate phosphate;
Isazofos (isazofos), chemical name: O, O-diethyl-O-(5-chloro-1-isopropyl-1,2,4-triazoles-3 base) thiophosphate;
Isofenphos (isofenphos), chemical name: phenyl N-isopropyl-O-ethyl-O-[(2-isopropoxy carbonyl)] the sulphur phosphoramidate;
Fosmethilan (fosmethilan), chemical name: S-[N-(2-chlorphenyl) butyramide methyl]-O, O-Methyl disulfide substituted phosphate;
Mobucin (isoprocarb), chemical name: o-isopropyl phenyl methyl carbamate;
Leaf looses and flies chemical name: N-methyl carbamic acid-O-(2, the 3-dimethyl benzyl) ester;
Dimethyl phenyl carbamate, chemical name: N-methyl carbamic acid Mixed XYLENE ester;
Bassa (BPMC), chemical name: o-sec-butyl phenyl methyl carbamate;
Carbaryl (carbaryl), chemical name: 1 naphthyl N methyl carbamate;
Meta-tolyl-N-methylcarbamate (MTMC) (MTMC), chemical name a: tolyl-N-methyl carbamate;
Carbofuran (carbofuran), chemical name: 2,3-dihydro-2,2-dimethyl-7-benzofuranyl-N-methyl carbamate;
Benfuracard micro (benfuracarb), chemical name: 2,3-dihydro-2, the amino sulfenyl of 2-dimethyl benzofuran-7-base-N-[N '-(2-ethoxycarbonyl-ethyl)-N '-isopropyl]-the N-methyl carbamate;
Carbosulfan (carbosulfan), chemical name: 2,3-dihydro-2,2-dimethyl benzofuran-7-base-N-(dibutyl amine sulfenyl)-N-methyl carbamate;
Aldicarb (aldicarb), chemical name: O-(methylamino formoxyl)-2-methyl-2-methylthio propionaldoxime;
Methomyl (methomyl), chemical name: 1-(methyl mercapto) ethylidene-N-methyl carbamate;
UC-51762 (thiodicarb), chemical name: N, N '-[two (azomethine base) the carbonyl oxygen bases of sulphur]-two methyl esters of diimine thioacetic acid;
Aphox (pirimicarb), chemical name: 5,6-dimethyl-2-dimethylamino-4-pyrimidine radicals-dimethylcarbamate;
Alanycarb (alanycarb), chemical name: sulphur ethyl (Z)-N-[(methyl (1-methyl mercapto ethyleneimino-oxygen carbonyl) amino)]-the beta Alanine ester;
Triaguron (triaguron), chemical name: (3-tertiary butyl-1-dimethylamino formyl-1H-1,2,4-triazole-5-base sulphur) ethyl acetate;
Cartap (cartap), chemical name: 1,3-two-(carbamyl sulphur)-2-dimethylaminopropanecompounds hydrochloride;
Dimehypo, chemical name: 2-N, N dimethylamine base-1, two (the thiosulfonic acid sodium base) propane of 3-;
The desinsection list, chemical name: 2-N, N dimethylamine base-1-sodium thiosulfate base-3-propane thiosulfate;
Desinsection peace (profurife-aminium), chemical name: 2-(N, N dimethylamine base)-1, the two thiosulfuric acid ammonium propane of 3-;
Thiocyclam (thiocyclam-hydrogenoxalate), chemical name: N, N-dimethyl-1,2,3-trithian-5-amine oxalate;
The fennel artemisin, chemical name: 3-oxo-5a-methyl cyclohexadiene (1b, 4) and 8-methyl-9-oxo-octahydro benzofuran;
Polythiane, chemical name: (1) 7-dimethylamino-1,2,3,4,5-pentasulfide cyclo-octanes, (2) 4-dimethylamino-1,2-two sulphur pentamethylene;
Thiazan (buprofezin), chemical name: 2-tertiary butyl imino group-3-isopropyl-5-phenyl-3,4,5,6-tetrahydrochysene-2H-1,3,5-sulphur diazole-4-ketone;
Diflubenzuron (diflubenzuron), chemical name: 1-(4-chlorphenyl)-3-(2, the 6-difluoro benzoyl) urea;
The young urea that goes out, adjacent chlorobenzene formacyl-3-(4-chlorphenyl) urea of chemical name: 1-;
UC 62644 (chlorfluazuron), chemical name: 1-[3,5-two chloro-4-(3-chloro-5-trifluoromethyl-2-pyridine oxygen base) phenyl]-3-(2, the 6-difluoro benzoyl) urea;
Diflubenzuron (telfubenzuron), chemical name: 1-(3,5-two chloro-2,4 difluorophenyls)-3-(2,6-two fluorobenzoyl) urea;
Flufenoxuron (flurenoxuron), chemical name: 1-[4-(α-three fluoro-is to toloxyl for 2-fluoro-α, α)-2-fluorophenyl]-3-(2, the 6-difluoro benzoyl) urea;
Rice full (tebufenozide), chemical name: 1-(1, the 1-dimethyl ethyl)-1-(4-ethylamino benzonitrile acyl group)-3,5-dimethyl benzene formylhydrazine;
Fluorine bell urea (hexafuluron), chemical name: N-[(3,5-two chloro-4-(1,1,2,2-tetrafluoro ethyoxyl) phenyl amino) carbonyl]-2,6-difluoro benzamide;
Cypermethrin (cypermethrin), chemical name: alpha-cyano-(3-benzyloxy phenoxy base) (1RS)-1R, 3R-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester;
Alpha-cypermethrin (alphamethrin), chemical name: (1R cis) S and (1S cis) R-alpha-cyano-(3-benzyloxy phenoxy base)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester;
Cyhalothrin (cyhalothrin), chemical name: 3-(2-chloro-3,3,3-trifluoro-propenyl)-2,2-dimethyl cyclopropane carboxylic acid-alpha-cyano-3-phenoxybenzyl ester;
Decis (deltamethrin), chemical name: alpha-cyano-3-benzyloxy phenoxy base (1R, 3R)-3-(2, the 2-dibromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
Biphenthrin (bifenthrin), chemical name: 3-(2-chloro-3,3,3-trifluoro propene-1-yl)-2,2-dimethyl cyclopropane carboxylic acid-2-methyl-3-phenylbenzyl ester;
Fenpropathrin (fenpropathrin), chemical name: alpha-cyano-3-phenoxy benzyl-2,2,3,3-4-methyl cyclopropane carboxylic acid ester;
Cyfloxylate (cyfluthrin), chemical name: alpha-cyano-3-phenoxy group-4-luorobenzyl (1R, 3R)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester;
Sumicidin (fenvalerate), chemical name: alpha-cyano-3-benzyloxy phenoxy base (R, S)-2-(4-chlorphenyl)-3 Methylbutanoic acid ester;
Efficient sumicidin (esfenvalerate), chemical name: (S)-alpha-cyano-3-benzyloxy phenoxy base (S)-2-(4-chlorphenyl)-3 Methylbutanoic acid ester;
Flucythrinate (flucythrinate), chemical name: (R, S)-alpha-cyano-3-benzyloxy phenoxy base-(R, S)-2-(4-difluoro-methoxy)-3 Methylbutanoic acid ester;
Taufluvalinate (fluvalinate), chemical name: N-(2-chloro-4-trifluoromethyl)-DL-valine-alpha-cyano (3-phenoxy phenyl) methyl ester;
Valerate, chemical name: (R, S)-3-benzyloxy phenoxy base (R, S)-2-(4-benzyl chloride base)-3 Methylbutanoic acid ester;
Trebon (ethofenprox), chemical name: 2-(4-ethoxyphenyl)-2-methyl-propyl-3-benzyloxy phenoxy base ether;
Tefluthrin (tefluthrin), chemical name: 2,3,5,6-tetrafluoro-4-methyl-benzyl (Z)-(1RS, 3RS)-3-(2-chloro-2,3,3-trifluoropropyl-1-thiazolinyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
Tralomethrin (tralomethrin), chemical name: (S)-a-cyano group-3-phenoxy benzyl (1R)-and suitable-2, the 2-dimethyl-3-[(RS)-1,2,2, and 2-tetrabromo ethyl] cyclopropanecarboxylcompound;
Cycloprothrin (cycloprothrin), chemical name: 3-phenoxy group-alpha-cyano benzyl-1-(4-ethoxyphenyl)-2,2-dichloro cyclopropanecarboxylcompound;
Cis cyfloxylate (beta-cyfluthrin), chemical name: alpha-cyano-3-phenoxy group-4-luorobenzyl (1R, 3R)-3-(2,2-difluoroethylene base)-2,2-dimethyl cyclopropane carboxylic acid ester;
Pink bollworm property lures element (gossyplure), chemical name: (suitable, suitable) and (suitable, anti-)-7,11-16 carbon dialkylene acetic acid esters;
Lindane (gamma-BHC or gamma-HCH), chemical name: γ-1,2,3,4,5,6-hexachlorocyclohexanes;
The bitter alkali (matrine) of giving birth to, chemical name: the bitter alkali alcohol of giving birth to, hardship is given birth to plain, aphid wax enemy;
Neat pier mycin (abamectin), chemical name: Avermectin, acetamiprid, the acarid element, Ah Buddhist's moldin, avermeetins is liked than rhzomorph, avermectin, the desinsection element, the evil utmost point goes out avermectin, worm mite light, MK936;
Imidacloprid (imidacloprid), chemical name: 1-(6-chloro-3-pyridylmethyl)-N-Nitroimidazoline-2-pitches amine;
Fluorine worm nitrile (fipronil), chemical name: (±)-5-amino-1-(2,6-two chloro-α, α, α-three chloro-β-tolyl-)-4-trifluoromethyl-sulfinyl pyrazoles-3-carbonization nitrile;
5a,6,9,9a-hexahydro-6,9-methano-2,4 (endosulfan), chemical name: (1,4,5,6,7,7-chlordene-8,9,10-trinorbornene-5-alkene-2,3-subunit dimethylene) Asia;
Bacillus thuringiensis,Bt (bacillus thuringiensis), chemical name: BT emulsion, bacillus thuringensis, bacillus thruingensis, bacterium medicine, 7216,82162;
Rotenone (rotenone);
Halizan (metaldehyde), chemical name: 2,4,6,8-tetramethyl-1,3,5,7 four oxocane;
Metaldehyde;
B. acaricide, for example
Dicofol (dicofol), chemical name: 2,2,2-three chloro-1, two (4-chlorphenyl) ethanol of 1-;
Amitraz (amitraz), chemical name: N, N-pair-(2,4-dimethylbenzene iminomethyl) methylamine;
Single carbonamidine (danjiami), chemical name: N-(2, the 4-xylyl)-N '-methyl amitraz hydrochloride;
Propargite (propargite), chemical name: 2-(4-tert-butyl benzene oxy) cyclohexyl-1-propinyl sulfite;
Hexythiazox (hexythiazox), chemical name: 5-(4-chlorphenyl)-3-(N-cyclohexyl carboxyamide)-4-methylthiazol alkane-2-ketone;
Fenbutatin oxide (fenbutatin oxide), chemical name: two [three (2,2-dimethyl-2-phenylethyl) tin] oxide;
Azacyclotin (azocyclotin), chemical name: 1-(thricyclohexyl stannyl)-1-hydrogen-1,2,4-triazole;
Fenisobromolate (bromopropylate), chemical name: 4,4 '-dibromo diphenylglycollic acid isopropyl ester;
Isocarbophos (isocarbophos), chemical name: O-methyl-O-(neighbour-isopropoxy carbonyl phenyl) thio-phosphamide;
Four mite piperazines (clofentezine), chemical name: 3,6 pairs of (2-chlorphenyls)-1,2,3,4-tetrazine;
Pyridaben (pyridaben), chemical name: 2-tertiary butyl-5-(4-tertiary butyl dibenzylsulfide)-4-chloro-2H-pyridazin-3-one;
Citrazon (benzoximate), chemical name: 3-chloro-α-ethoxy imino-2,6-dimethoxy-benzyl formic acid esters;
Azoles mite ester (fenpyroximate), chemical name: (E)-and α-4-[1,3-dimethyl-(5-phenoxy group pyrazoles-4-base methylene amino oxygen)-special butyl ester of 4-methyl benzoic acid];
Tebufenpyrad (tebufenpyrad), chemical name: N-(4-tertiary butyl benzyl)-4-chloro-3-ethyl-1-methyl-pyrazoles-5-base formamide;
Halfenprox (halfenprox or fluproxyfen), chemical name: [2-(4-bromine difluoro methyl oxygen base phenyl)-2-methyl] propyl group-(3-phenoxy group) benzylic ether;
Butyl ether urea (diafenthiuron), chemical name: 1-tertiary butyl-3-(2,6-diisopropyl-4-Phenoxyphenyl) thiocarbamide;
Acrinathrin (acrinathrin), chemical name: (S)-alpha-cyano-3-phenoxy benzyl (Z)-(1R, 3R)-3-(2,2,2-three fluoro-1-trifluoromethyl ethyoxyl formyls) vinyl-2,2-dimethyl cyclopropane carboxylic acid ester;
C. bactericide class, for example
Kitazine (kitazine), chemical name: O, O-diethyl-S-dibenzylsulfide substituted phosphate;
Iprobenfos (iprobenfes), chemical name: O, O-diisopropyl-S-dibenzylsulfide substituted phosphate;
Hinosan (edifenphos), chemical name: O-ethyl-S, S-diphenyl phosphorodithioate;
Thiophanate (thiophanate), chemical name: 1, two (3-carbethoxyl group-2-the ghiourea group)-benzene of 2-;
Thiophanate-methyl (thiophanate-methyl), chemical name: 1, two (3-methoxycarbonyl-2-the ghiourea group)-benzene of 2-;
Tricyclazole (tricylazole), chemical name: the 5-methyl isophthalic acid, 2, the 4-triazol (3,4-b) benzothiazole;
Isoprothiolane (isoprothiolane), chemical name: 1,3-dithiolane-2-fork-Diisopropyl malonate;
MBAMT, chemical name: N, N '-methylene-two (2-amino-5-sulfydryl-1,3,4-thiadiazoles);
Fenaminosulf (fenaminosulf), chemical name: to Dimethylaminobenzene diazosulfonic acid sodium;
Mazn (zine methanearsonate), chemical name: zinc methyl-arsenate;
Tuzet (tuzet), chemical name: the saturating habit taken off, and soil is practised and being taken off, and this takes off soil;
Standing grain fringe peaceful (pencycuron), chemical name: nitrogen-[(4-chlorphenyl)-methyl]-nitrogen-cyclopenta-nitrogen-phenylurea;
Tian Ning (MAFA), chemical name: ammonium ferric methylarsonate;
Propiconazole (propiconazole), chemical name: 1-[2-(2,4 dichloro benzene base)-4-propyl group-1,3-dioxolanes-2-methyl]-1-hydrogen-1,2, the 4-triazole;
Flutriafol (flutriafol), chemical name: 2-(2-chlorphenyl) (4-fluorophenyl)-1-hydrogen-1,2,4-triazole-1-ethanol;
Metalaxyl (metalaxyl), chemical name: N-(2-methoxyl group acetyl group)-N-(2, the 6-xylyl)-racemic-alanine methyl esters;
Procymidone (procymidone), chemical name: N-(3, the 5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-di carbonyl imide;
Alkene azoles alcohol (diniconazole), chemical name: (E)-and 1-(2,4 dichloro benzene base)-4,4-dimethyl-2-(1,2,4-triazole-1 base)-1-amylene-3-alcohol;
Tolelofos-methyl (tolcofos-metheyl), chemical name: O-(2,6-dichloro-p-toluene base)-O, O-dimethyl disulfide substituted phosphate;
Carboxin (carboxin), chemical name: 2,3-dihydro-5-formyl is for anilino--6-methyl isophthalic acid, 4-oxygen thia 5,6-dihydro-2-methyl isophthalic acid, 4-oxygen thia-the 3-formailide;
Anilazine (anilazine), chemical name: 2,4-two chloro-6-(2-chlorobenzene amino) s-triazine;
Hymexazo (hymexazol), chemical name: 3-hydroxy-5-methyl-isoxazole;
Te Fuling (triflumizole), chemical name: 2-trifluoromethyl-4-chloro-N-(1-imidazoles-1-base-2-third oxygen ethylidene) aniline;
Vinclozolin (vinclozolin), chemical name: 3-(3, the 5-dichlorophenyl)-5-methyl-5-vinyl-2,4 oxazolidinedione;
Iprodione (iprodione), chemical name: 3-(3, the 5-dichlorophenyl)-1-isopropyl-carbamoyl hydantoin;
Benzene thiophene cyanogen (TCMTB), chemical name: 2-(thiocyanogen methyl sulfo-) benzothiazole;
Network ammonia copper, chemical name: sulfuric acid four ammonia complex copper;
Tiger glue adipic acid copper (Copper succinate; Copper glutarate; Copper adipate), chemical name: succinic acid copper, glutaric acid copper, adipic acid copper;
Lime sulfur (lime sulphur), chemical name: calcium polysulfide;
Zineb (zineb), chemical name: zinc ethylenebisdithiocarbamate;
Mancozeb (mancozeb), chemical name: ethylene bisdithiocarbamic manganese and zinc ion coordination compound;
Tmtd (thiram), chemical name: tetramethyl thiuram disulfide;
Ziram (ziran), chemical name: zine dimethyldithiocarbamate;
Asomate (asomate), chemical name: three-N-dimethyl dithiocarbamic acid arsine;
Triazolone (triadimefon), chemical name: 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazole-1-yl)-2-butanone;
Tpn (chlorothalonil), chemical name: 2,4,5,6-tetrachloro-1,3-benzene dicarbonitrile;
Carbendazim (carbendazim), chemical name: N-(2-benzimidazolyl) methyl carbamate;
Phosethyl-Al (phosethyl-Al), chemical name: three-(ethylphosphonic acid) aluminium;
Tridemorph (tridemorph), chemical name: 2,6-methyl-4-tridecyl morpholine;
Pcnb (quintozene);
Dazomet (dazomet), chemical name: 3,5-dimethyl-tetrahydro-1,3,5-dihydro thiadiazine-2-thioketones;
Acid amides azoles (imibenconazole), chemical name: 4-benzyl chloride base-N-(2,4 dichloro benzene base)-2-(1H-1,2,4-triazol-1-yl) thioacetamide ester;
Flusilazole (flusilazole), chemical name: two (4-fluorophenyl) methyl (1H-1,2,4-triazol-1-yl methylene) silane;
Azoles bacterium nitrile (propanenitrile), chemical name: 4-(4-chlorphenyl)-2-phenyl-2-(1H-1,2,4-triazol-1-yl methyl) butyronitrile;
Propamocarb (propamocarb), chemical name: 3-(dimethylamino) propyl carbamic acid propyl ester;
Dimethachlon (dimethachlon), chemical name: N-3,5 dichlorophenyl succimides;
The bromine bacterium is clear, chemical name: 2-bromo-2-bromomethyl glutaronitrile;
Oxolinic acide (oxolinic acid), chemical name: 5-ethyl-5,8-dihydro-8-oxo (1,3)-Er Evil-(4,5g)-quinoline-7-carboxylic acid;
Flusulfamide (flusulfamide), chemical name: 2 ', 4-two chloro-α, α-three fluoro-4 '-nitro-tolylsulfonyl-amine;
Frost urea cyanogen (cymoxanil), chemical name: carbonyl 2-cyano group-N-[(acetyl group)]-2-(methoxyl group imido grpup) acetamide;
Kocide SD (copric hydroxide);
Evil frost spirit (oxadixyl), chemical name: 2-methoxyl group-N-(2-oxo-1,3-oxazolidine-3-yl) acetyl-2 ', 6 '-dimethylaniline;
Antibiotic mycin 120, chemical name: antibiotic in pyrimidine nucleoside class;
Blasticidin-S (blasticidin S), chemical name: right-benzene methanamine base sulfonic acid blasticidin S
S-{4-[3-amino-5 (amino formamino) methylamino-1-oxo pentyl] amino }-1-[4-amino-2-oxo 1 (2H) pyrimidine radicals-1,2,3,4-four deoxidations-β-D-is red] six-2-alkene pyranose aldehydic acid;
Polyoxin (polyoxin), chemical name: peptide pyridimine nucleosides antibiotic, main component are polyoxin A and polyoxin B.
Polyoxin B is 5-{[2-amino-5-0-(amino carbonyl)-2-deoxidation-L-xylosyl] amino }-1,5-dideoxy-1-[3,4 dihydros-5-(hydroxymethyl)-2,4-dioxo-1 (2H)-pyrimidine radicals]-the other furanose aldehydic acid of β-D-;
Kasugarnycin (kasugamycin), chemical name: [5-amino-2-methyl-6-(2,3,4,5,6-penta hydroxy group cyclohexyl oxo) pyrans-3-yl] amino-α IMDA;
Jinggangmeisu
Glucose well ridge azanol
N-[(1S)-and (1,4,6/5)-3-methylol-4,5,6-trihydroxy-2-cyclohexenyl group] [O-β-D-glucopyranosyl-(1 → 3)]-1S-(1,2,3,4/3,5)-2,3,4-trihydroxy-5-methylol-cyclo-hexylamine;
D. seed treatment class, for example
Antibacterial agent 402, chemical name: ethyl thiol sulfonic acid ethyl ester;
Seedvax, chemical name: 2-amino-4-methyl-5-(N-phenyl amino formyl) thiazole;
First furan anilide (fenfuran), chemical name: 2-methyl-furans-3-formyl is for aniline;
Fenpiclonil (fenpiclonil), chemical name: 4-(2, the 3-dichlorophenyl) pyrroles-3-nitrile;
Tebuconazole (tebuconazole), chemical name: (RS)-and 1-(4-chlorphenyl)-4,4-dimethyl-3 (1H-1,2,4-triazole methyl)-3-amylalcohol;
Triadimenol (triadimenol), chemical name: 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl) butyl-2-alcohol;
Pefurazoate (pefurazoate), chemical name: penta-4-thiazolinyl-N-furfuryl group-TMSIM N imidazole-1-base carbonyl-DL-high lactamine ester;
Dithiocyano-methane;
E. classes of herbicides, for example
Penta sodium pentachlorophenate (PCP-Na);
Nitrofen (nitrofen), chemical name: 2,4 dichloro benzene base-4 '-nitrobenzophenone ether;
Oxyfluorfen (oxyfluorfen), chemical name: 2-chloro-1-(3-ethyoxyl-4-nitrophenoxy)-4-trifluoromethylbenzene;
Fomesafen (fomesafen), chemical name: N-(methyl sulphonyl)-5-[2-chloro-4-(trifluoromethyl) phenoxy group]-the 2-nitrobenzamide;
Trefanocide (trifluralin), chemical name: 2,6-dinitro-N, N-di-4-5-trifluoromethylaniline;
(pendimethalin), chemical name: N-1-(ethyl propyl)-2,6-dinitro-3,4-dimethylaniline are led in weeding;
Amex820 (butralin), chemical name: N-isobutyl group-4-tertiary butyl-2,6-dinitroaniline;
2 first, 4 chlorine (metaxon), chemical name: 2-methyl-4-chlorophenoxyacetic acid;
2, and the 4-d butyl ester (2,4-D, butylate), chemical name: 2,4 dichlorophenoxyacetic acid butyl ester;
Quizalofop-ethyl (quizalofop-ethyl), chemical name: 2-[4-(6-chloro-2-quinoxalinyl oxo)-phenoxy group] ethyl propionate;
Quizalotop-ethyl (quizalpfop-p-ethyl), chemical name: (R)-and 2-[4-(6-chloro-2-quinolyl oxo)-phenoxy group] ethyl propionate;
Fluazifop (fluazifop-butyl), chemical name: 2-[4-(5-trifluoromethyl-2-pyridine oxygen base) phenoxy group] butyl propionate;
Efficient fluazifop (fluazifop-p-butyl), chemical name: (R)-and 2-{4-[(5-5-flumethiazine-2-yl) the oxygen base] phenoxy group } butyl propionate;
Pyrrole fluorine second grass spirit (haloxyfop), chemical name: 2-[-4-(5-trifluoromethyl-3-chloro-pyridine-2-oxygen base) phenoxy group] propionic acid ethoxyethyl ester;
Efficient pyrrole fluorine chlorine standing grain spirit (haoxyfop-R-methyl), chemical name: R-(+)-2-[4-(5-trifluoromethyl-3-chloro-pyridine oxygen base-2) phenoxy group] methyl propionate;
Fenoxaprop (fenoxaprop-p-ethyl), chemical name: (R)-and 2-[4-(6-chloro-2-benzoxazole oxygen base)-phenoxy group] ethyl propionate;
Nong Meili (bispyribac-sodium), chemical name: 2, two [(4, the 6-dimethoxypyridin-2-yl) oxygen] Sodium Benzoates of 6-;
Alachlor (alachlor), chemical name: N-(methoxyl methyl)-N-chloracetyl-2,6-diethylaniline;
Acetochlor (acetochor), chemical name: 2 '-ethyl-6 '-methyl-N '-(ethoxymethyl)-2-chloro acetanilide;
The third careless amine (pretilachlor), chemical name: α-chloro-2 ', 6 '-diethyl-N-(the 2-third oxygen ethyl)-acetanil;
Butachlor (butachlor), chemical name: 2,6-diethyl-N-(fourth oxygen methyl)-α-chloracetanilide;
Isopropyl methoxalamine (metolachlor), chemical name: 2-ethyl-6-methyl-N-(1 '-methyl-2 '-methoxyethyl) chloro acetanilide;
Naphthalene propionyl grass amine (napropamide), chemical name: N, N-diethyl-2-(1-naphthyl oxygen) propionamide;
Mefenacet (mefenacet), chemical name: 2-(1,3-benzothiazole-2-base oxygen)-N-methyl acetanil;
Stam F-34 (propanil), chemical name: 3, the 4-two chloro propionyl polyaniline;
Glyphosate (glyphosate), chemical name: N-(phosphine carboxymerhyl) glycine;
Clean piperazine phosphorus: by 4 parts of piperophoses and the clean mix preparation of forming of a penta grass
Chemical name: piperophos is S-[2-(2-methyl isophthalic acid-piperidyl)-2-oxoethyl]-O, O-dipropyl phosphorodithioate
Chemical name: penta grass is 4-(1,2-dimethyl-n-propylamine base)-2-ethylamino--6-methyl mercapto s-triazine only;
Benthiocarb (thiobencarb), chemical name: N, N-diethyl thiol carbamic acid is to the benzyl chloride ester;
Molinate (molinate), chemical name: N, N-hexamethylene thiol urethanes;
Dimepiperate (dimepiperate), chemical name: S-(α, α-Er Jiajibianji) piperidines-1-thiol formic acid esters;
Vernolate (vernolate), chemical name: S-propyl group-N, N-dipropyl thiocarbamate;
Isoproturon (isoproturon), chemical name: N-4-isopropyl phenyl-N ', N '-dimethyl urea;
Chlortoluron (chlorotoluron), chemical name: N-(3-chloro-4-aminomethyl phenyl)-N ', N '-dimethyl urea;
Diuron (diuror), chemical name: N-(3, the 4-dichlorophenyl)-N ', N '-dimethyl urea;
The Tianjin (atrazine) of withering, chemical name: 2-chloro-4-ethylamino--6-isopropylamine base-1,3,5-triazines;
Prometryn (prometryne), chemical name: 2-methyl mercapto-4,6-bis-isopropylamine base s-triazine;
Symetryne (simetryn), chemical name: 2-methyl mercapto-4,6-bis-ethylamino-s-triazine;
Piperazine humulone (metribuzin), chemical name: 4-amino-6-(1 ', 1 '-dimethyl ethyl)-3-(methyl mercapto)-1,2,4-triazine-5-(4H)-ketone;
Evil humulone (oxadiazon), chemical name: 5-tertiary butyl-3-(2,4-two chloro-5-o-phenyl-isopropyls)-1,3,4-oxadiazole quinoline-2-ketone;
Rice thinks to reach (oxadiargyl), chemical name: 5-tertiary butyl-3-[2,4-two chloro-5-(alkynes propoxyl group) phenyl]-1,3,4-oxadiazole-2-(3H)-ketone;
Clomazone (clomazone), chemical name: 2-(2-chlorphenyl) methyl-4,4-dimethyl isoxazole alkane-3-ketone;
Bentazone (bentazone), chemical name: the 3-isopropyl-(1H)-and benzo-2,1,3-thiadiazine-4-ketone-2,2-dioxide;
Dichloro quinolinic acid (quinclorac), chemical name: 3,7-two chloro-8-Quinoline Carboxylic Acids;
Benazolin (benazolin-ethyl), chemical name: 4-chloro-2-oxo-benzothiazole-3-guanidine-acetic acid ethyl ester;
Paraquat (paraquat), chemical name: 1,1 '-dimethyl-4,4 '-bipyridine cation salt;
Fluorine grass fixed (fluroxypyr), chemical name: 4-amino-3,5-two chloro-6-pyridine-2-fluoroacetic acid;
Difenzoquat (difenzoqnat), chemical name: 1,2-dimethyl-3,5-diphenylpypazole Methylsulfate;
Metsulfuron-methyl (metsulfuron-methyl), chemical name: 1-(2-methoxy methyl acyl group phenyl)-3-(4-methyl-6-methoxyl group-1,3,5-triazines-2-yl) sulfonylureas;
Bensulfuron-methyl (bensulfiron methyl), chemical name: 2-[[[[[(4,6-dimethoxypyridin-2) amino] the carbonyl acyl] amino] sulfonyl] methyl] methyl benzoate;
Pyrazosulfuron (pyrazosulfuron-ethyl), chemical name: 5-[3-(4,6-dimethoxypyridin-2-yl) ureido sulfuryl]-1-methylpyrazole-4-carboxylic acid, ethyl ester;
Chlorine sulphur swells (chlorsulfuron), chemical name: 1-(2-chlorphenyl)-3-(4-methyl-6-methoxyl group-1,3,5-triazole-2-yl) sulfonylureas;
Tribenuron-methyl (tribenuron methyl), chemical name: 2-[(4-methoxyl group-6-methyl isophthalic acid, 3,5-three pyridines-2-yl)-amino-carbonyl sulfamide groups] methyl benzoate;
The fen of thiophene sulphur is swelled (thifensulfuron methyl), chemical name: 3-[(4-methoxyl group-6-methyl isophthalic acid, 3,5-triazinyl-2-yl) the amino carbonyl amino sulfonyl]-the 2-Thiophene Carboxylic Acid methyl esters;
Ethametsulfuron (ethametsulfuron), chemical name: 3-(4-ethyoxyl-6-methylamino-1,3,5-triazines-2-yl)-1-(2-methoxy methyl acyl group phenyl) sulfonylureas;
Chlorimuronethyl (chlorimuron-ethyl), chemical name: 3-(4-chloro-6-methoxy pyrimidine-2-yl)-1-(2-ethoxy acetyl phenyl) sulfonylureas;
Nicosulfuron (nicosulfuron), chemical name: 3-(4,6-dimethoxypyridin-2-yl)-1-(3-dimethylamino formylpyridine-2-yl) sulfonylureas;
Cinosulfuron (cinosulfuron), chemical name: 3-(4,6-dimethoxy-1,3,5-triazines-2-yl)-1-[2-2-methoxy ethoxy-phenyl] sulfonylureas;
Imazethapyr (imzethapyr), chemical name: 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl)-3-picolinic acid;
Evil humulane in heptan (cinmethylin), chemical name: methoxyl group 1-methyl-4 (1-Methylethyl)-2-[(2-aminomethyl phenyl)]-7-Evil two ring (2,2,1) heptane;
Sethoxydim (sethoxydim), chemical name: 2-[1-(ethoxy amido) butyl]-5-[2-(ethylmercapto group) propyl group]-3-hydroxyl-2-cyclic ethylene-1-ketone;
F. plant growth regulator class, for example
Gibberellin (gibberellic acid), chemical name: 2,4a, 7-trihydroxy-1-methyl-8-methylene red mould-3-alkene-1,10-dicarboxylic acids-1,4a-lactone;
Drop-proof agent (4-CPA);
Growth promotor for crop
(1) sodium-para-nitrophenolate
Sodium onitrophenol
Sodium p-nitrophenoxide
5-nitro o-methoxyphenol sodium
(2) complex nitor-phenol potassium
ONP potassium
Right-nitrophenol potassium
2,2, 4-dinitrophenol potassium;
Methyl (α-naphthalene acetic acid), chemical name: α-Nai Yisuan;
Heteroauxin (IAA), chemical name: 2-(indol-3-yl) acetate;
Indolebutyric acid (IBA), chemical name: 4-(indol-3-yl) butyric acid;
Volume increase is plain, chemical name: 4-bromobenzene fluoroacetic acid;
Production increasing agent, chemical name: 4-iodobenzene fluoroacetic acid;
6-benzyl aminopurine (6-benzylaminopurine);
2,4-drip (2,4-D), chemical name: 2,4 dichlorophenoxyacetic acid;
Triacontanol (triacontanol), chemical name: triacontanol-1 (N-triacontanol);
Study on brassinolide (brassinolide), chemical name: (22R, 23R, 24R)-2 α, 3 α, 22,23-tetrahydroxy-B homogeneous phase-7 oxygen diindyl-5 α-lumistane-6-ketone;
Triapenthenol (triapentheno), chemical name: (E)-(ES)-and 1-cyclohexyl-4,4-dimethyl-2 (1H-1,2,4-triazol-1-yl) penta-1-alkene-3-alcohol;
Choline Chloride (choline chloride);
CPPU (forchlorfenuron), chemical name: 1-(2-chloro-4-pyridine)-3-phenylurea;
Uniconazole P (uniconazole), chemical name: (E)-(RS)-and 1-(4-chlorphenyl)-2-(1,2, the 4-triazol-1-yl)-4,4-dimethyl-1-amylene-3-alcohol;
Oxyenadenine (oxyenadenine), chemical name: 6-(4-hydroxy-3-methyl butene-2-amino) purine;
Green wind 95 plant growth regulator;
Naphthenate (naphthenate);
Naphthenate (sodium, ammonium);
Pyridine alcohol (pyripro panal), chemical name: 3-(2-pyridine radicals)-propyl alcohol;
Paclobutrazol (paclobutrazol), chemical name: (2RS, 3RS)-1-(4-chlorphenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)-penta-3-alcohol;
Regulate phosphine (fosamine ammonium), chemical name: carbamoyl phosphinic acid ethyl ester ammonium salt;
Flumetralim (flumetralim), chemical name: N-ethyl-N-(2-chloro-6-luorobenzyl)-4-trifluoromethyl-2,6-dinitroaniline;
Chlormequat (chlormequat chloride), chemical name: 2-chloroethyl-trimethyl ammonium chloride;
Help strong plain (mepiquat cholride), chemical name: 1,1-lupetidine iron drone chloride;
Morphactin (chlorflurecol-metyl), chemical name: 2-chloro-9-hydroxyphenyl fluorene-9-hydroxy acid methyl esters;
Alar-85 (daminozide), chemical name: N, the acid of N-Daminozide;
Triiodobenzoic acid (TIBA), chemical name: 2,3, the 5-Triiodobenzoic acid;
Maleic hydrazide (maleic hydrazide), chemical name: 1,2-dihydro-3,6-pyridazine diketone;
Ethrel (ethephon), chemical name: 2 chloroethyl phosphoric acid;
Thidiazuron (thidiazuron), chemical name: 1-phenyl-3-(1,2,3-thiadiazoles-5-yl) urea;
'Inshuzhi ' (efchlozate), chemical name: 5-chloro-1H-indol-3-yl ethyl acetate;
Increase sweet phosphine (glyphosine), chemical name: N, two (phosphine hydroxymethyl) glycine of N-;
Isopentennyladenine, chemical name: 6-(4-hydroxy-3-methyl-trans-2-butene base amino) purine
6-(3-methyl-2-butene base amino) purine;
G. storage pest is prevented and treated the agent class, for example
Pest control phosphorus;
Pirimiphos-methyl (pirimiphos-methyl), chemical name: O, O-dimethyl-O-(2-diethyl amido-6-methylpyrimidine-4-yl) thiophosphate;
Vikane (sulphuryl fluoride);
Celfume (methyl bromide);
Aluminum phosphate (aluminium phosphide);
Chloropicrin (chloropicrin), chemical name: trichloronitromethane.
In the present invention, used pesticide activity component can be for pesticide original medicine or its various dosage forms, as suspending agent, emulsion, wetting powder.
Composition pesticide according to a first aspect of the invention, wherein the content of pesticide activity component is 0.01～90.0% weight of composition weight, is preferably 10-80% weight, more preferably 30-70% weight; Hollow porous SiO 2Nano particle is 10～99.9% weight of composition weight, is preferably 20-90% weight, more preferably 30-70% weight.
Composition pesticide according to a first aspect of the invention wherein also contains additive, organic solvent or water that agricultural chemicals is used, and described additive is 0.01～35.0% weight of composition weight.
According to a second aspect of the invention, provide a kind of method for preparing composition pesticide, it comprises the steps:
A) pesticide activity component is dissolved in obtains a solution in organic solvent or the water;
B) with hollow porous SiO 2Nano particle in vacuum drying chamber in 90～600 ℃ of temperature,
Activate 1～24 hour under the condition of vacuum 0.01～0.1Mpa;
C) with the hollow porous SiO that obtains in the step b) 2Nano particle mixes with a) solution and soaked 0.5 hour～3 months;
D) randomly add additive and can obtain product emulsion;
E) maybe will be through soaking the hollow porous SiO of pesticide activity component 2The nano particle drying obtains solid product or is scattered in the water under high-speed stirred, forms aqua product.
Prepare emulsion, can select the device of the strong shearing force of many suitable generations for use.The inventive method is normally carried out in colloid mill.Nano controlled release agent of the present invention needs dilute with water when reality is used, use with conventional method, for example passes through spray application.Nano pesticide controlled release agent usage amount of the present invention can change within the specific limits, depends on to be applied object, and the content of agricultural chemicals in the nano pesticide controlled release agent.
Figure 12 represents the schematic diagram of hollow porous silica nano material embedding Avermectin.Figure 17 represents the hollow porous silica nano material schematic diagram after the embedding Avermectin.
Method according to a second aspect of the invention, wherein form emulsion after, drying obtains solid product.
The present invention also provides the method (seeing Figure 13) of another kind of production composition pesticide of the present invention.This method comprises:
(1) carbon dioxide of high pressure is transported to cooling device through pump and changes into postcritical CO 2 fluid;
(2) join in the reactor with pesticide activity component with as the hollow porous nano SiO 2 particle of carrier;
(3) postcritical CO 2 fluid is fed autoclave;
(4) through decompression, postcritical CO 2 fluid is discharged with carbonic acid gas institute body, obtains desired composition pesticide.
This method is called the high pressure investment.Because pesticide activity component has higher solvability in postcritical CO 2 fluid, therefore to compare with the infusion method of normal temperature and pressure, pesticide activity component can enter hollow porous nano SiO 2 particle quickly.
Being example below with the Avermectin is described in detail the preparation of composition pesticide of the present invention.
The composition of nano controlled release agent is as follows by quality representation:
The former medicine of Avermectin: 100g
Hollow porous SiO 2Controlled release carrier: 50g
Organic solvent (acetone): 900g
Emulsifier (softex kw): 10.0g
Dispersant (sodium polymethacrylate): 10.0g
Preservative (penta sodium pentachlorophenate): 10.0g
Protecting colloid (polyvinyl alcohol): 10.0g
Defoamer (tributyl phosphate): 5.0g
Antifreezing agent (glycerine): 10.0g
Wherein, the content of the former medicine of Avermectin is 98% (the biochemical Co., Ltd of Zhejiang Qian Jiang); Hollow porous SiO 2The average grain diameter of controlled release carrier is 70 nanometers, and wall thickness is about 10 nanometers, and the aperture on the wall is 4 nanometers, and Figure 14-16 is the phenogram of hollow porous silica controlled release carrier; Solvent is acetone, n-butanol, chloroform, thiacyclohexane, ethanol, isopropyl alcohol, kerosene, methyl alcohol, toluene etc.
Emulsifier is a nonionic emulsifier, cationic emulsifier or anion emulsifier; Nonionic emulsifier can be used tween type, sapn type or polyoxyethylene nonylphenol ether; Anion emulsifier is selected dodecyl phenenyl sulfate, neopelex or calcium dodecyl benzene sulfonate etc. for use.The preferred softex kw of cationic emulsifier; The dispersant that is fit to is the copolymer of poly-methyl acrylate, low molecular weight phenylethylene-maleate.Protecting colloid is: materials such as polyvinyl alcohol, Sodium Polyacrylate, methylcellulose, carboxymethyl cellulose, pectate, gelatin, gum Arabic or PEO; Preservative is penta sodium pentachlorophenate, adjacent chloro-m-cresol or a daconil M etc. commonly used in the polymer emulsion; Defoamer is silane derivative dimethyl silicone polymer class, tributyl phosphate or poly propane diols etc.; Antifreezing agent has ethylene glycol, glycerine, propane diols, 2-Butoxyethyl acetate, urea or sucrose etc.
The continuous phase of avermectin nanometer pesticide action-controlling agent is made up of as emulsifier, dispersant, protecting colloid, preservative, defoamer and antifreezing agent organic solvent and additive, and preferred ingredients is top those materials of mentioning.Continuous phase can also comprise a spot of dispersed phase component in addition.
The hollow porous SiO of avermectin nanometer pesticide action-controlling agent 2Controlled release carrier is formed and can also be changed within the specific limits.In system, the amount of disperse phase be generally by weight 5.0～50.0%, the concentration of each material following (by avermectin nanometer controlled release agent weight) in the disperse phase:
Hollow porous SiO 2Controlled release carrier: 0.01～99.5%;
The former medicine of Avermectin: 0.01～90.0%;
Additive is generally 0.01～35%, is preferably 5.0～20.0%.
The preparation method of avermectin nanometer controlled release agent comprises the steps:
Method one:
1) the 100.0g Avermectin is dissolved in the 900.0g acetone solvent, is made into 10.0% Avermectin acetone soln, stand-by;
2) take by weighing the hollow porous nanometer SiO of 50.0g 2Controlled release carrier, hollow porous SiO 2The average grain diameter of controlled release carrier is 70 nanometers, and wall thickness is about 10 nanometers, and the aperture on the wall is 4 nanometers.150 ℃ of temperature, under the vacuum 0.1MPa condition, activation 6h;
3) the hollow porous SiO after the taking-up activation 2Nano particle joins the 10% Avermectin acetone soln for preparing, and soaks embedding;
4) hollow porous SiO 2Basic mix with the organic solvent solution of former medicine soak embedding a period of time after, take out sample, oven dry, the hollow porous nanometer SiO of 50.0% Avermectin that promptly got embedding 2The mixture of carrier, stand-by;
5) emulsifier 10.0g and other additive are mixed, put into a container that has a stirring, add entry to 1.0kg, under high-speed stirred, the hollow porous nanometer SiO of Avermectin that added embedding 2Carrier is dispersed into emulsion, then, through the colloid mill homogeneous, can obtain the emulsion of good dispersion, adds additive, and discharging obtains avermectin nanometer controlled release agent (product), and the content of Avermectin is 5.0% in the product.Or be drying to obtain solid product.
Method two:
1), 2), 3) and, identical with method one; 4) hollow porous SiO 2Basic mix with the organic solvent solution of former medicine soak embedding a period of time after, emulsifier 10.0g and other additive added mix, then,, can obtain the emulsion of good dispersion through the colloid mill homogeneous, add additive, discharging.Promptly obtain avermectin nanometer controlled release agent (product).
Hollow porous SiO 2The performance evaluation of base avermectin nanometer controlled release agent:
1) takes by weighing a certain amount of porous hollow nanometer SiO 2Carrier activates 6h down at 150 ℃, adds the acetone soln of 10% Avermectin then, soaks at normal temperatures.Take out sample respectively in the different time periods, measure its embedding rate (adopting the method for thermogravimetric to measure its embedding rate).Different soak times are to the influence of Avermectin embedding rate, and along with the prolongation of soak time, carrier increases the embedding rate of Avermectin, reaches capacity after 14 days, and embedding rate is 58.30%.So just can control the release of medicine by control embedding rate size.Figure 17 is adsorbed on the schematic diagram of avermectin nanometer controlled release agent (Av-PHSN) for Avermectin.Figure 18 is the feature thermogravimetric analysis figure of avermectin nanometer controlled release agent (Av-PHSN).In the triphasic weightless corresponding avermectin nanometer controlled release agent respectively, be adsorbed on the amount of the Avermectin of outer surface, duct and hollow interior respectively.
2) the infared spectrum analysis of avermectin nanometer controlled release agent (Av-PHSN).Figure 19 is porous hollow nanometer SiO 2The infrared spectrum analysis of carrier, avermectin nanometer pesticide action-controlling agent (Av-PHSN) and the former medicine of Avermectin.As can be seen from the figure, avermectin nanometer pesticide action-controlling agent (Av-PHSN) does not produce new peak, so be physical adsorption.The various character to medicine do not exert an influence behind the carrier embedding medicinal like this
3) the feature controlled release behavior of avermectin nanometer pesticide action-controlling agent (Av-PHSN).The dissolution test of avermectin nanometer pesticide action-controlling agent (Av-PHSN), test is carried out at medicament dissolution instrument (Radio Factory of Tianjin Univ.'s product).Concrete operations are as follows: take by weighing a certain amount of avermectin nanometer pesticide action-controlling agent (Av-PHSN), join to be equipped with in the stripping rotor that 800ml contains 30% ethanolic solution and carry out stripping, under certain time interval, take out the liquid of stripping rotor and use high performance liquid chromatograph (Hitachi) to measure the concentration of solution Avermectin, with the dissolution time is abscissa, percentage with the stripping quantity of Avermectin is ordinate (being the total amount of the amount/avermectin nanometer pesticide action-controlling agent Av-PHSN of stripping Avermectin), and the curve of having done is the sustained release curve of nano-avermectin controlled release agent.The sustained release curve of nano-avermectin controlled release agent has following feature and release rule.
The comparison of the former medicine of A Wei, Jie's A Wei medicine stripping curve
Accompanying drawing 20 is former medicine of A Wei (solid-state) and porous hollow nanometer SiO 2The comparison diagram of the physical mixture of carrier (the former medicine content of A Wei is 33.50%), avermectin nanometer pesticide action-controlling agent (content of Avermectin is 58.30%) stripping curve.As can be seen from the figure, the former medicine of A Wei just reached dissolution equilibrium (the former medicine of contained A Wei this moment all dissolving is discharged in the solution) after tens minutes, and avermectin nanometer pesticide action-controlling agent (Av-PHSN) has good slowly-releasing behavior, just reaches balance to 2000min.This shows novel controlled release carrier porous hollow nanometer SiO 2Good slow release effect is arranged.
Figure 21-the 22nd, different pH values is the controlled release behavior of avermectin nanometer pesticide action-controlling agent (Av-PHSN) down.
Different pH values to the leaching condition of avermectin nanometer pesticide action-controlling agent (Av-PHSN) release behavior influence is: 30% ethanolic solution 800ml, and the temperature of medium is 21 ℃, mixing speed is 100 commentaries on classics/min, the pH value of medium is respectively 3.0,5.0,7.0,8.0,9.0,10.0.Figure 21～22 are the different pH value comparison diagram to nano pesticide controlled release agent (Av-PHSN) the release behavior influence of Avermectin.As can be seen from the figure, along with the increase of pH value, i.e. Jian Xing enhancing, acid weakens, and the rate of release of medicine Avermectin increases.
Figure 23 is the influence to avermectin nanometer pesticide action-controlling agent (Av-PHSN) release behavior of different medium temperature.Leaching condition is: 30% ethanolic solution 800ml, and the pH value of medium is neutral, and mixing speed is 100 commentaries on classics/min, and temperature is 21 ℃, 27 ℃, 37 ℃.Figure 12 is the release behavior of the avermectin nanometer pesticide action-controlling agent (Av-PHSN) under the different medium temperature.As can be seen from the figure, along with the rising of temperature, the release behavior of the nano pesticide controlled release agent (Av-PHSN) of Avermectin can be accelerated.
The inventive method can be carried out under normal pressure.Nano controlled release agent of the present invention needs dilute with water when reality is used, use with conventional method, for example passes through spray application.Nano pesticide controlled release agent usage amount of the present invention can change within the specific limits, depends on to be applied object, and the content of Avermectin in the nano pesticide controlled release agent.
The avermectin nanometer pesticide action-controlling agent has solved the problem of water baseization, high degree of dispersionization, stabilisation and the spansuleization of preparation comprehensively, and its drug effect is higher than other formulations, cost is lower than other common formulations, therefore has important generalization and application value.
The present invention utilizes hollow porous silica as controlled release carrier material, this material is a porous on the thin-walled of hollow, and thin-walled is made up of silica dioxide granule, the wall of described particle has the substantially radially duct of arranged vertical, can control the release of medicine by the thickness of control duct size and thin-walled.Perhaps, (can reach the control wall thickness by increasing silica concentration) reaches the purpose of control drug release time to select for use the controlled-release material of different wall thickness to control; In order to make medicine under different condition, control slow release speed, can design the nano particle of different pharmaceutical concentration and different wall degree, carry out mixed preparing in proportion, reach the control purpose of different release times.
Utilize distinct methods that various agricultural chemicals is filled into the middle vacancy of hollow porous silica, the condition of controling environment is controlled the release of medicine then.Because particle is thinner, be nanoscale, thereby its dissolubility is good, good dispersion can replace most organic solvent for water, thereby can significantly reduce the consumption of organic solvent, improve the fineness of agricultural chemicals in the opacifier or the aqueous solution, improve the drug effect and the effective rate of utilization of agricultural chemicals.
Composition pesticide of the present invention, owing to adopted the release of porous hollow nano carrier material control pesticide activity component, have polymolecularity, particle thin (for nanoscale), sustained release, super-high-efficient, long-acting, water base, with low cost, reduce advantage such as environmental pollution.And, slow down medicine decomposition or degraded, thereby reach the purpose of slowly-releasing owing to adopt the uvioresistant nano material to prevent from medicine is carried out photocatalysis.
With specific embodiment the present invention is carried out specific description below.But the invention is not restricted to the scheme of the embodiment that provides.
The mensuration of agricultural chemicals embedding rate:
The hollow porous SiO of eggshell type 2The nano controlled release carrier is to the embedding of agricultural chemicals, method is as follows: take by weighing a certain amount of porous hollow nanometer SiO2 carrier, activate 6h down at 145 ℃, add saturated pesticidal solutions then, carry out embedding, take out sample then, measure its embedding rate, its assay method adopts the thermogravimetric method to measure, and concrete operations are for using thermal analyzer (STA 449C
Figure C20041004331300351
Figure C20041004331300352
GmbH, Germany), test condition: programming rate is 10 ℃/minute, and 30 ℃-800 ℃ of intensification scopes adopt air as protection gas, and its weight-loss ratio is the embedding rate of agricultural chemicals.The agricultural chemicals embedding rate calculates according to following formula:
Gross weight * 100% of the amount of agricultural chemicals/controlled release medicament in the embedding rate of agricultural chemicals=controlled release medicament
Hollow porous SiO 2The preparation embodiment of nano particle
Hollow porous SiO 2Preparation of nanoparticles embodiment 1
Spherical hollow porous SiO 2The preparation method of nano particle (thin-shell type nano mesoporous balls)
Taking by weighing particle diameter is 40nm calcium carbonate powder (cube) 8.7g, adds deionized water 50g, adds 2.5g softex kw (CTMAB) and 13.2g (about 15ml) and analyzes pure ammoniacal liquor, add 60g ethanol again, at rotating speed is to stir 15min under the 300rpm, presses silicon/carbon dioxide acid calcium=0.15 (weight ratio) and adds ethyl orthosilicate (TEOS), stirred 2 hours, filtration, an amount of alcohol flushing of filter cake, dry in baking oven, 90 ℃ of temperature, muffle furnace roasting, 550 ℃ of temperature, the time is 5h.The sample diluted hydrochloric acid dissolution is kept pH less than 1, is drying to obtain product.
Hollow porous SiO 2Preparation of nanoparticles embodiment 2
Tubular, hollow porous SiO 2Nano particle (meso-porous hollow pipe) preparation method
Take by weighing diameter 200～300nm, draw ratio is 5 calcium carbonate powder (needle-like) 8.7g, add deionized water 50g, add 2.5g softex kw (CTMAB) and 13.2g (about 15ml) and analyze pure ammoniacal liquor, add 60g ethanol again, at rotating speed is to stir 15min under the 300rpm, press silicon/carbon dioxide acid calcium=0.2 (weight ratio) and add ethyl orthosilicate (TEOS), stirred 2 hours, filtration, an amount of alcohol flushing of filter cake, dry in baking oven, 90 ℃ of temperature, the muffle furnace roasting, 550 ℃ of temperature, the time is 5h.The sample diluted hydrochloric acid dissolution is kept pH less than 1, is drying to obtain product.
Hollow porous SiO 2Preparation of nanoparticles embodiment 3
Hollow porous SiO 2The preparation method of nano particle (thin-shell type nano mesoporous balls)
Take by weighing barium carbonate 100nm (sphere) powder 10g, add deionized water 50g, add 3g softex kw (CTMAB) and 13.2g (about 15ml) and analyze pure ammoniacal liquor, add 60g ethanol again, at rotating speed is to stir 15min under the 300rpm, presses silicon/carbon dioxide acid barium=0.2 (weight ratio) and adds ethyl orthosilicate (TEOS), stirred 2 hours, filtration, an amount of alcohol flushing of filter cake, dry in baking oven, 90 ℃ of temperature, muffle furnace roasting, 550 ℃ of temperature, the time is 5h.The sample diluted hydrochloric acid dissolution is kept pH less than 1, is drying to obtain product.
The hollow porous SiO of eggshell type 2Nanosphere prepares embodiment 4
The hollow porous SiO of eggshell type 2The preparation method of nanosphere
Measuring 500ml concentration and be 8.0% calcium carbonate average grain diameter is 40-50nm (sphere) suspension (determining concentration by capacity analysis), take by weighing 5g softex kw (CTMAB), mixing with calcium carbonate suspension, is to stir 30min under the 1800rpm at rotating speed.Accurately the silica containing concentration of preparation is 2% sodium silicate solution, press silicon/carbon dioxide acid calcium=1～50% (wt), suspension is risen to 80 degree, in 2 hours, evenly sodium silicate solution is joined in the calcium carbonate suspension, with concentration is that certain pH is kept in 10% hydrochloric acid adjustment, the reinforced ageing 2 hours that finishes, with its filtration, dry in baking oven, 100 ℃ of temperature, the muffle furnace roasting, 700 ℃ of temperature, the time is 5h.The sample diluted hydrochloric acid dissolution is kept pH less than 1, is drying to obtain the hollow porous SiO of eggshell type 2Nanosphere.
Composition pesticide prepares embodiment 1
The former medicine 10.0g of pesticidal active substance methyl abamectin benzoate (the biochemical Co., Ltd of Zhejiang Qian Jiang), hollow porous SiO 2Controlled release carrier 10.0g, hollow porous SiO 2Controlled release carrier is from preparation embodiment 4, and its average grain diameter is 70 nanometers, and the hollow mean inside diameter is that 50 wall thickness are about 10 nanometers, and the aperture on the wall is 4.5 nanometers, and the duct is that vertical channel is arranged.Toluene 90.0g, emulsifier (softex kw) 5.0g.The former medicine of 10.0g methyl abamectin benzoate is dissolved in the 90.0g toluene solvant, is made into 10.0% methyl abamectin benzoate toluene solution, stand-by; Take by weighing the hollow porous SiO of 10.0g 2The nano controlled release carrier, 150 ℃ of temperature, vacuum 0.1Mpa, activation 6h; Then, the hollow porous nanometer SiO after the taking-up activation 2Carrier joins in the 10.0% methyl abamectin benzoate toluene solution for preparing, and soaks 14 days; Take out sample, oven dry, the hollow porous nanometer SiO of 50.0% Avermectin that promptly got embedding 2The mixture of carrier, stand-by; Emulsifier 5.0g (softex kw) and cosolvent (methyl alcohol) 20g are mixed, put into a container that has a stirring, add entry to 1kg, under agitation, the hollow porous SiO of methyl abamectin benzoate that added embedding 2Nano-carrier is dispersed into emulsion, then, through the colloid mill homogeneous, can obtain the emulsion of good dispersion, adding preservative agent (penta sodium pentachlorophenate) 2g, discharging.The content of Avermectin is 1.0% in the product.Or be drying to obtain solid product.
Composition pesticide prepares embodiment 2
The former medicine of pyrazosulfuron (99.33%) (Shanghai Organic Chemistry Institute, Chinese Academy of Sciences) 35.0g, hollow porous nanometer SiO 2Controlled release carrier 20.0g, hollow porous nanometer SiO 2Controlled release carrier prepares the identical of embodiment 1 with composition pesticide.Ethyl acetate 965.0g, emulsifier (sorbester p17) 5.0g.The former medicine of 35.0g pyrazosulfuron is dissolved in the 965.0g ethyl acetate solvent, is made into 3.5% pyrazosulfuron ethyl acetate solution, stand-by; Take by weighing the hollow porous nanometer SiO of 20.0g 2Controlled release carrier, 150 ℃ of temperature, vacuum 0.1Mpa, activation 6h; Then, the hollow porous nanometer SiO after the taking-up activation 2Carrier joins in the 3.5% pyrazosulfuron ethyl acetate solution for preparing, and soaks 30 days; Take out sample, oven dry, the hollow porous nanometer SiO of pyrazosulfuron that promptly got embedding 2The mixture of carrier, stand-by; Emulsifier (sorbester p17) 5.0g and protecting colloid (polyvinyl alcohol) 1.0g are mixed, put into a container that has a stirring, add benzene to 1.0kg, under agitation, the hollow porous nanometer SiO of pyrazosulfuron that added embedding 2Carrier is dispersed into emulsion, then, through the colloid mill homogeneous, can obtain the emulsion of good dispersion, adds adding preservative agent (adjacent chloro-m-cresol) 2g, discharging.The content that can be made into pyrazosulfuron is 0.5%, 1.0%, 1.5% product.Or be drying to obtain solid product.
Composition pesticide prepares embodiment 3
The former medicine 20.0g of jinggangmeisu (the biochemical Co., Ltd of Zhejiang Qian Jiang), hollow porous SiO 2Controlled release carrier 20.0g uses hollow porous nanometer SiO 2Controlled release carrier prepares the identical of embodiment 1 with composition pesticide.Water 80.0g, emulsifier 5.0g.The former medicine of 20g jinggangmeisu is dissolved in the 80.0g water, is made into the 20.0% jinggangmeisu aqueous solution, stand-by; Take by weighing the hollow porous SiO of 20.0g 2The nano controlled release carrier, 150 ℃ of temperature, vacuum 0.10Mpa, activation 6h; Then, the hollow porous SiO after the taking-up activation 2Nano-carrier joins in the 20.0% jinggangmeisu aqueous solution for preparing, and soaks 10 days; Take out sample, oven dry, the hollow porous nanometer SiO of jinggangmeisu that promptly got embedding 2The mixture of carrier, stand-by; Emulsifier (neopelex) 5.0g and preservative (penta sodium pentachlorophenate) 3g are mixed, put into a container that has a stirring, add entry to 1.0kg, under agitation, the hollow porous SiO of jinggangmeisu that added embedding 2Nano-carrier is dispersed into emulsion, then, through the colloid mill homogeneous, can obtain the solution of good dispersion, adds antifreezing agent (glycerine) 3g, discharging.The content of jinggangmeisu can be 1.0%, 2.0% in the product, and 5.0%.Or be drying to obtain solid product.
Composition pesticide prepares embodiment 4
The former medicine 35.0g of gibberellin (the biochemical Co., Ltd of Zhejiang Qian Jiang), hollow porous SiO 2Controlled release carrier 20.0g uses hollow porous nanometer SiO 2Controlled release carrier prepares the identical of embodiment 1 with composition pesticide.Methanol/ethanol/ethyl acetate 965.0g, emulsifier (polyoxyethylene nonylphenol ether) 5.0g.The former medicine of 35.0g gibberellin is dissolved in 965.0g methanol/ethanol/ethyl acetate solvent, is made into 3.5% gibberellin methanol/ethanol/ethyl acetate solution, stand-by; Take by weighing the hollow porous SiO of 20.0g 2The nano controlled release carrier, 150 ℃ of temperature, vacuum 0.10Mpa, activation 6h; Then, the hollow porous SiO after the taking-up activation 2Nano-carrier joins in the 3.5% gibberellin methanol/ethanol/ethyl acetate solution for preparing, and soaks 15 days; Take out sample, oven dry, the hollow porous nanometer SiO of gibberellin that promptly got embedding 2The mixture of carrier, stand-by; Emulsifier (polyoxyethylene nonylphenol ether) 5.0g and cosolvent (chloroform) 20g are mixed, put into a container that has a stirring, add methyl alcohol to 1.0kg, under agitation, the hollow porous SiO of gibberellin that added embedding 2Nano-carrier is dispersed into emulsion, then, through the colloid mill homogeneous, can obtain the emulsion of good dispersion, adds antifreezing agent (glycerine) 3g, discharging.The content of gibberellin is 0.5%, 1.0%, 2.0%, 5.0% in the product.Or be drying to obtain solid product.
Composition pesticide prepares embodiment 5
The former medicine of chlorophos (90%) (Xinfeng, Hebei pesticide chemical limited company product) 15g, hollow porous SiO 2Controlled release carrier 20.0g uses hollow porous nanometer SiO 2Controlled release carrier prepares the identical of embodiment 1 with composition pesticide.Water 85g, emulsifier (neopelex) 5.0g.The former medicine of 15.0g chlorophos is dissolved in the 85.0g aqueous solution, is made into the 15.0% chlorophos aqueous solution, stand-by; Take by weighing the hollow porous SiO of 20.0g 2The nano controlled release carrier, 150 ℃ of temperature, vacuum 0.10Mpa, activation 6h; Then, the hollow porous SiO after the taking-up activation 2Nano-carrier joins in the 15.0% chlorophos aqueous solution for preparing, and soaks 30 days; Take out sample, oven dry, the hollow porous nanometer SiO of chlorophos that promptly got embedding 2The mixture of carrier, stand-by; Emulsifier (neopelex) 5.0g and antifreezing agent (ethylene glycol) are mixed, put into a container that has a stirring, add entry to 1.0kg, under agitation, the hollow porous SiO of chlorophos that added embedding 2Nano-carrier is dispersed into solution, then, through the colloid mill homogeneous, can obtain the clear solution of good dispersion, adding preservative agent (penta sodium pentachlorophenate) 2g, discharging.The content of chlorophos can be 1.0%, 2.0% in the product, and 3.0%, 5.0%.Or be drying to obtain solid product.
Composition pesticide prepares embodiment 6
Happy former medicine 35.0g, hollow porous SiO 2Controlled release carrier 20.0g uses hollow porous nanometer SiO 2Controlled release carrier prepares the identical of embodiment 1 with composition pesticide.Toluene 965.0g, emulsifier (sorbester p17) 5.0.The happy former medicine of 35.0g is dissolved in 965.0 toluene solvants, is made into 3.5% happy toluene solution, stand-by; Take by weighing the hollow porous SiO of 20.0g 2The nano controlled release carrier, 150 ℃ of temperature, vacuum 0.1Mpa, activation 6h; Then, the hollow porous SiO after the taking-up activation 2Nano-carrier joins in the 3.5% happy toluene solution for preparing, and soaks 15 days; Take out sample, oven dry, the hollow porous nanometer SiO of happiness that promptly get embedding 2The mixture of carrier, stand-by; Emulsifier (sorbester p17) 5.0g and protecting colloid (Sodium Polyacrylate) 1.0g are mixed, put into a container that has a stirring, add dimethylbenzene to 1.0kg, under agitation, the happy hollow porous SiO that added embedding 2Nano-carrier is dispersed into emulsion, then, through the colloid mill homogeneous, can obtain the emulsion of good dispersion, adding preservative agent (daconil M) 2g, discharging.Content happy in the product can be 1.0%, 2.0%, 3.0%, 5.0%.Or be drying to obtain solid product.
Composition pesticide prepares embodiment 7
The former medicine 50.0g of fluorine worm nitrile, hollow porous SiO 2Controlled release carrier 30.0g uses hollow porous nanometer SiO 2Controlled release carrier prepares the identical of embodiment 1 with composition pesticide.Acetone 50.0g, emulsifier (sorbitan monooleate) 5.0g.The former medicine of 50.0g fluorine worm nitrile is dissolved in the 50.0g acetone solvent, is made into 50.0% fluorine worm nitrile acetone soln, stand-by; Take by weighing the hollow porous SiO of 30.0g 2The nano controlled release carrier, 150 ℃ of temperature, vacuum 0.1Mpa, activation 6h; Then, the hollow porous SiO after the taking-up activation 2Nano-carrier joins in the 50.0% fluorine worm nitrile acetone soln for preparing, and soaks 10 days; Take out sample, oven dry, the hollow porous nanometer SiO of fluorine worm nitrile that promptly got embedding 2The mixture of carrier, stand-by; Emulsifier (sorbitan monooleate) 5.0g and antifreezing agent (2-Butoxyethyl acetate) 3.0g are mixed, put into a molten device that has a stirring, add entry to 1.0kg, under agitation, the hollow porous SiO of fluorine worm nitrile that added embedding 2Nano-carrier is dispersed into emulsion, then, through the colloid mill homogeneous, can obtain the emulsion of good dispersion, adding preservative agent (penta sodium pentachlorophenate) 2g, discharging.The content of fluorine worm nitrile can be 1.0%, 2.0% in the product, and 3.0%, 5.0%, 10.0%, 20.0%.Or be drying to obtain solid product.
Composition pesticide prepares embodiment 8
Cypermethrin technical material 35.0g, hollow porous SiO 2Controlled release carrier 20.0g uses hollow porous nanometer SiO 2Controlled release carrier prepares the identical of embodiment 1 with composition pesticide.Toluene 965.0g, emulsifier (sorbitan monooleate) 5.0g.The 35.0g cypermethrin technical material is dissolved in 965.0 toluene solvants, is made into 3.5% cypermethrin toluene solution, stand-by; Take by weighing the hollow porous SiO of 20.0g 2The nano controlled release carrier, 150 ℃ of temperature, vacuum 0.1Mpa, activation 6h; Then, the hollow porous SiO after the taking-up activation 2Nano-carrier joins in the 3.5% cypermethrin toluene solution for preparing, and soaks 15 days; Take out sample, oven dry, the hollow porous nanometer SiO of cypermethrin that promptly got embedding 2The mixture of carrier, stand-by; Emulsifier (sorbitan monooleate) 5.0g and antifreezing agent (2-Butoxyethyl acetate) 3.0g are mixed, put into a container that has a stirring, add entry to 1.0kg, under agitation, the hollow porous SiO of cypermethrin that added embedding 2Nano-carrier is dispersed into emulsion, then, through the colloid mill homogeneous, can obtain the emulsion of good dispersion, adding preservative agent (penta sodium pentachlorophenate) 2g, discharging.The content of cypermethrin can be 1.0%, 2.0% in the product, and 3.0%, 5.0%, 10.0%, 20.0%.Or be drying to obtain solid product.
Composition pesticide prepares embodiment 9
Deltamethrin original medicine 35.0g, hollow porous SiO 2Controlled release carrier 20.0g uses hollow porous nanometer SiO 2Controlled release carrier prepares the identical of embodiment 1 with composition pesticide.Dimethylbenzene 965.0g, emulsifier 5.0g.The 35.0g deltamethrin original medicine is dissolved in the 965.0g xylene solvent, is made into 3.5% decis xylene solution, stand-by; Take by weighing the hollow porous SiO of 20.0g 2The nano controlled release carrier, 150 ℃ of temperature, vacuum 0.1Mpa, activation 6h; Then, the hollow porous SiO after the taking-up activation 2Nano-carrier joins in the 3.5% decis xylene solution for preparing, and soaks 15 days; Take out sample, oven dry, the hollow porous nanometer SiO of decis that promptly got embedding 2The mixture of carrier, stand-by; Emulsifier (sorbitan monooleate) 5.0g and cosolvent (dimethylbenzene) 3.0g are mixed, put into a container that has a stirring, add acetone to 1.0kg, under agitation, the hollow porous SiO of decis that added embedding 2Nano-carrier is dispersed into emulsion, then, through the colloid mill homogeneous, can obtain the emulsion of good dispersion, adds antifreezing agent (2-Butoxyethyl acetate) 3.0g and adding preservative agent (penta sodium pentachlorophenate) 2.0g, discharging.The content of decis can be 0.5%, 1.0% in the product, and 2.0%, 3.0%.Or be drying to obtain solid product.
The present invention compares with conventional art, and the present invention has at least one following progress:
1) improved drug effect. Conventional cream preparation is made into soup oil droplet fineness when spraying emulsion and is 0.1～1.0 micron, and the oil droplet fineness of the sprinkling missible oil that the nano pesticide controlled release agent is joined is less than 100 nanometers only For the one thousandth of microcapsules or littler, can make the agricultural chemicals high degree of dispersion. The emulsion of this moment has been transparent Or translucent true solution. Its particle diameter is very little, and surface tension is low, thus it have fabulous permeability, Wetability, levelability and rheological characteristic can directly be infiltrated in the fine capillary channel of plant plant; Improved The pesticide active ingredient AVM has improved anti-to the penetrating ability of insect and plant and the uniformity of sprawling Control the effective rate of utilization of effect and medicament.
2) the stable dependence nano-hollow porous SiO of nano pesticide controlled release agent particle2The characteristic of particle self, Dispersiveness such as nano level solid particle is all fine, and the electric double layer of cyst wall self, is a kind of chemistry Bonding force is compared with the decentralized photo mechanism of other formulation such as microemulsion, and stability improves.
3) have the function that control discharges, prolonged the lasting period of same dose agricultural chemicals, improved agricultural chemicals Utilization rate has reduced dosage, thereby has reduced cost and agricultural chemicals to the pollution of environment. Because on adopting State the medicine of technical scheme made, drug molecule can be loaded into the nano particle of many microporous inorganics matter In, and be attached on the surface of nano particle, avoided disposable release or the drug degradation of medicine;
4) suppressed environmental factor (as: light, heat, rainwater, soil, microorganism and other chemical substances) The medicine that causes decomposes and runs off, and has improved the stability of medicament itself, is conducive to ecological environment.
5) reduce acute toxicity, phytotoxicity and residual poison.
6) hold the nano particle of medicine owing to the effect of surface-active and dispersant, so that medicine is to acceptor Great affinity and adhesive force are arranged, reduced the loss of medicine, particularly at blade face, the soil of crop And there is great meaning seed medicine processing aspect.
7) owing to adopt technique scheme to prepare medicine, it is dense to hold medicine according to the design of acceptor situation Degree, the control drug dose, according to the THICKNESS CONTROL release time of wall, and with variable concentrations, different thick Degree hold drug particle mixing use, avoided the acceptor left drug excessive, and the EDD mistake Long defective.
8) owing to adopt technique scheme, can with the female agent of the medicament sustained-release nano particle of preparation, be used for Make in the medicines such as liquid, powder, particle, block, the control slow release speed prolongs EDD.
9) the nano pesticide controlled release agent has solved the problem of water baseization, high degree of dispersionization, stabilisation and the control-release long-actingization of preparation comprehensively, and its drug effect is higher than other formulations, cost is lower than other common formulations, therefore has important generalization and application value.
In sum, utilize the porous hollow nano-carrier to prepare nano pesticide controlled release agent method, drug prepared reduces using dosage, reduces use cost, to the release time and the speed of drug effect, can reach the purpose of sustained release by the adjustment of prescription, parameter.And this technical scheme can be applied in a flexible way, as the preparation of various medicine classes such as preparation missible oil, wettable powder, pulvis, granule, aqua, emulsifiable concentrate, dried outstanding agent, capsule, aerosol and clothing film, solid formulation.

Claims (20)

1. a composition pesticide comprises one or more pesticide activity components and hollow porous SiO 2Nano particle; Wherein said hollow porous SiO 2The wall of nano particle has the duct of basic arranged radially; And wherein said hollow porous SiO 2Nano particle is loaded with the described agricultural chemicals that content is 0.01～90.0% weight of composition weight.
2. the composition pesticide of claim 1, wherein said hollow porous SiO 2The particle diameter of nano particle is 5～500 nanometers.
3. the composition pesticide of claim 1, wherein said hollow porous SiO 2The particle diameter of nano particle is 40～150 nanometers.
4. the composition pesticide of claim 1, wherein said hollow porous SiO 2The particle diameter of nano particle is 50～100 nanometers.
5. the composition pesticide of claim 1, wherein said hollow porous SiO 2The thickness of nano particle wall is 5～100 nanometers.
6. the composition pesticide of claim 1, wherein said hollow porous SiO 2The thickness of nano particle wall is 8～20 nanometers.
7. the composition pesticide of claim 1, wherein said hollow porous SiO 2The thickness of nano particle wall is 10～15 nanometers.
8. the composition pesticide of claim 1, wherein said hollow porous SiO 2Nano particle is spherical, needle-like, cube, spindle, petal, sheet, fibrous.
9. the composition pesticide of claim 1, wherein said hollow porous SiO 2The average pore size in the duct on the nano particle wall is the 1-50 nanometer.
10. the composition pesticide of claim 1, wherein said hollow porous SiO 2The average pore size in the duct on the nano particle wall is the 2-40 nanometer.
11. the composition pesticide of claim 1, wherein said hollow porous SiO 2The average pore size in the duct on the nano particle wall is the 1-10 nanometer.
12. the composition pesticide of claim 1, wherein hollow porous SiO 2Nano particle is 10～99.9% weight of composition weight.
13. the composition pesticide of claim 1, wherein the content of pesticide activity component is the 10-80% weight of composition weight; Hollow porous SiO 2Nano particle is the 20-90% weight of composition weight.
14. the composition pesticide of claim 1, wherein the content of pesticide activity component is the 30-70% weight of composition weight; Hollow porous SiO 2Nano particle is the 30-70% weight of composition weight.
15. the composition pesticide of claim 1 wherein also contains additive, organic solvent or water that agricultural chemicals is used, described additive is 0.01～35.0% weight of composition weight.
16. the composition pesticide of claim 8, wherein said spherical hollow porous SiO 2The internal diameter of nano particle is the 2-150 nanometer.
17. the composition pesticide of claim 8, wherein said spherical hollow porous SiO 2The internal diameter of nano particle is the 10-120 nanometer.
18. the composition pesticide of claim 8, wherein said spherical hollow porous SiO 2The internal diameter of nano particle is the 30-100 nanometer.
19. one of claim 1-18 the preparation method of composition pesticide; It comprises the steps:
A) pesticide activity component is dissolved in obtains a solution in organic solvent or the water;
B) with hollow porous SiO 2Nano particle in vacuum drying chamber under the condition of 90～600 ℃ of temperature, vacuum 0.01～0.1Mpa, activating 1～24 hour;
C) with the hollow porous SiO that obtains in the step b) 2Nano particle mixes with a) solution and soaked 0.5 hour～3 months;
D) randomly add additive, can obtain product emulsion; Maybe will be through soaking the hollow porous SiO of pesticide activity component 2The nano particle drying obtains solid product or is scattered in the water under high-speed stirred, forms aqua product.
20. the formed product emulsion of the method for claim 19, solid product or aqua product.
CNB2004100433131A 2004-05-14 2004-05-14 Compsn. of agricultural pesticide and preparation method Expired - Fee Related CN100417324C (en)

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