CN101389216A - Pesticide delivery system - Google Patents

Abstract

An improved pesticide delivery system is disclosed. The system is based on a microblend comprising (a) an first amphophilic compound containing at least one hydrophilic group and at least one hydrophobic group and (b) a second compound. Compositions based on the microblend and methods of using the compositions to control pests are also disclosed.

Description

Pesticide delivery system

The cross reference of related application

According to 35U.S.C.119 (e), the application requires the rights and interests of No. the 60/757641st, the U.S. Provisional Application of submitting on January 10th, 2006 and the U.S. Provisional Application of submitting on April 7th, 2006 No. 60/790381, and their full text all is incorporated into this paper by reference.

Technical field

The present invention relates to comprise the insecticides of little blend, described blend comprises (1) amphoteric compound and (2) second compounds, also relates to and utilizes described composition for preventing and controlling nuisance.

Background technology

Pesticide delivery system is known in the art.These systems comprise insecticide usually and add carrier (generally being water) and various additive and excipient.But normal suspension concentrate solution body, emulsion, microemulsion, multiple emulsion and other systems used in pesticide delivery system.Insecticidal preparation commonly used is a concentrate, dilutes with quite a large amount of liquid before use, makes the dispersion of using then with the control nuisance.

For example, water dispersible pow-ders (WP) is trickle solid insecticidal preparation, and it is used at dilute with water and after suspending in water.Such preparation production and packing cost are low, easily handle, and purposes is wide, but they are difficult to mix in aerosol can, may produce dust harzard, and poor with the compatibility of other preparations.In some cases, they use with water-soluble sachet, to overcome the harm problem of handling dust.

Water-dispersible granule (WG) is the solid pharmaceutical preparation of another kind of type, and they can be dispersed or dissolved in the water in the aerosol can.Compare with other solid pharmaceutical preparations, these preparations have important advantage, and are even as grain graininess, can free-flow, and topple over easily and measure, can in water, form good dispersion/solution, under high temperature and low temperature, have long-time stability.Water dispersible or water-soluble granular can utilize various treatment technology preparations.Yet can process for preparation successfully depend on the physico chemical property of active component, and preparation lipophile active component is quite difficult.

Suspending concentrate (SC) is the very little stable suspension of insecticide particle in liquid.Suspending concentrate available water or oil dilution, but nearly all suspending concentrate preparation all is dispersed in the water at present.Suspending concentrate can be used to prepare the very strong active component of lipophile.These preparations are toppled over easily and are measured, and water fluid is not flammable, but stability of formulation is very responsive to the small variations of raw material quality, and these preparations need prevent to freeze.The granularity of particle is several microns in the suspending concentrate, thereby described particle has big surface area.Because them and the hydrophobic effect of environmental surfaces, this will cause the animal migration of particle low, the interior absorption (systemicity) and the bioavilability of the active component of serious these formulation delivered of restriction use.

Solvable liquid concentrate (SL) is a settled solution, and the solution after can dilute with water is used.Solvable liquid is based on water or based on complete and water-soluble mixed solvent mixture.The solution concentration thing is easy to handle and preparation, and only need be diluted in the water in aerosol can.But many insecticides can be prepared by solvable liquid concentrate, and they are subjected to the restriction of the solvability and the stability of active component in water.

Special preparation is a water-base preparation such as microemulsion, because drop size very little (usually between 50-100 nanometers), they are thermodynamically stable in wide temperature range, are considered to solubilising micellar solution sometimes.They comprise active component, solvent, surface active agent solubilization agent (surfactantsolubilizer), cosurfactant and water usually.The normal expression of surface active agent solubilization agent has the blend of the surfactant of different hydrophilic/lipophilic balance value (HLB).This preparation is non-flammable, has long storage life, and is flammable low, but is applicable to that the quantity of the surfactant system of active component also is limited, and the application on the target market may be limited.

In the pharmaceutical products field, preparation usually by be coated on skin, oral or injection comes administration.The specificity of these administration environment is very strong, is subjected to the strict control of health.The transdermal effect of active component depends on the permeability of skin, and this point is similar to most of patients.Oral preparation will experience different environment successively, and for example the alkali condition in saliva, hydrochloric acid in gastric juice and the intestines is absorbed in the blood flow then, and these conditions remain similar on one's body each patient.The preparation of injection will experience a different set of specificity environmental condition; These environment remain similar on one's body each patient.Concerning the preparation that is used for all these environment, excipient is very important for the performance of activating agent.Absorption, dissolubility, permeate through cell membranes shift the intermediary's character that all depends on excipient.Therefore, be present in all patients specificity environment and specificity using method design preparation on one's body at predicting.

On the contrary, in agricultural and/or insecticide application, a kind of active component can be used for handling the crops or the nuisance of many types in multiple similar preparation and similar application process.The environmental condition difference of different regions and Various Seasonal is very big.Agrotechnical formulation must be in very wide condition and range effectively, and the Agrotechnical formulation that must make has this strong effect.

For agriculturally useful compositions, surface/air interface is than much important in the situation of medical composition, because medical composition is to play a role in the closed system of health.In addition, agricultural environment comprises different key elements, as clay, heavy metal and the different surfaces such as leaf (wax hydrophobic structure).The range of temperature of soil is also big than body temperature excursion, can change between 0 degree centigrade and 54 degrees centigrade usually.The pH scope of soil is about 4.5 to 10, and does not also discharge in medical composition of preparing usually even the wide pH scope between whole 5-9.

The method that Agrotechnical formulation is used is sprayed directly on the preparation of dilute with water in the farmland normally after crops/weeds grow preceding or grow.When preparation must the contact target plant the leaf growth site time, spray formulation is useful.Dried granular preparation is also used always, often uses by the mode of spreading.It is effective that these preparations were used before crops and weeds grow.In this case, active component must be retained in the soil, is preferably placed at the zone of the long root of target plant or the zone of targeted insect activity.

Summary of the invention

The present invention relates to comprise the insecticides of little blend, described blend comprises (a) amphoteric compound and (b) second compound.The invention still further relates to and utilize described composition for preventing and controlling nuisance.Composition of the present invention is the form of concentrate, just forms small-particle (micella) behind the dilute with water.Compare with existing composition, insecticides of the present invention has improved character, as bioavilability, interior absorption, soil animal migration (soilmobility) etc.

Description of drawings

Fig. 1 is the commercially available insecticidal preparation of the bifenthrin (Bifenthrin) that obtains by food dish test (Diet Disk assay) and the LD of embodiment 3 ₅₀The figure of amount [PPM concentration (ppm)].

Fig. 2 is the figure of the LD50 amount [PPM concentration (ppm)] of a kind of industrial insecticidal preparation that obtains by leaf dish test (leafDisk assay) and embodiment 9.

Fig. 3 is a kind of industrial insecticidal preparation that obtains by leaf dish test and the % inhibition-time plot of embodiment A 9.

Fig. 4 is the % consumption leaf spirogram of leaf, polymer blank sample, industrial insecticidal preparation and embodiment 9 of being untreated.

Fig. 5 is the image that is used to comprise behind the soil TLC plate development (development) of little blend of various Pu Luluonike (Pluronic), Tetronic and Su Bofu (Soprophor) component.The concentration of bifenthrin is 1% (w/w) in little blend.Use the aqueous dispersion of 50 microlitres, 10% little blend onboard.

Fig. 6 is that the soil TLC plate (A) that is used to comprise little blend of the Pu Luluonike P123 of various ratios and Su Bofu 4D384 component launches back and (B) image after launching for the second time for the first time.The concentration of bifenthrin is 1% (w/w) in little blend.Use the aqueous dispersion of 50 microlitres, 10% little blend onboard.

Embodiment

Used following term has the appointment implication in this specification, is explained as follows:

Ampholytes: both can be used as the material that acid also can be used as alkali.

Amphoteric surfactant: the surfactant that comprises ion or ionizable polarity headgroup and one or more hydrophobicity tail bases.

Main chain: in the graft copolymer name, be used for describing the chain that forms graft thereon.

Block copolymer: two or the combination of many chains that connects in the line style mode by covalent bond each other with not isostructure or configuration characteristic.

Branched polymer: the combination of two or many chains connected to one another, wherein at least one chain is along bonding on certain point of another chain.

Chain: the polymer molecule that monomeric unit is connected to form by covalent bond.

Configuration: atom can only be by the fracture of main chemical bond and formation generation change again along the organizational form of polymer chain.

Structure picture: the arrangement that atom on the polymer chain and substituting group take place because of the rotation around singly-bound.

Copolymer: the polymer that comes by more than one monomer derived.

Crosslinked: as two or many polymer chains to be bonded together and the structure that forms.

Dendritic: many branched polymers that side chain stretches out from one or more centers.

Dilution: a certain amount of water added in the composition of the present invention form dispersion, wherein the amount of dispersion surpasses at least one order of magnitude of quality of composition, preferred water: composition is 10:1 to 10000:1, more preferably 100:1 to 1000:1, even more preferably 25:1 to 200:1.

Dispersion: particle matter is dispersed in the whole continuous media.

Graft copolymer: a based block copolymer, expression has two or the combination of many chains of not isostructure or configuration characteristic, and wherein a chain is as main chain, and at least one chain constitutes side chain along certain the some bonding on the main chain.

Homopolymers: by the polymer that forms with a kind of monomer derived.

Connect (link): the covalent chemical bond between two atoms, comprise between two monomeric units or two polymer chains between key.

LogP: octanol/water distribution coefficient (P) is measuring of the different solubilities of a kind of compound in these two kinds of solvents of hot alcohol and water.LogP is the logarithm of the concentration ratio of solute in these two kinds of solvents.

Little blend: the composition (a) that forms by the homogeneous mixture of first amphoteric compound and second compound and/or insecticide, after described mixture (b) dilutes in water, form the dispersion of granularity in the nanoscale scope, promptly less than about 500 nanometers, preferably less than about 300 nanometers, be more preferably less than about 100 nanometers, be more preferably less than about 50 nanometers.Water: the typical thinner ratio of composition is 100:1 to 1000:1.

Polymer network: the three-dimensional polymer structure, wherein all chains couple together by crosslinked.

Insecticide: the mixture of a kind of material or material is used for preventing, kill, drive, reduce or preventing and treating nuisance, as to the harmful insect of growth crop, domestic animal, pet, people and structure, weeds, acarid, fungi, nematode etc.The example of insecticide comprises bactericide, weed killer herbicide, fungicide, insecticide (for example ovicide, larvicide or adulticide), miticide, nematocide, rodenticide, virucide, plant growth regulator etc.Insecticide also can be can be scheduled to as the arbitrary substance of plant modifying agent, defoliant or desiccant or the mixture of multiple material.

Polyampholyte: polymer chain with anion and cation mixed characteristic.

Polyanion: contained repetitive comprises the polymer chain that causes forming the ionogen of negative electrical charge on polymer chain.

Polycation: contained repetitive comprises the polymer chain that causes forming the ionogen of positive charge on polymer chain.

Polyion: contained repetitive comprises the polymer chain that Ionized group can take place that causes forming positive charge and/or negative electrical charge on the polymer chain in the aqueous solution.

Polymer blend: two or more have the even combination of polymer chain or other compounds of not isostructure or configuration characteristic, and described polymer chain or other compounds do not have chemical bonding each other.

Polymer blocks: the part of polymer molecule, monomeric unit wherein have structure or the configuration characteristic that at least one adjacent portions branch does not have.This term of polymer blocks can exchange with polymer segment or polymer segments and use.

Poorly water-soluble: the dissolubility in the water is, under 25 ℃ and normal pressure, the solvability in deionized water is about 500ppm to about 1000ppm.

Repetitive: be connected to the monomeric unit in the polymer chain.

Side chain: the grafted chain in the graft copolymer.

Stable: using little blend composition in the necessary duration, active component does not form precipitation, chemical breakdown does not take place.

Star block copolymer: three or many chains with not isostructure or configuration characteristic at one end link together by a core.

Star polymer: three or many chains at one end link together by a core.

Surfactant: have surface-active reagent.

Water insoluble: under 25 ℃ and normal pressure, the solvability in deionized water is less than 500ppm, preferably less than 100ppm.

Amphion: the ionic group and the net charge that comprise opposite charge are zero dipole ion.

Preferred implementation

The present invention relates to comprise the insecticides of little blend, described blend comprises (a) first amphoteric compound and (b) second compound.These two kinds of components will be discussed respectively below.

(a) first amphoteric compound

Be used for the polymer that amphoteric compound of the present invention normally comprises at least one hydrophilic segment and at least one hydrophobic part.The representative amphoteric compound comprises hydrophilic-hydrophobic block copolymer, as mentioned below those.The block copolymer of preferred PEO and another kind of polyalkylene oxide, particularly polyethylene/polypropylene oxides block copolymer hereinafter described.

(b) second compound

Second compound can mix the little blend of formation with first amphoteric compound, and second compound can be selected from:

-hydrophobicity homopolymers or random copolymer

-contain the amphoteric compound of the part identical with first amphoteric compound, but have the length difference of a hydrophilic or hydrophobic part, perhaps the configuration difference of polymer chain at least

-comprise the amphoteric compound of at least one part that chemically is different from the hydrophilic or hydrophobic part in first amphoteric compound

-comprise the hydrophobicity block copolymer of at least two different hydrophobic blocks

-hydrophobic molecule

-the hydrophobic molecule that is connected with hydrophilic polymer.

If second compound of the present invention is hydrophobicity homopolymers or random copolymer, it is selected from hereinafter listed hydrophobic polymer.

If second compound is the amphoteric compound that contains the part identical with first amphoteric compound, but the length difference that has a hydrophilic segment or hydrophobic part at least, the perhaps configuration difference of polymer chain, then the hydrophobicity of preferred this compound is stronger than first amphoteric compound.If the HLB of second compound is less than the HLB of first compound, then the hydrophobicity of second compound is stronger than first compound.

If second compound is the amphoteric compound that comprises at least one part that chemically is different from the hydrophilic or hydrophobic part in first amphoteric compound, then same preferred its hydrophobicity is stronger than first compound.Chemically different parts has the monomer that different chemical is arranged.The example of second compound that this hydrophobicity is stronger includes but not limited to that its hydrophobic block has the more block copolymer of strong-hydrophobicity than the hydrophobic block of first compound, and perhaps its hydrophilic block has the more block copolymer of slightly water-wet than the hydrophilic block of first compound.

If second compound is the block copolymer that comprises at least two different hydrophobic blocks, then this copolymer can not have hydrophilic block.The example of this hydrophobic block copolymer comprises elastomer, as KRATON

Polymer.KRATON D polymer and and compound have block in the undersaturated rubber (styrene-butadiene-styrene and styrene-isoprene-styrene).KRATON G polymer and compound have saturated middle block (styrene-ethylene/butylene-styrene and styrene-ethylene/propene-styrene).KRATON FG polymer the has been grafting G polymer of the functional group such as maleic anhydride.The KRATON isoprene rubber is the HMW polyisoprene.Particularly preferred copolymer is polystyrene-polyisoprene copolymers: (styrene-content is 44% available from the Vector 4411A of Dexco Polymers LP, MW 75000), available from the KRATON D1117P (styrene-content is 17%) of shell chemical company with available from polystyrene-polybutadiene-polystyrene copolymer of Dexco Polymers LP, Vector8505 (styrene-content is 29%).

If second compound is a hydrophobic molecule, then it can be in fact to comprise aliphatic hydrocarbon or aromatic hydrocarbon or carbon fluoro compound group, perhaps comprises any organic molecule of the mixed structure of hydrocarbon and fluorocarbon part.If hydrophobic molecule is a fluorocarbon, then it can comprise fluoro-alkyl or fluorinated aryl part.Hydrophobic molecule also can be the aromatics polycyclic compound.For how ring-like second compound of aromatics, preferably has the compound that is less than about 20 rings.It is about 2500 that the molecular weight of this hydrophobic molecule is lower than, and preferably is lower than about 1500.Preferred hydrophobe comprises poly-aryl triphenyl phenol.One preferred embodiment in, this second compound is an insecticide.

If second compound is the hydrophobic molecule that is connected with hydrophilic polymer, then it can be an amphoteric surfactant.In this embodiment, preferred especially polyoxy ethylization surfactant comprises the surfactant of non-polymer hereinafter described.Hydrophobic molecule can be in fact to comprise aliphatic hydrocarbon or aromatic hydrocarbon or carbon fluoro compound group, perhaps comprises any organic molecule of the mixed structure of hydrocarbon and fluorocarbon part.If hydrophobic molecule is a fluorocarbon, then it can comprise fluoro-alkyl or fluorinated aryl part.Hydrophobic molecule also can be the aromatics polycyclic compound.For how ring-like second compound of aromatics, preferably has the compound that is less than about 20 rings.It is about 2500 that the molecular weight of this hydrophobic molecule is lower than, and preferably is lower than about 1500.Preferred hydrophobe comprises poly-aryl triphenyl phenol.Hydrophobic molecule preferably with hydrophilic molecule, preferred poly-(oxirane) connects.Preferably, in the surfactant of this non-polymer the number of ethylene oxide unit between 3-50.It is about 2500 that the molecular weight of hydrophobic polymer is lower than, and preferably is lower than about 1500.It is about 2500 that the molecular weight of hydrophilic polymer is lower than, and preferably is lower than about 1500.In preferred embodiment, the surfactant of these non-polymers can comprise at least one charged part, and it can be cationic or anionic.Preferably, this charged group is an anionic group, more preferably sulfo group or phosphonate group (phosphate group).

In first preferred implementation, the invention provides concentrated little blend composition, produce the stable aqueous dispersions of granularity behind the said composition dilute with water in the nanoscale scope.Be not subjected in the present invention under the situation of restriction of concrete preparation, can with this slightly the blend composition be formulated as powder preparation, water-dispersible granule, sheet, liquid, wettable powder, or before using the similar dry preparation of dilute with water, perhaps with using of concentrating as solid form or liquid form.Preferred this composition is substantially free of the water or the water miscibility organic solvent of adding.In content of the present invention, be substantially free of the water of adding or water miscibility solvent and mean and contain water or the water miscibility solvent that is less than or equal to 0.1% adding.

In second preferred implementation, the invention provides concentrated little blend composition, said composition comprises at least a water miscibility organic solvent or other liquid components, produces the stable aqueous dispersion of granularity in the nanoscale scope behind the said composition dilute with water.Be not subjected in the present invention this blend composition to be formulated as the water dispersible liquid concentrate or the gel of dilute with water before using under the situation of restriction of concrete preparation, perhaps with using of concentrating as liquid form.

In another preferred embodiment of the present invention, when preparing little blend composition, it further comprises charged molecule, and as cationic or anionic amphoteric compound, this compound comprises and has the hydrophilic-hydrophobic block copolymer of charged repetitive separately.In another aspect of this invention, described cationic or anionic amphoteric surfactant can add in the insecticides.

Insecticide

Can be used for insecticide of the present invention and comprise for example insecticide, weed killer herbicide, fungicide, miticide and nematocide.Insecticide is the active component in the little blend composition of the present invention.For insecticide, preferred logP is at least 0, preferably is at least 1, more preferably is at least 2.Representative insecticide includes but not limited to the listed active component of following table:

^{* *}LogP=2.605 and the luxuriant and rich with fragrance logP=6.266 of benzo [9,10] based on toluene ^{* *}

Demarcate with mark in toluene and the luxuriant and rich with fragrance work of benzo [9,10]

Insecticide comprises for example Bifenazate quinalphos, Tebupirimphos, the full phosphorus of worm, triazotion, phenthoate dimephenthoate cidial, endrin, dieldrin, 5a,6,9,9a-hexahydro-6,9-methano-2,4, fenthion, diazinon, Fonofos, chlorpyrifos-methyl, sulfluramid karphos, cadusafos, milbemycin A4, milbemycin A3, bioallethrin, bioallethrin S-cyclopentenyl isomer (bioallethrin S-cyclopentenyl isomer), allethrin, terbufos, benthiocarb, orbencarb, Buprofezin, Resistox, methoxyfenozide, tetramethrin, tetramethrin [(1R)-isomer] tetramethrin[(1R)-isomers], phoxim, Phosalone, the worm hydrazides, alkynes mite spy, pyridaben, Teflubenzuron, ABG-6215, chlopyrifos, Profenofos, pyrethrin, ring worm hydrazides, ethion, heptachlor, Amex820, two three flufenoxurons, plictran, amitraz, capillary, the pyrrole propyl ether, Swebate, Toyodan, fenpropathrin, the fluorine third oxygen urea, resmethrin, bioresmethrin, Rimon, tefluthrin, dicofol, fluorine bell urea, it is grand to kill mite sulphur, betacyfluthrin, karathane, cyfloxylate (cyhalothrin), karathane, azoles mite ester, flucythrinate, cypermethrin, θ-cypermethrin, ζ-cypermethrin, α-cypermethrin, β-cypermethrin, kinoprene, cyfloxylate, β-cyfloxylate, decis, DDT, esfenvalerate, sumicidin, permethrin, ether chrysanthemum ester, bifenthrin, tralomethrin, acrinathrin, the taufluvalinate and the mite quinone that goes out.

Weed killer herbicide comprises for example cafenstrole, the wheat straw volt, mefenacet, metosulam, cloransulammethyl, 2 first, 2 chloroethene thioesters (MCPA-thioethyl), oxadiargyl, proproanmide, fluorine ketazolam grass, KIH 6127, dinitramine, pyrazoxyfen, alkynes grass ester, disulfoton, diflubenzuron, butachlor, bromofenoxim, fluacrypyrim, isoxaben, kill the bell urea, butylate, bromobutide, neburea, triflusulfuronmethyl, isofenphos, cycloxydim, fluorine chloramines pyridine (fluroxypyr-meptyl), daimuron, fluazifop, naproanilide, ethyl-pyrimidine phosphorus (pirimiphos-ethyl), pyrrole grass ether, anilofos, cinmethylin, bensulide, fluridone, sethoxydim, dithiopyr, ethalfluralin, strong FLAMPROP (flamprop-M-isopropyl), pyrazolate, triallate, fluchloraline, quizalofop-ethyl-acid (quizalofop-acid), propaquizafop-acid (propaquizafop-acid), aclonifen, prosulfocarb fenoxaprop, the spirit of pyrrole fluorine chlorine standing grain, pendimethalin, clethodim, prodiamine, Lonster, fluoroglycofen-ethyl, clomeprop, two careless ethers, haloxyfop-P-methyl, trefanocide, benfluralin, Amex820, cinidon-ethyl, acifluorfen, acifluorfen, diclofop-methyl, pyributicarb, Diflufenican, bifenox, cyhalofop-butyl, quizalofop-ethyl, Quizalotop-ethyl, pyrrole fluorine chlorine standing grain spirit fenoxaprop, the sulphur phenylate swells (sulcofuron), diclofop-methyl; butroxydim; bromoxynil octanoate; fluoroglycofen-ethyl; fluorine pyrrole acyl grass amine (picolinafen); Flumiclorac pentyl; clefoxidim; lactofen; efficient fluazifop; Oxyfluorfen; ioxynil octanoate; flumetralim oxazine humulone; 2 methyl 4 chlorophenoxyacetic acid 2-ethylhexyl (MCPA-2-ethylhexyl) and propaquizafop.

Fungicide comprises for example tolyfluanid (tolylfluanid), biphenyl, zoxamide, the pyridine of fluorine chloramines, Milstem, tecnazene, the fluorine mepanipyrim, penconazole, plant the bacterium azoles, chlozolinate, pentachlorophenol, edifenphos, Rabcide, silicon metsulfovax (silthiofam), tolelofos-methyl, pcnb, KTU 3616, flusulfamide, dimethomorph, prochloraz, Pencycuron, Fu Ma Suan Evil imidazoles (oxpoconazole fumarate), volution bacterium amine Difenoconazole, SSF 126, disease is spent spirit, pyributicarb, the nitrile Fluoxastrobin, fluazinam; butadiene morpholine; the benzene rust is fixed; karathane; dodemorph; tridemorph and oleic acid.

Nematocide comprises for example isazofos, phonamiphos, Hostathion, cadusafos and terbufos.

Above-mentioned and other insecticide can be used for insecticides of the present invention alone or in combination.In addition, if the logP of insecticide is higher, promptly be about 2 or more than, then insecticide also might play second hydrophobic compound in insecticides, in the case, little blend comprises amphoteric compound and insecticide.Preferably, insecticide poorly water-soluble used herein.Particularly preferably be, insecticide is water insoluble.

Hydrophilic-the hydrophobic block copolymer

In a preferred embodiment, the present invention relates to amphiphilic block copolymer, it comprises at least one hydrophilic block connected to one another and at least one hydrophobic block (also claiming hydrophilic-hydrophobic block copolymer at this).Do not describe aforementioned generality of the present invention, describing below mutually, various combination is used for forming the hydrophily of hydrophilic-hydrophobic block copolymer and the example of hydrophobic polymer and polymer blocks.Those skilled in the art can synthesize and can be used for following polymer of the present invention and other polymer, with the preparation insecticides.

Hydrophilic polymer and polymer blocks:

Hydrophilic block can be non-ionic polyalcohol, anionic polymer (polyanion), cation type polymer (polycation), anionic/cationic polymer (polyampholyte) and amphoteric ion polymer (poly-amphion).These polymer or polymer blocks can be the copolymer of homopolymers or two or more different monomers separately.

The example of non-ionic hydrophilic polymer of the present invention and polymer blocks includes but not limited to the polymer of contained repetitive derived from following one or more different monomers: the ester of ethylenic unsaturated carboxylic acid or dicarboxylic acids, the perhaps N substitutive derivative of the ester of ethylenic unsaturated carboxylic acid or dicarboxylic acids, the acid amides of unsaturated carboxylic acid, the 2-hydroxyl ethyl ester of acrylic acid and methacrylic acid, methacrylic acid 2-hydroxypropyl acrylate, acrylamide, Methacrylamide, oxirane (also claiming ethylene glycol or ethylene oxide), vinyl monomer (as vinyl pyrrolidone).The example of non-ionic hydrophilic polymer and polymer blocks includes but not limited to PEO (also claiming polyethylene glycol or polyoxyethylene); polysaccharide, polyacrylamide, PMAm; poly-(methacrylic acid 2-hydroxypropyl acrylate); polyglycerol, polyvinyl alcohol, PVP(polyvinyl pyrrolidone); polyvinylpyridine N-oxide; the copolymer of polyvinylpyridine N-oxide and vinylpyridine, poly-oxazoline, perhaps polypropylene acyl group morpholine or derivatives thereof.Non-ionic hydrophilic polymer and polymer blocks can be the copolymers that comprises the monomeric unit of more than one types separately, comprise the combination of at least a hydrophily nonionic unit and at least a charged unit or hydrophobic unit.Do not limiting under the general situation of the present invention, the part of charged unit or hydrophobic unit is preferably less relatively, and polymer or polymer blocks just can keep nonionic and hydrophily largely like this.

The example of polyanion and polyanion block includes but not limited to: contained unit is derived from following one or more polymer of monomers or its salt: the ethylenic unsaturated monocarboxylic acid, the ethylenic unsaturated dicarboxylic acid, comprise sulfonic ethylenic monomer, their alkali metal salt and ammonium salt.The example of these monomers comprises acrylic acid, methacrylic acid, aspartic acid, α-acrylamido methyl propane sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, citrazinic acid, citraconic acid, trans-cinnamic acid, the 4-hydroxycinnamic acid, trans glutaconate, glutamic acid, itaconic acid, fumaric acid, linoleic acid, linolenic acid, maleic acid, nucleic acid, trans β-hydrogen muconic acid, trans-trans-muconic acid, oleic acid, 1,4-phenylene diacrylate, 2-propylene-1-sulfonic acid phosphonate ester, castor oil acid, the 4-styrene sulfonic acid, styrene sulfonic acid, methacrylic acid 2-sulfo group ethyl ester, trans traumatic acid, vinyl sulfonic acid, vinylbenzenesulfonic acid, vinyl phosphoric acid, vinyl benzoic acid and vinylglycollic acid etc., and carboxylic acid dextran, the sulfonation dextran, heparin etc.The polyanion block has some ionogens that can form net negative charge.Preferably, the polyanion block has at least about 3 negative electrical charges, more preferably at least about 6, is more preferably at least about 12.The example of polyanion includes but not limited to: poly, poly-aspartate, polyglutamic acid, polylysine, polyacrylic acid, polymethylacrylic acid, polyaminoacid etc.Polyanion and polyanion block can by itself may not be anion or not the monomer polymerization of possess hydrophilic property form, as metering system tert-butyl acrylate or citraconic anhydride, pass through the various chemical reactions of monomeric unit then, for example hydrolysis, be converted into the polyanion form, thereby obtain ionogen.The conversion of monomeric unit may be not exclusively, and some copolymerization units does not have ionogen in the copolymer that the result obtains, as the copolymer of metering system tert-butyl acrylate and methacrylic acid.Polyanion and polyanion block can be the copolymer that comprises the monomeric unit of more than one types separately, comprise the combination between the unit of anionic units and at least a other types, the unit of described other types comprises anionic units, cation unit, amphion unit, hydrophily nonionic unit or hydrophobic unit.This polyanion can obtain by the chemically different monomer copolymerization of more than one types with the polyanion block.Do not limit under the general situation of the present invention, the part of non-anionic units is preferably less relatively, and polymer or polymer blocks just can keep anionic property and hydrophily largely like this.

The example of polycation and polycation block includes but not limited to: contained unit is derived from following one or more polymer of monomers and salt thereof: primary amine, secondary amine and tertiary amine, they separately can be partially or completely quaternized, forms quaternary ammonium salt.The example of these monomers comprises that cationic amino acid is (as lysine, arginine, histidine), alkyleneimines is (as ethylene imine, 2-methyl ethylene imine, the 2-ethyl ethylene-imine, 2-propyl group ethylene imine, 2-butyl ethylene imine etc.), spermine, vinyl monomer is (as caprolactam, vinylpyridine etc.), acrylate and methacrylate are (as acrylic acid N, the N-dimethylamino ethyl ester, methacrylic acid N, the N-dimethylamino ethyl ester, acrylic acid N, N-diethylamino ethyl ester, methacrylic acid N, N-diethylamino ethyl ester, t-butylaminoethyl methacrylate, acryloxy ethyl-trimethyl ammonium halide, acryloxy ethyl dimethyl benzyl ammonium halide, methacrylamido oxypropyl trimethyl ammonium halide etc.), allyl monomer (as dimethyl diallyl ammonium chloride), the aliphatic series ionene, heterocycle ionene or aromatics ionene.The polycation block has some ionogens that can form clean positive charge.Preferably, the polycation block has at least about 3 negative electrical charges, more preferably at least about 6, also preferably at least about 12.Polycation and polycation block can be by itself may not being that cationic monomer polymerization forms, and as 4-vinylpridine, by the various chemical reactions of monomeric unit, for example alkylation is converted into the polycation form, thereby obtains ionogen then.The conversion of monomeric unit may be incomplete, and some unit does not have ionogen in the copolymer as a result, as the copolymer of vinylpyridine and N-alkyl vinyl halogenation pyridine.Polycation and polycation block can be the copolymer that comprises the monomeric unit of more than one types separately, comprise the combination between the unit of cation unit and at least a other types, the unit of described other types comprises cation unit, anionic units, amphion unit, hydrophily nonionic unit or hydrophobic unit.This polycation can obtain by the chemically different monomer copolymerization of more than one types with the polycation block.Do not limit under the general situation of the present invention, the part of non-cationic unit is preferably less relatively, and polymer or polymer blocks just can keep cationic largely like this.The example of the polycation that can buy on the market comprises poly-ethylene imine, polylysine, poly arginine, polyhistidyl, polyvinylpyridine and quaternary ammonium salt thereof, the copolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate (Agrimer), caprolactam, the copolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate (can available from ISP), guar hydroxypropyl trimonium chloride (guar hydroxypropyltrimonium chloride) and hydroxypropyl guar gum hydroxypropyl-trimethyl ammonium chloride (hydroxypropyl guar hydroxypropyltriammoniumchloride) be [can available from Rhodia (Rhodia)] (Jaguar), the copolymer (polyquaternium-64) of 2-methacryl-oxygen base ethyl phosphonic acid choline and 2-hydroxy-3-methyl acryloyl-oxy oxypropyl trimethyl ammonium chloride [can available from NOF company (Tokyo)], N, N-dimethyl-N-2-allyl chloride (N, N-dimethyl-N-2-propenyl-chloride) or N, N-dimethyl-N-2-acrylic-2-propylene-1-ammonium chloride (polyquaternium-7) (N, N-dimethyl-N-2-propenyl-2-propen-1-aminiumchloride (Polyquaternium-7), carry out the quaternized hydroxyethylcellulos polymer that cation replaces (can available from the Dow Chemical Company) with trimethyl ammonium and dimethyl dodecyl ammonium, the quaternized copolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate (polyquaternium-11), the copolymer of vinyl pyrrolidone and quaternized vinyl imidazole (polyquaternium-16 and polyquaternium-44), caprolactam, the copolymer of vinyl pyrrolidone and quaternized vinyl imidazole (polyquaternium-46) (can available from BASF AG), the quaternary ammonium salt (polyquaternium-10) that the epoxide reaction that hydroxyethylcellulose and trimethyl ammonium replace obtains (can available from the Dow Chemical Company).

The example of polyampholyte and polyampholyte block includes but not limited to: but comprise the polymer of the unit that contains cationizable groups of the unit that contains anionizable group of at least a type and at least a type, derived from the various combinations of contained monomer in above-mentioned polyanion and the polycation.For example, polyampholyte comprises the copolymer of [(methacrylamido) propyl group] trimethyl ammonium chloride and SSS etc.Polyampholyte and polyampholyte block can be copolymer separately, it comprises the combination of the unit of anionic units and cation unit and at least a other types, and the unit of described other types comprises amphion unit, hydrophily nonionic unit or hydrophobic unit.

Amphoteric ion polymer and polymer blocks include but not limited to the polymer of contained unit derived from following one or more zwitterionic monomers: the betaine type monomer, as N-(3-sulfo group propyl group)-N-methacryl ethoxyethyl group-N, N-Dimethyl Ammonium betain, N-(3-sulfo group propyl group)-N-methacrylamido propyl group-N, N-Dimethyl Ammonium betain; Phosphocholine type monomer is as 2-methylacryoyloxyethyl phosphocholine; 2-methacryloxy-2 '-trimethyl ammonium ethyl phosphonic acid inner salt, propane sulfonic acid 3-dimethyl (methylacryoyloxyethyl) ammonium, 1,1 '-dinaphthalene-2,2 '-dihydrogen orthophosphate, and other contain the monomer of amphion group.Amphoteric ion polymer and polymer blocks can be copolymer separately, it comprises the combination of the unit of amphion unit and at least a other types, and the unit of described other types comprises anionic units, cation unit, hydrophily nonionic unit or hydrophobic unit.Do not limit under the general situation of the present invention, the part of non-amphion unit is preferably less relatively, and polymer or polymer blocks just can keep zwitterionic character largely like this.

It is generally acknowledged that polyanion, polycation, polyampholyte and some poly-zwitterionic functional groups can be in aqueous environment intermediate ionization or disassociations, the result forms electric charge on polymer chain.Degree of ionization depend on the ionizable monomeric unit chemical property, exist and these polymer in adjacent monomer unit, distribution and the environmental parameter of these unit in polymer chain, described environmental parameter comprises pH, chemical composition and solute concentration (as other electrolytical character and concentration of existing in solution), temperature and other parameters.For example, poly-acid is with more negative electrical charges as polyacrylic acid under higher pH condition, and is with still less negative electrical charge or neutral under low pH condition.Poly-alkali is with more positive charges as poly-ethylene imine under low pH condition, and is with still less positive charge or neutral under higher pH condition.Polyampholyte, positively charged under low pH condition as the copolymer of methacrylic acid and polymethylacrylic acid (dimethylamino) ethyl ester, neutral under medium pH condition, and electronegative under higher pH condition.Do not wish to make the present invention be limited to particular theory, it is generally acknowledged, occur electric charge on the polymer chain and will make this polymer hydrophily stronger and hydrophobicity is more weak, vice versa.The disappearance of electric charge will make polymer hydrophobic stronger and hydrophily is more weak.In addition, the polymer that hydrophily is stronger is generally more soluble in water.Otherwise the polymer that hydrophobicity is stronger more is insoluble in water.

Hydrophobic polymer and polymer blocks:

The example of hydrophobic polymer or block includes but not limited to that contained unit is derived from following polymer of monomers: the alkylene oxide beyond the oxirane, as expoxy propane or epoxy butane; Acrylic acid and methacrylic acid and hydrogenation or fluoridize C ₁-C ₁₂The ester of alcohol; The vinyl nitrites that contains 3 to 12 carbon atoms, vinyl carboxylates, vinyl halide, the vinyl amine amide comprises the ethylenically unsaturated monomers of secondary amine or tertiary amine groups, perhaps has the ethylenically unsaturated monomers of nitrogen heterocycle, perhaps styrene.The example of preferred hydrophobicity block comprises that contained unit is derived from following polymer of monomers: methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-EHA, tert-butyl acrylate, methyl methacrylate, EMA, n-BMA, isobutyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, tertiary ethylene carbonate (versatate), propionate, vinyl formamide, vinyl acetamide, vinylpyridine, vinyl imidazole, (methyl) acrylic-amino Arrcostab, aminoalkyl (methyl) acrylamide, the acrylic acid dimethylamino ethyl ester, dimethylaminoethyl methacrylate, acrylic acid di-t-butyl amino ethyl ester, methacrylic acid di-t-butyl amino ethyl ester, dimethyl aminoethyl acrylamide or dimethyl aminoethyl Methacrylamide.Hydrophobic polymer and polymer blocks comprise poly-(L-aspartic acid β-benzyl ester), poly-(L-glutamic acid gamma-benzyl ester), poly-(β-replacement L-aspartate), poly-(γ-replacement L-glutamate), poly-(L-leucine), poly-(L-valine), poly-(L-phenylalanine), the hydrophobicity polyaminoacid, polystyrene, polyalkyl methacrylate, polyalkyl acrylate, PMAm, polyacrylamide, polyamide, polyester (as PLA), polyalkylene oxide beyond the PEO, as poly(propylene oxide) (also claiming polypropylene glycol or polypropylene oxide), and hydrophobic polyolefin.Hydrophobic polymer or polymer blocks can be homopolymers or the copolymer that contains more than one monomeric units, described monomeric unit comprises the combination of the unit of hydrophobic unit and at least a other types, and the unit of described other types comprises anionic unit, cationic unit, amphion unit or hydrophily nonionic unit.Do not limit under the general situation of the present invention, the part of non-hydrophobic unit is preferably less relatively, and polymer or polymer blocks just can keep hydrophobicity largely like this.The hydrophobic polymer that comprises a small amount of ionic group is called ionomer.Be used for hydrophobic polymer of the present invention and polymer blocks and also can comprise ionogen and repetitive, their neutrals and have hydrophobicity under certain environmental conditions, described condition comprise that preparation insecticides, dilute with water are so that the condition after using or using in environment such as plant, soil.

Hydrophily-hydrophobicity block copolymer:

The example that comprises the block copolymer of hydrophily block and hydrophobicity block includes but not limited to PEO-polystyrene block copolymer, PEO-butadiene block copolymer, PEO-polyisoprene blocks copolymer, PEO-polypropylene block copolymer, PEO-polyethylene block copolymer, PEO-poly-(aspartic acid β-benzyl ester) block copolymer, PEO-poly-(glutamic acid gamma-benzyl ester) block copolymer, PEO-poly-(alanine) block copolymer, PEO-poly-(phenylalanine) block copolymer, PEO-poly-(leucine) block copolymer, PEO-poly-(isoleucine) block copolymer, PEO-poly-(valine) block copolymer, polyacrylic acid-polystyrene block copolymer, polyacrylic acid-butadiene block copolymer, polyacrylic acid-polyisoprene blocks copolymer, polyacrylic acid-polypropylene block copolymer, polyacrylic acid-polyethylene block copolymer, polyacrylic acid-poly-(aspartic acid β-benzyl ester) block copolymer, polyacrylic acid-poly-(glutamic acid gamma-benzyl ester) block copolymer, polyacrylic acid-poly-(alanine) block copolymer, polyacrylic acid-poly-(phenylalanine) block copolymer, polyacrylic acid-poly-(leucine) block copolymer, polyacrylic acid-poly-(isoleucine) block copolymer, polyacrylic acid-poly-(valine) block copolymer, polymethylacrylic acid-polystyrene block copolymer, polymethylacrylic acid-butadiene block copolymer, polymethylacrylic acid-polyisoprene blocks copolymer, polymethylacrylic acid-polypropylene block copolymer, polymethylacrylic acid-polyethylene block copolymer, polymethylacrylic acid-poly-(aspartic acid β-benzyl ester) block copolymer, polymethylacrylic acid-poly-(glutamic acid gamma-benzyl ester) block copolymer, polymethylacrylic acid-poly-(alanine) block copolymer, polymethylacrylic acid-poly-(phenylalanine) block copolymer, polymethylacrylic acid-poly-(leucine) block copolymer, polymethylacrylic acid-poly-(isoleucine) block copolymer, polymethylacrylic acid-poly-(valine) block copolymer, poly-(N-vinyl pyrrolidone)-polystyrene block copolymer, poly-(N-vinyl pyrrolidone)-butadiene block copolymer, poly-(N-vinyl pyrrolidone)-polyisoprene blocks copolymer, poly-(N-vinyl pyrrolidone)-polypropylene block copolymer, poly-(N-vinyl pyrrolidone)-polyethylene block copolymer, poly-(N-vinyl pyrrolidone)-poly-(aspartic acid β-benzyl ester) block copolymer, poly-(N-vinyl pyrrolidone)-poly-(glutamic acid gamma-benzyl ester) block copolymer, poly-(N-vinyl pyrrolidone)-poly-(alanine) block copolymer, poly-(N-vinyl pyrrolidone)-poly-(phenylalanine) block copolymer, poly-(N-vinyl pyrrolidone)-poly-(leucine) block copolymer, (N-vinyl pyrrolidone)-poly-(isoleucine) block copolymer, poly-(N-vinyl pyrrolidone)-poly-(valine) block copolymer, poly-(aspartic acid)-polystyrene block copolymer, poly-(aspartic acid)-butadiene block copolymer, poly-(aspartic acid)-polyisoprene blocks copolymer, poly-(aspartic acid)-polypropylene block copolymer, poly-(aspartic acid)-polyethylene block copolymer, poly-(aspartic acid)-poly-(aspartic acid β-benzyl ester) block copolymer, poly-(aspartic acid)-poly-(glutamic acid gamma-benzyl ester) block copolymer, poly-(aspartic acid)-poly-(alanine) block copolymer, poly-(aspartic acid)-poly-(phenylalanine) block copolymer, poly-(aspartic acid)-poly-(leucine) block copolymer, poly-(aspartic acid)-poly-(isoleucine) block copolymer, poly-(aspartic acid)-poly-(valine) block copolymer, poly-(glutamic acid)-polystyrene block copolymer, poly-(glutamic acid)-butadiene block copolymer, poly-(glutamic acid)-polyisoprene blocks copolymer, poly-(glutamic acid)-polypropylene block copolymer, poly-(glutamic acid)-polyethylene block copolymer, poly-(glutamic acid)-poly-(aspartic acid β-benzyl ester) block copolymer, poly-(glutamic acid)-poly-(glutamic acid gamma-benzyl ester) block copolymer, poly-(glutamic acid)-poly-(alanine) block copolymer, poly-(glutamic acid)-poly-(phenylalanine) block copolymer, poly-(glutamic acid)-poly-(leucine) block copolymer, poly-(glutamic acid)-poly-(isoleucine) block copolymer and poly-(glutamic acid)-poly-(valine) block copolymer.The example of hydrophily-hydrophobicity block copolymer comprises the copolymer with ionogen and repetitive, described ionogen and repetitive neutral and have hydrophobicity under certain environmental conditions.For example, poly-[2-(methacryloxy) ethyl phosphonic acid choline-methacrylic acid 2-(diisopropylaminoethyl) ethyl ester] block copolymer is to the pH sensitivity: two blocks are 2 o'clock all possess hydrophilic properties relatively at pH, and environment pH be about 6 and more than situation under, methacrylic acid 2-(diisopropylaminoethyl) ethyl ester block becomes and has hydrophobicity relatively, and poly-2-(methacryloxy) ethyl phosphonic acid choline block keeps its hydrophily.

Be used for block copolymer of the present invention and can have the not polymer chain of isomorphism type, described polymer chain comprises the different block of arrangement mode, as line-type block polymer, graft copolymer, star block copolymer, dendroid block copolymer etc.Hydrophily block and hydrophobicity block are linear polymer, randomly branched polymer, block copolymer, graft copolymer, radial copolymer, star block copolymer, dendritic independently of each other, perhaps have other structures, comprise the combination of said structure.The degree of polymerization of hydrophily block and hydrophobicity block is independently of each other between about 3 to about 100000.The described degree of polymerization more preferably between about 5 to about 10000, is more preferably between about 10 to about 1000.

The block copolymer of oxirane and other alkylene oxides:

In a preferred embodiment of the present invention, comprise the amphiphilic block copolymer of at least a non-ionic hydrophilic block and at least a hydrophobic block as amphoteric compound.This copolymer can have the repetitive of varying number in each block, and different polymer chain configurations, comprises quantity, orientation and the order of polymer blocks.Other alkylene oxide comprises for example expoxy propane, epoxy butane, epoxy hexane and styrene oxide.Do not wish to limit under the general situation of the present invention,, hereinafter described the such amphoteric compound of a class as an example, i.e. the block copolymer of oxirane and expoxy propane, its chemical formula is as follows:

Or,

Wherein the value of x, y, z, i and j is about 2-800, be preferably about 5 to 200, more preferably about 5 to 80, and for every couple of R ¹, R ², one is hydrogen, another is a methyl.

Chemical formula (I) to (III) oversimplification, because in practice, the orientation of isopropylidene can be random or regular in the poly(propylene oxide) block.This point shows in chemical formula (VI), and this formula is more complete.Such PEO-poly(propylene oxide) compound is described in the Am.Perfumer Cosmet.72 (4) of Santon: the Loc.cit.82 (7) of 54-58 (1958), Schmolka: 25 (1967), the Non-ionicSurfactants of Schick, pp.300-371 (Dekker, NY, 1967).Many such compounds can be buied from the market such as " poloxamer (poloxamers) ", " Pu Luluonike (pluronics) " and " Xin Poluonike (synperonics) " such general commodity name.The Pu Luluonike polymer of B-A-B formula often is called " contrary " Pu Luluonike, " Pu Luluonike R " or " Metro gram bed ripples (meroxapol) "." poly-Acker Sa amine (polyoxamine) " shown in the chemical formula (IV) polymer can trade mark Tetronic ^TMAvailable from BASF (Wyandotte, MI).The PEO of representing in the chemical formula (IV) and the order of poly(propylene oxide) block be [chemical formula (IV-A)] conversely, obtains Tetronic R ^TM, equally can be available from BASF.Referring to Schmolka, J.Am.Oil Soc., 59:110 (1979).The also available hydrophily block design that comprises the oxirane and the expoxy propane repetitive of random mixing of PEO-poly(propylene oxide) block copolymer.For keeping the hydrophily of block, oxirane will occupy the majority.Similarly, the hydrophobicity block can be the mixture of oxirane and expoxy propane repetitive.This block copolymer can trade name Pluradot ^TMAvailable from BASF.

The Pu Luluonike that diamines shown in the chemical formula (IV) connects also can be a member in oxirane-poly(propylene oxide) polymer class of connecting of diamines shown in the following chemical formula:

Wherein dotted line is represented the polyethers of the symmetry that extends out from second nitrogen-atoms; R ^*Be the alkylidene that contains 2 to 6 carbon atoms, ring alkylidene or the phenylene that contains 5 to 8 carbon atoms; For R ¹And R ², or (a) the two is hydrogen, otherwise (b) one be hydrogen, another is a methyl; For R ³And R ⁴, or (a) the two is hydrogen, otherwise (b) one be hydrogen, another is a methyl; If R ³And R ⁴Be hydrogen, then R ⁵And R ⁶In one be hydrogen and another is a methyl; If R ³And R ⁴In one be methyl, R then ⁵And R ⁶Be hydrogen.

Those of ordinary skill in the art will recognize that according to content discussed here, even enforcement of the present invention is confined to for example PEO-poly(propylene oxide) compound, above-mentioned exemplary chemical formula also limits too narrowly.Therefore, the unit that constitutes first block not necessarily only is made up of oxirane.Similarly, be not that the second all class blocks must only be made up of propylene oxide units.But described block can comprise the monomer the monomer that is limited except that chemical formula (I) to (V), as long as the parameter of this first embodiment remains unchanged.Therefore, in simple example, have at least a monomer to replace in the hydrophily block with the side-chain radical that the front was described.

In addition, block copolymer can be used the ionic groups end-blocking, as sulfate and phosphate.Preferred PEO-poly(propylene oxide) compound comprises three blocks poly-(oxirane)-poly-(expoxy propane)-poly-(oxirane) copolymer with the phosphate end-blocking (can available from Clariant (Clariant) company).

In amphiphilic block copolymer shown in the chemical formula (I-V), the molecular weight of poly(propylene oxide) block is about 100 to about 20000 dalton, preferably about 900 between about 15000 dalton, more preferably about 1500 dalton between about 10000 dalton, be more preferably at about 2000 dalton between about 4500 dalton.Irrelevant with the poly(propylene oxide) block, the molecular weight of poly-ethylene oxide block is about 100 to about 30000 dalton.

Chemical formula (I) to (IV) is for example understood the amphiphilic block copolymer with different polymer chain configurations.Can buy many such have different hydrophilic or hydrophobic polymer block structures, the copolymer of perhaps different polymer chain configurations, they all can be used as amphoteric compound, in order to prepare insecticides of the present invention.This amphoteric compound comprises various hydrophilies and hydrophobic polymer block, and is illustrational as top institute, and they can be cationic, cationic, amphoteric ion type or nonionic.

In one aspect of the invention, the mixture of preferred PEO-polyalkylene oxide block copolymer.In the case, preferred little compositions of mixing comprises the block copolymer that at least a PEO content is equal to or greater than 50 weight %, can be used as first amphoteric compound, and at least a PEO content less than 50 weight %, can be used as the block copolymer of second compound.If two kinds of block copolymers in the mixture all are PEO-poly(propylene oxide) copolymers, it specifically is the PEO-PPO-PEO triblock copolymer, then the PEO content of preferred a kind of copolymer is more than or equal to 70%, and alternative PEO content is between about 10% to 50%, preferably between about 15% to 30%, be more preferably between about 25% to 30%.

Amphoteric surfactant

First amphoteric compound of the present invention can be an amphoteric surfactant.Second compound can be the amphoteric surfactant that is independent of first compound.If first compound in the present composition is the nonionic amphoteric surfactant, second compound also is the nonionic amphoteric surfactant, then the cloud point of first and second compounds all is at least 25 ℃, and wherein cloud point is measured according to DIN method (DIN 53917).Yet, except that first and second compounds, have any cloud point values, comprise that the nonionic surfactant that is lower than 25 ℃ also can be used as the part of the present composition.

Surfactant can be nonionic, cationic or anionic (for example soap).Amphoteric surfactant can be polymer-type with non-polymeric.In a preferred implementation, surfactant is a non-polymeric.The functional character of amphoteric surfactant can be improved by chemical constitution that changes hydrophobic part and the structure that is connected in the hydrophilic segment of hydrophobic part, as the length or the degree of change ethoxylation, and then changes HLB.Suitable surfactant also comprises the surfactant that contains an above headgroup, is called Gemini (Gemini) surfactant.

The surfactant that is used for main class of the present invention comprises but is not limited to alkylphenol ethoxylate, chain triacontanol ethoxylate, alkylamine ethoxylate, Isosorbide Dinitrate and ethoxylate thereof, castor oil ethoxylate, ethylene oxide/propylene oxide block copolymer, alkanol/expoxy propane/ethylene oxide copolymer.

Can be used in the present composition and the example of the surfactant that can obtain from the insecticidal preparation field includes but not limited to the poly-glycosides of alkoxylated triglyceride, alkylphenol ethoxylate, ethoxylized fatty alcohol, alkoxylated fatty acid, alkoxylated alkyl, alkoxylated fats amine, fatty acid polyethylene glycol ester, polyalcohol ethoxylate ester, Isosorbide Dinitrate etc.For example, below having the amphoteric surfactant of the oxirane of different length and expoxy propane part can be available from peaceful (Cognis) company of for example section: ethoxylated castor oil (Agnique CSO), ethoxylation soybean oil (Agnique SBO), alkoxylate rapeseed oil (AgniqueRSO), ethoxylation octyl phenol and nonyl phenol (Agnique Op and Agnique NP), ethoxylation C12-14 alcohol, C12-18 alcohol, C6-12 alcohol, C16-18 alcohol, C9-11 alcohol, oil base-cetyl alcohol, decyl alcohol, isodecanol, tridecanol, octanol, stearyl alcohol (Agnique FOH); Ethoxylation C18 oleic acid (Agnique FAC); The ethoxylation cocoa amine; Ethoxylation oil base amine; Ethoxylated tallow amine; Ethoxylation C8 methyl ester; Ethoxylation triphenyl vinyl phenol (Agnique TSP).

Suitable nonionic surface active agent includes but not limited to the compound by the ethoxylation formation of long-chain alcohol and alkylphenol (comprising anhydro sorbitol and other monose, disaccharides and polysaccharide) or long-chain fat amine and diamines.The number of ethylene oxide unit is preferably between 3 to 50.

Preferred amphoteric surfactant comprises the positive alkyl phenyl APEO that contains various anion (comprising sulfate and phosphate), positive alkyl polyoxyethylene ether (Triton for example ^TM), Isosorbide Dinitrate (Span for example ^TM), polyethylene glycol ether surface active agent (Tergitol ^TM), polyethenoxy sorbitan (tween for example ^TM), polyoxyethylene sorbitan fatty acid ester, polyoxy ethylization ethylene glycol mono-ether (Brij for example ^TM), Lubrol, polyoxy ethylization fluorine-containing surfactant (for example

Fluorine-containing surfactant can be available from E.I.Du Pont Company), ABC type block copolymer (as Xin Poluonike NPE and Atlas G series, available from Uniqema), poly-aryl phenol ethoxylate.

Particularly preferably be polyoxy ethylization aromatics surfactant, as triphenyl vinyl phenol, as Su Bofu available from Rhodia ^TMSurfactant.Wherein, the compound that preferably comprises sulfate and phosphate.The example of the Su Bofu that is commercially available comprises Su Bofu 4D 384, Su Bofu 3D-33, Su Bofu 3D 33LN, Su Bofu 796/P, Su Bofu BSU, Su Bofu CY8, Su Bofu FLK, Su Bofu S/40-FLAKE, Su Bofu TS/54, Su Bofu S25/80, Su Bofu S25, Su Bofu TS54, Su Bofu TS10 and Su Bofu TS29.Su Bofu 4D 384 (2,4,6-three [1-(phenyl) ethyl] phenyl-ω-hydroxyl gathers (oxygen ethene) sulphate) has following structure:

Other Su Bofu surfactants have and top similar structure, and difference is that the length of ethylene oxide chain changes between 3 to 50 oxirane repetitives, and sulfate phosphoric acid base replaces.

The preparation of little blend

Little blend is by mixing first amphoteric compound, at least a second compound and insecticide (unless second compound is an insecticide, this situation is only used two kinds of components), stirs the suitable time then to prepare.Can use the mixture of more than one second compound, they can be from same group that lists above, also can be from different groups.These components need evenly to mix, so that form little blend.In a kind of preferable methods, described component simply fuses together, and stirs, and forms little blend.In another approach, described components dissolved is in common or compatible organic solvent, and stirring, forms little blend.But evaporating solvent is isolated little blend then.

Also preferred second compound is the important component of composition, and its amount surpasses 0.1 weight %.The amount of second compound in the composition preferably accounts between 0.1 weight % to the 90 weight % of composition, more preferably greater than 10 weight % to 50 weight %, more preferably greater than 10 weight % to 30 weight %.The weight ratio of first amphoteric compound and second compound is between 1:1 to 20:1, between the preferred 1:1 to 10:1.If second compound is the non-polymeric surfactant that above limits, then its content in composition is at least 1% of first composition weight, preferably is at least 10% of first composition weight.In the fluid composition of the water miscibility organic solvent that contains adding in a preferred embodiment, the content of this non-polymeric surfactant must be at least 10 weight % of first component.

In the described duration, the stability of little blend is very crucial for the application of this insecticide combination in the final moisture prose style free from parallelism at preamble.Discover, when insecticides obtains by the blending amphoteric compound with as the insecticide of second compound, it is less that the amount of insecticide should keep, so that keep preferred granularity in official hour, avoids active component precipitation and/or little blend dispersion to decompose.In this bi-component blend, the content of insecticide preferably less than about 50 weight % of blend, is more preferably less than about 30 weight %, is more preferably less than about 20 weight %, most preferably less than about 10 weight %.If second compound in little blend is homopolymers or random copolymer, amphoteric compound, the hydrophobic molecule beyond the insecticide and is connected in the hydrophobic molecule on the hydrophilic polymer any one, then can adopt the insecticide of high level usually.But the content of insecticide in this composition preferably still is no more than 60 weight %, perhaps preferably less than 30 weight %.Hydrophily-hydrophobicity block copolymer and nonionic surfactant are preferably used as second compound in the insecticides of the present invention.

Little blend can be destroyed by low amounts of water, so they should not comprise the water that adds as component or solvent, unless water mixes with water-soluble solvent or water soluble compound.Particularly, the content of water should preferably less than 1 weight %, be more preferably less than 0.1 weight % less than 10 weight % in little blend, is more preferably not add water.Having realized that the component that is used to prepare little blend, as first amphoteric compound, second compound, active component, surfactant etc., can be hydration.For example, water can be closely or is incorporated into surfactant, polyethylene glycol, polypropylene glycol etc. inherently.The combination water of this hydration may not destroyed little blend.The aqueous solution of first amphoteric compound, second compound or insecticide or colloidal dispersion should not be used for preparing little blend, unless water is removed with the adoptable any method in this area at that time.If water is inevitable, then can make little blend stable by adding a certain amount of water miscibility or water-miscible organic solvent or another kind of water soluble compound, the addition of described solvent or compound is that per 1 parts by volume water adds at least 2 parts by volume, preferred 5 parts by volume, the more preferably solvent of 10 parts by volume or compound.

Can in little blend composition, add water miscibility solvent or water-soluble solvent or other water soluble compounds,, perhaps prepare liquid or gel concentrate formulation to improve the miscibility of little blend component and active component.If add the water miscibility solvent in said composition, the preferred ratio that adds is a water: solvent is greater than 1:2.

Can add water miscibility or water-soluble solvent in any stage of the little blend of preparation.The example of this kind solvent includes but not limited to following: acetate, acetone, acetonitrile, the 1-butanols, the 2-butanols, cyclohexanone, gamma-butyrolacton, diacetone alcohol, diethoxol, diethylene glycol (DEG), dimethyl sulfoxide (DMSO), ethanol, ethylene glycol, ethyl acetate, ethyl lactate, the grape acid lactone, glycerine, isophorone, isopropyl alcohol, isopropyl alcohol, ethanol, methyl alcohol, methyl cyclohexanone, the N-N-methyl-2-2-pyrrolidone N-, positive Plantacare 818, polyethylene glycol, normal propyl alcohol, propane diols, oxolane, tetrahydrofurfuryl alcohol, triethylene glycol, trimethyl propane etc.The low solvent of preferred plant toxicity in some applications.Behind little blend dilute with water, in final aqueous dispersion, the amount of organic solvent should be less than about 4%, preferably less than about 2%, is more preferably less than about 1%.Most preferably less than about 0.5%.

Water-soluble polymeric compounds or oligomer compounds, as ethylene glycol or glycol polymers or oligomer, the perhaps copolymer of ethylene glycol and propane diols, the perhaps mixture of these compounds and water or also can add in any stage with the mixture of water miscibility solvent is with the preparation appropriate formulation.Can use this solvent or compound to dissolve a kind of, multiple or whole components in little blend, solvent can add before these components, or added in the stage of mixing little blend component, or adding after forming little fusion.

Preferably avoid adding the solvent of water immiscibility, perhaps the consumption of this solvent is kept lower,, reduce the stability of little blend because this solvent of more amount can destroy the tight contact between the component of little blend, increase granularity, perhaps destroy little blend composition.Yet if second compound is aromatic compounds or hydrophobic polymer, said composition can contain the solvent of water immiscibility.The solvability of the solvent of water immiscibility in water is preferably less than 10 grams per liters.In addition, by in these compositions, adding the solvent of water immiscibility, can form gel.

Generality of the present invention be not limited under the situation of concrete using method, before using, little blend can dissolve in aqueous environment, forms aqueous dispersion.In another kind of preparation method, little blend original position in aqueous environment forms, and specific practice is to mix first amphoteric compound and second compound/insecticide, and stirs the sufficiently long time.One or more components of can different order and/or mixing little blend in different solvents are removed and are desolvated, and then they are stirred with water, form aqueous dispersion, prepare insecticides of the present invention thus.For example, the solution of first amphoteric compound can mix with the solution of second compound, stirs the sufficiently long time, forms little blend, then evaporating solvent.Because crosslinked polymer network is not easy blending each other, they should be foreclosed; Yet compound of the present invention can include a certain amount of chain by crosslinked polymer connected to one another, as long as this polymer can form little blend.

The dispersion that the dilution back forms is not necessarily thermodynamically stable.Yet, in water, after the dilution, in about 12 hours, more preferably in 24 hours, be more preferably in about 48 hours at least, most preferably in a couple of days, the granularity of dispersion should remain in the nanoscale scope.The granularity of the little micella that the dilution back forms preferably in about 10 to 300 nanometer range, more preferably in about 15 to 200 nanometer range, is more preferably in about 20 to 100 nanometer range.Granularity increases gradually in time and does not mean that its deficient in stability, as long as particle mean size remains in the nanoscale scope.Preferably, composition of the present invention should not be diluted to the degree that does not have particle because of dilution.Those skilled in the art will appreciate that, this particle size range can be with actual environment for use difference, in actual environment for use, many environmental factors (temperature, pH etc.) and other components have (a trace metal, naturally occurring inorganic matter such as calcium carbonate in the water, the micro-size particles that adds or the nanometer particle of separate sources, colloidal metal, metal oxide or hydroxide etc.) can influence the mensuration of granularity.

On the one hand, the little blend composition that the present invention relates to concentrate, (a) it comprises amphoteric compound and insecticide, (b) it can be one of liquid, paste, solid, powder or gel, (c) in water the dilution after, it disperses easily, forms the aqueous dispersion of granularity in the nanoscale scope, and (d) this dispersion keeps stable in the required time of use.As shown in the following examples, this insecticides can utilize the various amphoteric compounds and the preparation of other components of little blend described in the invention.

A major advantage of little blend composition is, but these compositions can be mixed with the employed powder preparation of field of pesticides, water-dispersible granule, sheet wet powder or similar dry preparation.Generality of the present invention is not limited under the situation of concrete preparation type or method, the routine techniques of insecticide can be used to prepare this insecticidal preparation.For example, utilize disk granulation method, mixed at high speed agglomeration process, extruding pelletization method, fluidized bed prilling method, fluidized bed spray granulation method and spray drying process, can obtain water-dispersible granule or powder.Can add the used conventional excipients of formulation art, to promote process for preparation.By using low boiling point solvent can reduce baking temperature.Pei Zhi little blend is toppled over easily and is measured like this, can disperse fast in aerosol can, has the storage life of prolongation.

In a second aspect of the present invention, in being fit to the composition that uses with the field of pesticides common method, adopt above-mentioned little blend.Therefore, for example, little blend can be the form of water-dispersible granule discussed above, suspending concentrate and solvable liquid concentrate, after water mixes, is sprayed onto the place that exists or estimate to have pest.Can adopt the known conventional preparation technique of technical staff, adjuvant in insecticidal preparation field etc.Dispersion should be at least 24 hours to keeping stable in a couple of days at most.

Of the present invention aspect another, in field of pesticides method commonly used, adopt above-mentioned composition.Therefore, for example, said composition can be mixed with water, is sprayed onto the place that exists or estimate to have pest.

In addition, above-mentioned composition can micellar solution form use, just comprising (normal) micella or anti-(inverted) micella, oil-in-water microemulsion (also claiming " water is outside " microemulsion), water-in-oil microemulsion (also claiming " oil is outside " microemulsion) or molecule solution (cosolution) altogether.Composition also can be mixed with gel, comprise liquid crystal, and can comprise laminar, cylindric or chondritic.

Concentrate can pulvis, powder and the so undiluted state of particle use.This preparation can comprise the known conventional additives of those of ordinary skill in the art, for example carrier.Carrier comprises bleaching earth, kaolin, silica and other high-absorbables, easy moistening inorganic diluents.When being mixed with pulvis, insecticides of the present invention is with trickle solid (as talcum), natural clay, diatomite, powder (as walnut shell powder powder and cottonseed meal) and other are used as the dispersant of insecticide and the organic and inoganic solids of carrier mixes.

Little blend composition can utilize field of pesticides packing method commonly used to pack.For example, after these compositions were mixed with dry preparation, liquid preparation or gel preparation and do not contain the water of adding, they can be packaged in the water-soluble film bag.Described film is made with polyvinyl alcohol usually.

An importance of the present invention is, the little blend of insecticide can with one or more active component blending, perhaps with other different compound blending, as long as these compounds can improve the biologically active of insecticide or insecticidal preparation, reduce metabolism, reduce toxicity, increase chemistry or photochemical stability.Its example comprises adding antiultraviolet compound, metabolism control agent etc.By other components in insecticide and the little blend composition are mixed inherently, can improve activity (for example active and stability of insecticide), reduce toxicity simultaneously and to the harm of environment.

Composition of the present invention also can comprise safener, as benoxacor, cloquintocetmexyl, cyometrinil, cyprosulfamide, allyl dichloride amine (dichlormid), dicyclonon, dietholate, fenchlorazole, fenclorim, separate careless amine, fluxofenim, separate careless oxazole, two benzene oxazole acid (isoxadifen), mefenpyrdiethyl (mefenpyr), mephenate, naphthalic anhydride and oxabetrinil.

Described composition also can comprise cationic and anionic surfactant.The example of suitable cationic amphoteric surfactant includes but not limited to dialkyl group (C8-C18) alkyl dimethyl ammonium chloride, methyl ethoxy (3-15) alkyl (C8-C18) ammonium chloride, monoalkyl and dialkyl group (C8-C18) ammonium chloride etc. that methylates.The example of suitable anionic amphoteric surfactant includes but not limited to: fatty alcohol ether sulphate, alkylnaphthalene sulfonate, diisopropyl naphthalene sulfonate, diisopropyl naphthalene sulfonate, alkyl sulfate, alkylbenzenesulfonate, naphthalenesulfonate condensation compound, naphthalene sulfonate-formaldehyde condensation products etc.The consumption of this anionic or cationic surface active agent is preferably low than other components contents in the insecticides, but is enough to improve the performance of said composition.

Unexpectedly, compare with the conventional formulation of being accepted in the agricultural practice to active component, insecticides of the present invention shows excellent performance.Surprisingly, find that little blend composition has improved the biologically active of insecticidal preparation, thereby can prevent and treat nuisance more effectively.They can improve bioavilability at the target nuisance, comprise the oral administration biaavailability or the local bioavilability of insecticide, thereby can prevent and treat nuisance more effectively.Surprisingly, the insecticide that they can also increase nuisance picked-up effective dose for example reduces the chance that nuisance is avoided insecticide, perhaps reduces the medicament of having taken in and casts aside, thereby can prevent and treat nuisance more effectively.

In addition, this slightly the blend composition can change the pharmacokinetic property of insecticide in target organism, produce excellent activity, more effectively suppress nuisance.In another aspect of this invention, described little blend composition has improved the killing rate of target nuisance, causes more effectively preventing and treating nuisance equally.This insecticides takes effect faster, to shielded plant better protection is provided and the infringement that causes still less.Surprisingly, compare with the conventional formulation of being accepted in the agricultural practice that comprises identical active component, described little blend composition can also be than the infringement that reduces under the low dosage plant.For example, nuisance is used up or the percentage of the leaf of destruction reduces.

Aspect another, little blend composition can change the animal migration of insecticide in soil, thereby can prevent and treat the soil nuisance better of the present invention.Under the situation that does not limit the present invention to concrete theory or application practice, as an example, insecticides can improve insecticide, as the animal migration of oleophylic active component in soil, strengthens the control to the nuisance that is in desired depth.In another example, little blend composition can reduce the animal migration of insecticide in soil, for example prevents that active component is penetrated in the underground water, perhaps promotes active component to be retained in plant surface.By hydrophobicity and the hydrophily that changes component in little blend, perhaps by adding charged component, as cationic or anionic amphoteric compound, perhaps cationic or anionic surfactant can be realized this point.

Aspect another, little blend composition can increase the chance that insecticide enters plant of the present invention, and absorption in therefore improving, for example, even the non-internal-absorting active component, also can improve interior absorption by root, bud or leaf absorption mode.Compare with the conventional formulation that comprises identical or other active components that agricultural practice is accepted, little blend composition of the present invention allows to reduce the amount of application of insecticide.Under the situation that does not limit the present invention to concrete using method,, perhaps,, can reduce the amount of application of insecticide perhaps with the two combination by reducing the amount of application of preparation by in insecticidal preparation, using the active component of low concentration.Because these unexpected discoveries, insecticides of the present invention provide considerable economy and environmental benefit.Insecticides of the present invention can be used to add the active component of wide range, comprises the active component that traditional compound method can't be prepared, and perhaps with after the conventional method preparation, can not provide the active component of enough nuisance control efficiency.

In order to describe the present invention in more detail, provided the preparation that following examples: embodiment 1 and 2 has illustrated little blend, wherein little blend original position in aqueous environment forms.Remaining embodiment has illustrated the preparation (embodiment 3-50) of little blend and to the test (embodiment 51-56) of insecticides.

The composition of embodiment 1 bifenthrin and nonionic block copolymer

Hydrophily-hydrophobicity PEO-poly(propylene oxide) block copolymer EOn-POm-EOn with the oxirane (EO) of different length and expoxy propane (PO) block is as the amphoteric compound in the present embodiment: PLURONIC P85 (n=26, m=40), Pu Luluonike L61 (n=4, m=31) and Pu Luluonike F127 (n=100, m=65).Thick bifenthrin powder (n-octyl alcohol distribution coefficient logP〉6) and 1.5 milliliters of copolymer solutions that form in the salt solution of making buffer with phosphate (pH7.4,0.15M NaCl) are mixed.The composition of final mixture is shown in table 1.

Table 1

Component	PLURONIC P85	PLURONIC P85	Pu Luluonike L61/ Pu Luluonike F127 (mixture of 1:8)
				Copolymer total concentration (weight %)	1.0	3.0	2.25
Bifenthrin (milligram)	5.4	5.5	5.2

With suspension jolting at room temperature 40 hours, under the rotating speed of 13000rpm centrifugal 10 minutes then.The concentration of the bifenthrin in the supernatant is by the UV spectrophotometry.For this reason, utilizing concentration is the liquid storage of bifenthrin in acetonitrile of 8.7 mg/ml, and preparation concentration is the standard liquid of bifenthrin in ethanol of 0 to 0.58 mg/ml.Utilize Perkin-Elmer Lambda 25 spectrophotometers, measure the absorbance of these standard liquids, thereby obtain calibration curve in 260 nanometers.The calibration curve of gained bifenthrin is as follows: absorbance=0.0125+4.3694C _Bifenthrin, r ²=0.999.PLURONIC P85 solution for 1% and 3%, the meltage of bifenthrin in the PLURONIC P85 dispersion is respectively 0.032 mg/ml and 0.073 mg/ml.Bifenthrin is 0.22 mg/ml at the meltage that the Propiram Buddhist nun restrains in the mixture of L61 and Pu Luluonike F127 copolymer.Adopt " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)), utilize 30 millivolts of solid-state lasers, under the wavelength of 635 nanometers, work, by the granularity of particle in the formed dispersion of dynamic light scattering determination.The mensuration that the dispersion that comprises bifenthrin and PLURONIC P85 is carried out shows that the diameter of formed particle surpasses 400 nanometers.In the dispersion of Pu Luluonike L61 that comprises bifenthrin and Pu Luluonike F127, the granularity of particle is 34 nanometers.Therefore, compare with the dispersion that contains a kind of amphoteric compound, the formed dispersion of mixture by the amphoteric compound of two kinds of hydrophilies with different length and hydrophobic parts has comprised more insecticide, has formed littler particle.

The composition of embodiment 2 bifenthrins and nonionic block copolymer mixture

Mixture with the EO of different length and the PEO of PO block-poly(propylene oxide) block copolymer EOn-POm-EOn is as the amphoteric compound in the present embodiment: Pu Luluonike P123 (n=20, m=69), Pu Luluonike L121 (n=5, m=58) and Pu Luluonike F127 (n=100, m=65).The salt solution (pH7.4,0.15M NaCl) of making buffer in water or with phosphate mixes Pu Luluonike P123 and Pu Luluonike L127 in (PBS).As previously mentioned, at elevated temperatures, the mixture of preparation Pu Luluonike P121 and Pu Luluonike L127 in water, the content of each copolymer be 0.1% (J.Controlled Rel.2004,94,411-422).The bifenthrin fine powder of particles contained granularity less than 425mkm mixed with the solution of 1 milliliter of copolymer mixture.The composition of final mixture is shown in table 2.

Table 2

Component	Pu Luluonike P123/ Pu Luluonike F127	Pu Luluonike P123/ Pu Luluonike F127	Pu Luluonike L121/ Pu Luluonike F127
				The composition of Pu Luluonike mixture	1:1	1:1	1:1
Copolymer total concentration (weight %)	2.0	2.0	0.2
				Solvent	Water	PBS	Water
Bifenthrin (milligram)	3.1	3.2	3.1

After adding bifenthrin, then with suspension jolting at room temperature 96 hours, under the rotating speed of 13000rpm centrifugal 10 minutes again.The concentration of the bifenthrin in the supernatant and grain graininess are measured as described in embodiment 1.Be dissolved in the concentration (mg/ml) of the bifenthrin in the dispersion and the load capacity of bifenthrin (shared percetage by weight in the blend that forms with amphoteric compound) and list in table 3.

Table 3

Component	Pu Luluonike P123/ Pu Luluonike F127	Pu Luluonike P123/ Pu Luluonike F127	Pu Luluonike L121/ Pu Luluonike F127
				Solvent	Water	PBS	Water
Bifenthrin concentration (mg/ml)	0.55	0.61	0.22
				Load capacity (% w/w)	2.75	3.05	10.9
Granularity (nanometer)	31	57	107

Therefore, but original position forms the dispersion with small grain size, its insecticide that comprises account for the blend that it forms with amphoteric compound weight 2% to 10%, yet, need the incorporation time of length.

Little blend of embodiment 3 bifenthrins and nonionic block copolymer melt

Utilize the melt of Pu Luluonike block copolymer mixture to prepare little blend of bifenthrin.In brief, 43.7 milligrams the first amphoteric compound Pu Luluonike F127 are added round-bottomed flask, in water-bath, melt in 85 ℃ of following rotation fusing of margins.43.7 milligram of second amphoteric compound Pu Luluonike P123 in 0.65 milliliter of acetonitrile/methanol mixture (2:1 volume/volume) added in the gained melt, by rotating thorough mixing, the water of evaporating solvent and trace under vacuum condition then.8.74 milligrams of bifenthrins that will be in 87.4 microlitre acetonitriles and copolymer melt mixed, evaporating solvent is 30 minutes under vacuum condition.With the melt composition cool to room temperature, hydration in 8.74 ml waters while stirring then.After 1 hour, form opaque slightly aqueous dispersion.The total concentration of Pu Luluonike copolymer in dispersion is 1%.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven InstrumentCo.)) to carry out dynamic light scattering, the granularity of copolymer pellet is 77 nanometers.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin in little blend is 1 mg/ml.Little blend is 10% w/w (0.1 milligram of bifenthrin/1 milligram copolymer) to the load capacity of bifenthrin.Prepared little blend aqueous dispersion was not observed deposited phenomenon in 4 days.Subsequent measurements shows, load the granularity of little blend of bifenthrin do not change.Therefore, utilize concentrated little blend melt of insecticide and amphoteric compound can easily prepare stable aqueous dispersions with small grain size.

Little blend of embodiment 4 bifenthrins and nonionic block copolymer melt

42.3 milligrams of Pu Luluonike F127 and 43 milligrams of Pu Luluonike P123 are added round-bottomed flask, in water-bath,,, under vacuum condition, evaporate the water of trace then by rotating thorough mixing in 85 ℃ of fusions.8.5 milligrams of bifenthrins that will be in 85 microlitre acetonitriles and copolymer melt mixed, evaporating solvent is 30 minutes under vacuum condition.Little blend composition cools to room temperature, is replenished 4.5 ml waters then, and stirring is spent the night.Form opaque dispersion.The total concentration of Pu Luluonike copolymer in dispersion is 1.9%.Although do not observe the bifenthrin visible precipitate, final dispersion under the speed of 13000rpm centrifugal 5 minutes.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (BrookhavenInstrument Co.)) to carry out dynamic light scattering, the granularity of dispersions obtained middle particle is 102 nanometers.Use the UV spectrophotometry as described in embodiment A1, the concentration of bifenthrin in this dispersion is 1.82 mg/ml.Little blend is 9.63% w/w to the load capacity of bifenthrin.At room temperature, dispersion was stable in 30 hours at least.After this, having observed tiny white crystal in dispersion forms.Therefore, utilize concentrated little blend melt of insecticide and amphoteric compound to prepare stable aqueous dispersions with small grain size.

Little blend of embodiment 5 bifenthrins and nonionic block copolymer melt

43.5 milligrams of Pu Luluonike F127 are added round-bottomed flask, in water-bath, melt in 85 ℃ of following rotation fusing of margins.43.5 milligrams of Pu Luluonike P123 in 0.65 milliliter of acetonitrile/methanol mixture (2:1 volume/volume) are added in the gained melts, by rotating thorough mixing, the water of evaporating solvent and trace under vacuum condition then.17.4 milligrams of bifenthrins in 174 microlitre acetonitriles are mixed with the blend of copolymer, and evaporating solvent is 30 minutes under vacuum condition.Copolymer: bifenthrin is 5:1 (weight ratio).With the melt composition cool to room temperature, be dispersed in then in 8.7 ml waters, stirring is spent the night.The total concentration of Pu Luluonike copolymer in mixture is 1%.The result forms the white suspension body that comprises the bifenthrin fine crystals.This suspended substance under the speed of 13000rpm centrifugal 10 minutes.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is 88 nanometers in the supernatant.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin in dispersion is 1.09 mg/ml.Little blend is 10.9% w/w to the load capacity of bifenthrin.Therefore, utilize concentrated little blend melt of insecticide and amphoteric compound to prepare stable aqueous dispersions with small grain size.

Little blend of embodiment 6 bifenthrins and nonionic block copolymer melt

Described according to embodiment 3, the mixture melt of use Pu Luluonike block copolymer, little blend of preparation bifenthrin.In brief, with the first amphoteric compound Pu Luluonike F127 adding round-bottomed flask of ormal weight, in water-bath, melt in 85 ℃ of following rotation fusing of margins.Then the solution of Er Pu Luluonike copolymer in organic solvent (acetonitrile or methyl alcohol) is added in the same flask, the gained copolymer passes through rotation thoroughly to be mixed, and removes the water that desolvates with trace then under vacuum condition.Solution and the copolymer melt mixed of bifenthrin in acetonitrile, evaporating solvent is 30 minutes under vacuum condition.With the melt composition cool to room temperature, water contract 16 hours in water while stirring then.The composition of final mixture is shown in table 4.

Table 4

Component	Pu Luluonike F127/ Pu Luluonike P123	Pu Luluonike F127/ Pu Luluonike P123	Pu Luluonike F127/ PLURONIC P85	Pu Luluonike F127/ Pu Luluonike L121
					The composition of Pu Luluonike mixture	9:1	9:1	1:1	5:1
Copolymer total concentration (weight %)	1.0	2.0	1.0	1.0
					Water	10	5	6.6	6
Bifenthrin (milligram)	10	10	6.6	6

In all cases, observing the white suspension body that comprises the bifenthrin fine crystals forms.This suspended substance under the speed of 13000rpm centrifugal 10 minutes.As the granularity of the concentration of mensuration bifenthrin as described in the embodiment 1 in this dispersion, copolymer pellet and little blend load capacity to bifenthrin.These parameters are shown in table 5.

Table 5

Component	Pu Luluonike F127/ Pu Luluonike P123 (9:1)	Pu Luluonike F127/ Pu Luluonike P123 (9:1)	Pu Luluonike F127/ PLURONIC P85 (1:1)	Pu Luluonike F127/ Pu Luluonike L121 (5:1)
					Copolymer total concentration (weight %)	1.0	2.0	1.0	1.0
Bifenthrin (mg/ml)	0.13	0.12	0.05	0.25
					Load capacity (% w/w)	1.3	0.6	0.5	2.5
Granularity (nanometer)	235	>700	57	137

By the result with experiment 3 of this result relatively, can draw such conclusion: granularity and the load capacity of insecticide in little blend aqueous dispersion depends on that the mixture that is used for preparing little blend is formed and the chemical constitution of amphoteric compound.

Little blend of embodiment 7 bifenthrins and nonionic block copolymer melt

Utilize the melt of Pu Luluonike block copolymer mixture to prepare little blend of bifenthrin, but not with an organic solvent.The second amphoteric compound Pu Luluonike P123 of 124 milligrams the first amphoteric compound Pu Luluonike F127 and 124 milligrams is added round-bottomed flask, in water-bath, melt in 85 ℃ of following rotation fusing of margins, by rotating thorough mixing, under vacuum condition, evaporate the water of trace then.The bifenthrin fine powder of 24.8 milligrams of granularities less than 425mkm mixed with copolymer, under vacuum condition, in 60 minutes, be fused together.Copolymer: the charge ratio of bifenthrin is 10:1.With the melt composition cool to room temperature, in 24.8 ml waters, disperse while stirring then.After 1 hour, form milky slightly dispersion.The total concentration of Pu Luluonike copolymer in dispersion is 1 weight %.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is 82 nanometers.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin in dispersion is 1 mg/ml.Little blend is 10% w/w to the load capacity of bifenthrin.Dispersion prepared is at room temperature deposited and was not observed deposited phenomenon in 24 hours.Subsequent measurements shows that the granularity of particle does not change in this dispersion.After 24 hours, observed the bifenthrin fine crystals and formed.Suspended substance under the speed of 13000rpm centrifugal 3 minutes.The concentration of bifenthrin in supernatant is 0.58 mg/ml, and grain graininess is about 93 nanometers.The dispersion of same little blend is stable under 8 ℃ of lower like this temperature.In the case, dispersion is muddy more, is not separated but observed in 96 hours at least.Show that 15 ℃ of granulometries of carrying out the diameter of particle is about 145 nanometers in the dispersion.Temperature is when 15 ℃ are elevated to 25 ℃, and grain graininess increases to 230 nanometers thereupon.Though deposited phenomenon is arranged, after room temperature and 8 ℃ were deposited 12 days, the residue dispersion contained the bifenthrin of 40% initial load.This shows that the aqueous dispersion of little blend is stable at low temperatures.

Little blend of embodiment 8 bifenthrins and nonionic block copolymer melt

Present embodiment has been described the little blend of three kinds of different amphoteric compounds and insecticide.42.5 milligrams of Pu Luluonike F127 are added round-bottomed flask, in water-bath, melt in 85 ℃ of following rotation fusing of margins.34 milligrams of Pu Luluonike P123 and 8.5 milligrams of Pu Luluonike L121 in 0.085 milliliter of acetonitrile that will be in 0.5 milliliter of acetonitrile/methanol mixture (2:1 volume/volume) add in the gained melts, by rotating thorough mixing, under vacuum condition, rotate the water of evaporating solvent and trace then.8.5 milligrams of bifenthrins that will be in 85 microlitre acetonitriles and copolymer melt mixed, evaporating solvent is 30 minutes under vacuum condition.Copolymer: the charge ratio of bifenthrin is 10:1.With the melt composition cool to room temperature, in 8.5 ml waters, disperse while stirring then.The total concentration of Pu Luluonike copolymer in dispersion is 1 weight %.After 1 hour, form milky dispersion.In at least 24 hours, do not observe the bifenthrin precipitation.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin in dispersion is 0.98 mg/ml.Little blend is 9.8% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is 152 nanometers.Under the speed of 13000rpm with centrifugal 3 minutes of the little blend of equal portions.The concentration of the bifenthrin in the supernatant is 0.7 mg/ml.Therefore, utilize little blend of three kinds of different amphoteric compounds and insecticide can obtain stable aqueous dispersion.

Little blend of embodiment 9 bifenthrins and nonionic block copolymer melt

Present embodiment has been described the little blend of three kinds of different amphoteric compounds and insecticide.63 milligrams of Pu Luluonike F127,50.4 milligrams of Pu Luluonike P123 and 11.9 milligrams of Pu Luluonike L101 are added round-bottomed flask, in water-bath,, under vacuum condition, evaporate the water of trace then in 85 ℃ of following fusions.The composition of the mixture of block copolymer is Pu Luluonike F127: Pu Luluonike P123: Pu Luluonike L101=5:4:1 (weight).With 12.4 milligrams of particles contained granularities is that 425 microns and following bifenthrin fine powder mix with copolymer, is fused together in 60 minutes under vacuum condition.Copolymer: the charge ratio of bifenthrin is 10:1.With the melt composition cool to room temperature, in 12.5 ml waters, disperse while stirring then.The total concentration of Pu Luluonike copolymer in mixture is 1 weight %.After 1 hour, form milky dispersion.In at least 24 hours, do not observe bifenthrin generation visible precipitate.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin in dispersion is 0.98 mg/ml.Little blend is 9.8% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is 144 nanometers.Having observed the bifenthrin fine crystals after 40 hours forms.Under the speed of 13000rpm with centrifugal 3 minutes of the little blend of equal portions.The concentration of the bifenthrin in the supernatant is 0.58 mg/ml.Though deposited phenomenon is arranged, after room temperature was deposited 12 days, the residue dispersion contained the bifenthrin of 40% load.

Little blend that the mixture of embodiment 10 bifenthrins and the block copolymer of the hydrophobicity block with different chemical structures forms

In the present embodiment, utilize the block copolymer of hydrophobicity block, i.e. Pu Luluonike F127 (PEO with different chemical structures ₁₀₀-PPO ₆₅-PEO ₁₀₀) and polystyrene polyethylene oxide (PS ₉₁-PEO ₁₈₂Or PS-PEO) melt of the binary mixture of block copolymer prepares little blend of insecticide.In round-bottomed flask, 42.5 milligrams of Pu Luluonike F127 mix with 8.5 milligrams of PS-PEO in 85 microlitre oxolanes.In water-bath, thoroughly mix the gained viscosity solution by rotation down, under vacuum condition, remove then and desolvate in 85 ℃.The bifenthrin fine powder of 5.1 milligrams of granularities less than 425mkm mixed with copolymer mixture, under vacuum condition, in 30 minutes, be fused together, then the water of rotary evaporation trace under vacuum condition.The composition of copolymer mixture is Pu Luluonike F127:PS-PEO=8.3:1.7 (weight).Copolymer: the charge ratio of bifenthrin is 10:1.With the melt composition cool to room temperature, in 5.1 ml waters, disperse while stirring then.The total concentration of copolymer in dispersion is 1 weight %.After 1 hour, form milky dispersion.In 6 hours, do not observe bifenthrin generation visible precipitate.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin in dispersion is 0.95 mg/ml.Little blend is 9.5% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is 119 nanometers.Under the speed of 13000rpm with centrifugal 3 minutes of the little blend of equal portions.The concentration of the bifenthrin in the supernatant is 0.91 mg/ml, and grain graininess is 74 nanometers.After 6 hours, form the white suspension body that comprises the bifenthrin fine crystals.Insulation still comprised the particle that diameter is about 60 nanometers in the residue dispersion, and comprises the bifenthrin of the initial load of 11 weight % after 48 hours under the room temperature.After depositing 2 days under the room temperature, the concentration of bifenthrin in dispersion is 0.1 mg/ml, and grain graininess is 60 nanometers.Therefore, utilize the formed little blend of amphoteric compound of the insecticide hydrophobic parts different, can obtain stable aqueous dispersion with having chemical constitution.

Little blend that the mixture of embodiment 11 bifenthrins and the nonionic block copolymer of the hydrophobicity block with different chemical structures forms

Utilization has the block copolymer of the hydrophobicity block of different chemical structures, i.e. Pu Luluonike F127 (PEO ₁₀₀-PPO ₆₅-PEO ₁₀₀), Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀) and PS-PEO (PS ₉₁-PEO ₁₈₂) the melt of ternary mixture prepare little blend of bifenthrin.In round-bottomed flask, 13.8 milligrams of Pu Luluonike F127 and 13.8 milligrams of Pu Luluonike P123 mix with 18.4 milligrams of PS-PEO in 184 microlitre oxolanes.In water-bath, thoroughly mix the gained viscosity solution by rotation down, under vacuum condition, remove then and desolvate in 85 ℃.The bifenthrin fine powder of 4.5 milligrams of granularities less than 425mkm mixed with copolymer mixture, under vacuum condition, in 30 minutes, be fused together.The composition of gained copolymer mixture is Pu Luluonike F127: Pu Luluonike P123:PS-PEO=3:3:4 (weight).Copolymer: the charge ratio of bifenthrin is 10:1.With the melt composition cool to room temperature, in 4.6 ml waters, disperse while stirring then.The total concentration of copolymer in dispersion is 1 weight %.After 12 hours, form the milky dispersion that has some small thin slices.Do not observe bifenthrin generation visible precipitate.Use the UV spectrophotometry as described in embodiment A1, the concentration of bifenthrin in little blend is 0.93 mg/ml.Little blend is 9.5% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven InstrumentCo.)) to carry out dynamic light scattering, load the granularity of copolymer pellet of bifenthrin be 96 nanometers.Under the speed of 13000rpm with centrifugal 3 minutes of the little blend of equal portions.The concentration of the bifenthrin in the supernatant is 0.9 mg/ml, and grain graininess is 84 nanometers.In following 40 hours of the room temperature, prepared little blend keeps stable.After this observing the adularescent thin slice forms.After at room temperature depositing 48 hours, under the speed of 13000rpm with centrifugal 3 minutes of suspended substance.The concentration of bifenthrin in little blend is 0.86 mg/ml.The granularity of particle is about 91 nanometers in the dispersion.Insulation is after 60 hours under the room temperature, and the residue dispersion comprises the bifenthrin of 62% initial load.Insulation still comprised the bifenthrin of 13% initial load after 5 days under the room temperature in the dispersion.Therefore, utilize the formed little blend of ternary mixture of amphoteric compound, can make the stable aqueous dispersions of insoluble insecticide with the different hydrophobic parts of chemical constitution.

The formed little blend of embodiment 12 bifenthrins and nonionic block copolymer and nonionic surfactant mixtures

In the present embodiment, utilize the melt of PEO-poly(propylene oxide) block copolymer and nonionic surfactant mixtures to prepare little blend of bifenthrin, wherein said nonionic surfactant is the Zonyl FS300 (E.I.Du Pont Company) that comprises perfluorinate hydrophobic parts and hydrophilic polyethylene oxide chain.This surfactant and Pu Luluonike copolymer, i.e. Pu Luluonike F127 (PEO ₁₀₀-PPO ₆₅-PEO ₁₀₀) and Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀) be used in combination.In round-bottomed flask, 147 milligrams of Pu Luluonike F127 and 147 milligrams of Pu Luluonike P123 are mixed with 49 milligrams of Zonyl FS300 (122.5 microlitres, 40% aqueous solution).In water-bath, thoroughly mix the gained mixture by rotation down, under vacuum condition, remove then and anhydrate in 85 ℃.The bifenthrin fine powder of 48 milligrams of granularities less than 425mkm mixed with copolymer/surfactant viscosity blend, under vacuum condition, in 30 minutes, be fused together, under vacuum condition, remove the water of trace then.The composition of gained copolymer/surfactant mixture is Pu Luluonike F127: Pu Luluonike P123:Zonyl FS300=3:3:1 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 7:1.With the melt composition cool to room temperature.Final preparation is yellow waxy solid.Under agitation, 74.4 milligrams of solid pharmaceutical preparations are dispersed in 7.44 ml waters, after 1 hour, form the milky dispersion.The total concentration of copolymer/surface active agent composition in mixture is about 0.88%.Do not observe bifenthrin generation visible precipitate.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin in dispersion is 1.2 mg/ml.Little blend is 14% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is 56 nanometers in the dispersion.In at least 6 hours, dispersion is stable.After 18 hours, observed the bifenthrin fine crystals and formed.This moment under the speed of 13000rpm with centrifugal 3 minutes of suspended substance.The concentration of the bifenthrin in the supernatant is 0.83 mg/ml.Insulation is after 67 hours under the room temperature, and residue still comprises the bifenthrin of 32% initial load in the dispersion.

The mixture of embodiment 13. bifenthrins and nonionic block copolymer and amphoteric surfactant formed little blend in the presence of organic solvent

Described according to embodiment 12, use the melt of the mixture of identical nonionic block copolymer and amphoteric surfactant to prepare little blend of bifenthrin.Copolymer/surfactant mixture consist of Pu Luluonike F127: Pu Luluonike P123:Zonyl FS300=3:3:1 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 7:1.The preparation of 40.1 milligrams of preparations is dissolved in 100 microliter methanol.The fluid composition of little blend of forming is dispersed in 3.9 ml waters.Form milky a little dispersion at once.The total concentration of copolymer/surface active agent composition is about 0.88% in this dispersion; Methanol concentration is 2.5% volume/volume.Use the UV spectrophotometry as described in example 1 above, the concentration of bifenthrin is 1.2mg/ml in the dispersion.Little blend is 14% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is 31 nanometers in this dispersion.In at least 24 hours, dispersion is stable.After 40 hours, observed the bifenthrin fine crystals and formed.This moment under the speed of 13000rpm with centrifugal 3 minutes of an equal portions dispersion.The concentration of the bifenthrin in the supernatant is 1.13 mg/ml, and grain graininess is 33.5 nanometers.Insulation is after 67 hours under the room temperature, and residue still comprises the bifenthrin of 92% load in the dispersion.Therefore, adding low amounts of water miscibility organic solvent in the little blend composition of liquid can promote the formation of insecticide aqueous dispersion and improve its stability.

Embodiment 14. bifenthrins and nonionic block copolymer and amphoteric surfactant formed little blend in the presence of organic solvent

Described according to embodiment 12, use the melt of the mixture of identical nonionic block copolymer and amphoteric surfactant to prepare little blend of bifenthrin.Copolymer/surfactant mixture consist of Pu Luluonike F127: Pu Luluonike P123:Zonyl FS300=3:3:1 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 7:1.The aimed concn that uses various water miscibility organic solvents to prepare bifenthrin is about the aqueous dispersion of little blend of 0.3 mg/ml.The characteristic of final dispersion is shown in table 6.

Table 6

Solvent	Methyl alcohol	Ethanol	Isopropyl alcohol
				Final solvent, volume %	2.0	1.5	1.5
The total concentration of copolymer and surface active agent composition, weight %	0.2	0.2	0.23
				Bifenthrin concentration (calculating), mg/ml	0.3	0.3	0.32
Granularity, nanometer	41	232	62
				Store bifenthrin concentration after 24 hours, mg/ml	0.3	0.1	0.1

The dispersion that is formed by little blend of the bifenthrin that contains ethanol and isopropyl alcohol was stable at least 6 hours, and the little blend that contains the bifenthrin of methyl alcohol can be stablized 24 hours at least.The little blend of each of equal portions is 13, under the 000rpm centrifugal 3 minutes.Described according to embodiment 1, adopt bifenthrin content in the UV-spectrophotometry supernatant, the gained data are shown in table 6.

Little blend that embodiment 15. bifenthrins and nonionic block copolymer and nonionic surfactant mixtures form

Described according to embodiment 12, use the melt of the mixture of identical nonionic block copolymer and amphoteric surfactant to prepare little blend of bifenthrin, but the concentration of bifenthrin is higher.Particularly, in round-bottomed flask, 126 milligrams of Pu Luluonike F127 and 126 milligrams of Pu Luluonike P123 and 42 milligrams of Zonyl FS300 are blended in 105 microlitres, 40% aqueous solution.In 85 ℃ water-bath, by rotating this mixture of thorough mixing, vacuum is removed water.The bifenthrin fine powder of 140 milligrams of granularities less than 425mkm mixed with the viscosity blend of copolymer/surfactant, and under vacuum condition fusion 30 minutes together, the water of vacuum evaporation trace then.Copolymer/surfactant mixture consist of Pu Luluonike F127: Pu Luluonike P123:Zonyl FS300=3:3:1 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 7:3.3.With the composition cools of fusion to room temperature.Final composition is yellow waxy solid.According to the following aqueous dispersion of preparation shown in the table 7.

Table 7

Solvent	Water	Water/carbinol mixture (A)	Water/carbinol mixture (A)
				Organic solvent, volume %	0	1.64	0.5
The total concentration of copolymer and surface active agent composition, weight %	0.13	0.2	0.07
				Bifenthrin concentration (calculating), mg/ml	0.6	1	0.32

Store bifenthrin concentration after 18 hours, mg/ml

0.04

0.98

0.26

After storing 18 hours under the room temperature, form small white bifenthrin crystallization in the dispersion that under the condition that does not have organic solvent to exist, prepares.On the contrary, two kinds of dispersions that prepare with the water miscibility organic solvent all are stable, do not see the precipitation of bifenthrin.Each dispersion of equal portions is 13, under the 000rpm centrifugal 3 minutes.Described according to embodiment 1, adopt bifenthrin concentration in the UV-spectrophotometry supernatant.To little blend A, at least 26 hours, it is stable that dispersion keeps, and do not observe to be separated; To little blend B, dispersion keeps stable at least 41 hours, does not observe to be separated.The identical little blend (A and B) that contains organic solvent also is stable under the rising temperature.Particularly, little blend B kept stable at 37 ℃ at least 20 hours., observe in the dispersion of little blend A and form white flakes after 5 hours in 37 ℃ of storages.But the bifenthrin that all still detects load in two dispersions is about 97%.Therefore, use the little blend composition that contains 26-33 weight % insecticide can prepare stable aqueous dispersion.

Little blend that embodiment 16. bifenthrins and nonionic block copolymer and nonionic surfactant mixture form

Use the mixture melt of nonionic block copolymer and ethoxylated surfactant to prepare the little blend of bifenthrin.Particularly, (Su Bofu BSU (Rhodia) and Pu Luluonike copolymer, promptly Pu Luluonike F127 and Pu Luluonike P123 mix to use tristyrylphenol ethoxylates.51.5 milligrams of Pu Luluonike F127 and 50.2 milligrams of Pu Luluonike P123 are mixed in 85 ℃ in vial with 82 milligrams of Su Bofu BSU.The fine powder of 48 milligrams of granularities less than the bifenthrin of 425mkm mixed with the viscosity blend of copolymer/surfactant, and fusion 30 minutes together.Copolymer/surfactant mixture consist of Pu Luluonike F127: Pu Luluonike P123: Su Bofu BSU=1:1:1.6 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 10:1.With the composition cools of fusion to room temperature.Final preparation is yellow waxy solid.Under the stirring condition 54 milligrams of little blend preparations of solid are dispersed in 5.4 ml waters.In such 2 hours, form transparent dispersion.The total concentration of copolymer/surface active agent composition is about 0.9 weight % in the mixture.Use the UV spectrophotometry as described in example 1 above, the concentration of bifenthrin is 0.94 mg/ml in little blend.This little blend is 10.4% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is 19 nanometers in the dispersion.This dispersion is stable at least 30 hours, does not have the variation of grain graininess and the precipitation of bifenthrin.

The formed little blend of embodiment 17 bifenthrins and nonionic block copolymer and nonionic surfactant mixtures

The melt of the mixture of use nonionic block copolymer and ethoxylated surfactant prepares little blend of bifenthrin.Specifically, with ethoxylized fatty alcohol (Agnique 90C-3, Kening Co.,Ltd) and Pu Luluonike copolymer, promptly Pu Luluonike F127 and Pu Luluonike P123 are used in combination.In vial, under 90 ℃, 72.7 milligrams of Pu Luluonike F127 and 72.6 milligrams of Pu Luluonike P123 are mixed with 95.7 milligrams of Agnique 90C-3.The bifenthrin fine powder of 26 milligrams of granularities less than 425 microns mixed, be fused together in 30 minutes with copolymer/surfactant viscosity blend.The composition of gained copolymer/surfactant mixture is Pu Luluonike F127: Pu Luluonike P123:Agnique90C-3=1:1:1.3 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 10:1.08.With the melt composition cool to room temperature.Final preparation is a waxy solid.Under agitation, 52 milligrams of little blend compositions of solid are dispersed in 5.2 ml waters.In 2 hours, form the milky dispersion like this.The total concentration of copolymer/surface active agent composition in mixture is about 0.9%.Under the speed of 13000rpm with centrifugal 3 minutes of the little blend of equal portions.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin is 0.54 mg/ml in the supernatant.Little blend is 5.4% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is about 250 nanometers in the dispersion.After this dispersion at room temperature is incubated 24 hours, form white precipitate.Although observe deposited phenomenon, grain graininess is about 315 nanometers in the residue dispersion, and this dispersion still comprises the bifenthrin of 53% initial load.

Little blend of embodiment 18. bifenthrins and single nonionic surfactant

Use (a) to prepare little blend with (b) bifenthrin as second compound as the Zonyl FS300 of first amphoteric compound that comprises the hydrophobic perfluorinated part that is connected on the hydrophilic polyethylene oxide chain.823 milligrams of 40% aqueous solution that comprise 329 milligrams of Zonyl FS300 are heated to 100 ℃.With 32.6 milligrams of granularities less than the bifenthrin fine powder of 425mkm and surfactant melt mixed 30 minutes.Surfactant: the charge ratio of bifenthrin is 10:1.With the melt composition cool to room temperature, obtain yellow waxy solid.Under agitation, 70 milligrams of such solid composites are dispersed in 7 ml waters.After 2 hours, form the milky dispersion like this.Dispersion that equal portions are such is centrifugal 3 minutes under the speed of 13000rpm.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin is 0.18 mg/ml in the supernatant.Little blend is 1.8% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is about 217 nanometers in little blend dispersion.Observe precipitation after 24 hours.Only in dispersion, detect the bifenthrin of 1% initial load this moment.By comparing present embodiment and embodiment 12 and 13, can draw such conclusion: the dispersion stable that the dispersion that forms by the little blend that comprises single amphoteric compound forms not as the little blend by this amphoteric compound and at least a other amphoteric compounds.

Little blend of embodiment 19. bifenthrins and single nonionic block copolymer

Use (a) to restrain F127 and prepare little blend with (b) bifenthrin as second compound as the Propiram Buddhist nun of first amphoteric compound.71.6 milligrams of Pu Luluonike F127 are mixed with the bifenthrin fine powder of 7.1 milligrams of granularities less than 425mkm, and described component is fused together in 30 minutes at 90 ℃.Copolymer: the charge ratio of bifenthrin is 10:1.With the melt composition cool to room temperature, then under agitation, be dispersed in 7.16 ml waters.The total concentration of Pu Luluonike F127 in mixture is 1 weight %.After 1 hour, form milky slightly dispersion.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin is 1 mg/ml in the dispersion.Little blend is 10% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is 90.5 nanometers in the dispersion.In at least 8 hours, do not observe visible bifenthrin precipitation.After 24 hours, observe the white suspension body that comprises the bifenthrin fine crystals and form.Under the speed of 13000rpm with centrifugal 3 minutes of the little blend of equal portions.The concentration of bifenthrin only is 0.07 mg/ml in the supernatant.By relatively this experiment and experiment 3, can draw such conclusion: the formed aqueous dispersion of little blend that utilizes single hydrophily-hydrophobicity block copolymer preparation is not as utilizing the formed aqueous dispersion of little blend that comprises same block copolymer and at least a other amphoteric compounds stable.

Little blend of embodiment 20. bifenthrins and nonionic block copolymer melt

Use (a) to prepare little blend with (b) bifenthrin as second compound as the Tetronic T908 of first hydrophilic compounds (molecular weight is about 25000, EO content: 81%, HLB〉24).36 milligrams of Tetronic T908 are mixed with the bifenthrin fine powder of 4 milligrams of granularities less than 425mkm, in 30 minutes, be fused together at 90 ℃.Copolymer: the charge ratio of bifenthrin is 9:1.With the melt composition cool to room temperature, be dispersed in then in 4 ml waters.The total concentration of Tetronic T908 in mixture is 0.9 weight %.After 2 hours, form the milky dispersion.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin is 1 mg/ml in the dispersion.Little blend is 10% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of particle is 119 nanometers in the dispersion.In at least 32 hours, do not observe visible bifenthrin precipitation.After 24 hours, grain graininess is increased to 158 nanometers.

Little blend of embodiment 21. bifenthrins and nonionic block copolymer melt

Use (a) to prepare little blend with (b) bifenthrin as second compound as the Tetronic T1107 of first hydrophilic compounds (molecular weight is about 15000, EO content: 71%, HLB is 18 to 23).71 milligrams of Tetronic T1107 are mixed with the bifenthrin fine powder of 7.8 milligrams of granularities less than 425mkm, in 30 minutes, be fused together at 90 ℃.Copolymer: the charge ratio of bifenthrin is 9:1.With the melt composition cool to room temperature, then under agitation, 22.1 milligrams of solid composites are dispersed in 2.21 ml waters.After 2 hours, form the milky dispersion like this.The total concentration of Tetronic T1107 in mixture is 0.9 weight %.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin is 0.98 mg/ml in little blend.Little blend is 11% w/w to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (BrookhavenInstrument Co.)) to carry out dynamic light scattering, the granularity of the particle that forms in the dispersion is 89 nanometers.In at least 32 hours, do not observe visible bifenthrin precipitation.After 24 hours, grain graininess is increased to 142 nanometers.

Little blend of the binary mixture of embodiment 22. bifenthrins and nonionic block copolymer

(HLB is 22 as the Pu Luluonike F127 of first amphoteric compound to use (a), EO content: 70%) with (b) (molecular weight is about 6900 as the Tetronic T90R4 of second compound, EO content: 49%, HLB is 1-7) the little blend of preparation bifenthrin.84.1 milligrams of Pu Luluonike F127,81.2 milligrams of Tetronic T90R4 are mixed with the bifenthrin fine powder of 16.7 milligrams of granularities less than 425mkm, in 30 minutes, be fused together at 90 ℃.With the melt composition cool to room temperature.Copolymer mixture consist of F127:Tetronic T90R4=1:1 (weight).Copolymer: the charge ratio of bifenthrin is 10:1.46.5 milligrams of solid composites are dispersed in 4.65 ml waters.After 2 hours, form the milky dispersion like this.The total concentration of copolymer in mixture is 0.9 weight %.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin is 0.9 mg/ml in little blend.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 88 nanometers that load has the granularity of the copolymer pellet of bifenthrin.In at least 32 hours, do not observe visible bifenthrin precipitation.After 24 hours, grain graininess is increased to 125 nanometers.

Little blend of embodiment 23. bifenthrins and nonionic block copolymer and hydrophobicity homopolymers

Use (a) Pu Luluonike F127 (PEO as first amphoteric compound ₁₀₀-PPO ₆₅-PEO ₁₀₀) with (b) as the little blend of the homopolymers poly(propylene oxide) (PPO36, molecular weight are 2000) of second compound preparation bifenthrin.In brief, the component (Pu Luluonike F127, PPO and bifenthrin) of ormal weight is mixed, in 30 minutes, be fused together at 80 ℃.The composition of prepared melt is shown in table 8.

Table 8

Composition	Dispersion A	Dispersion B
			The composition Pu Luluonike F127:PPO of mixture: bifenthrin	3:2:0.5	3:1:0.4
Charge ratio polymer: bifenthrin	10:1	10:1

With the melt composition cool to room temperature, be dispersed in the water then.The total concentration of polymer in dispersion is about 0.9 weight %.Muddy dispersion forms very lentamente.Do not observe visible bifenthrin precipitation.For dispersion A and dispersion B, the grain graininess in these dispersions is respectively 184 nanometers and 191 nanometers { utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (BrookhavenInstrument Co.)) to carry out dynamic light scattering measures }.At least in 24 hours, do not observe visible bifenthrin precipitation.After this under the speed of 13000rpm with centrifugal 3 minutes of the little blend of equal portions, measure the concentration of bifenthrin in the supernatant.For dispersion A and B, these concentration are respectively 0.24 and 0.37 mg/ml, corresponding to 25% and 43% of the bifenthrin of initial load.By comparing present embodiment and embodiment 19, can draw such conclusion:, can improve the stability of the insecticide aqueous dispersion that forms by this little blend by in little blend, adding hydrophobic polymer as second compound.

The formed little blend of the mixture of embodiment 24. bifenthrins and nonionic block copolymer and nonionic ethoxylated surfactant

Utilize tristyrylphenol ethoxylates Su Bofu BSU (Rhodia) and Pu Luluonike F127 (PEO ₁₀₀-PPO ₆₅-PEO ₁₀₀) the little blend of combined preparation bifenthrin.In vial, under 90 ℃, 151.8 milligrams of Pu Luluonike F127 and 37.8 milligrams of Su Bofu BSU are mixed.The bifenthrin fine powder of 20 milligrams of granularities less than 425mkm mixed, be fused together in 30 minutes with copolymer/surfactant viscosity blend.The composition of gained copolymer/surfactant mixture is that the Propiram Buddhist nun restrains F127: Su Bofu BSU=4:1:0.53 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 9.5:1.With the melt cool to room temperature, obtain white solid matter.Under agitation, 20.5 milligrams of these compositions are dispersed in 3.9 ml waters.In about 40 minutes, form transparent in fact dispersion like this.The total concentration of copolymer/surface active agent composition in mixture is about 0.5%.Use the UV spectrophotometry as described in embodiment 1, the concentration of bifenthrin is 0.5 mg/ml in little blend.Little blend holds ability 10.6% w/w to the load of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, the granularity of the particle that forms is about 25.6 nanometers in the dispersion.At least in 18 hours, this dispersion is stable, and grain graininess does not change.

The formed little blend of the binary mixture of embodiment 25. bifenthrins and nonionic block copolymer and nonionic ethoxylated surfactant

Use the melt of the binary mixture of nonionic block copolymer and ethoxylated surfactant to prepare the little blend of bifenthrin.Specifically, tristyrylphenol ethoxylates (Su Bofu BSU, Rhodia) and Pu Luluonike copolymer F127 (PEO ₁₀₀-PPO ₆₅-PEO ₁₀₀) be used in combination.In vial, under 90 ℃, 151.8 milligrams of Pu Luluonike F127 and 37.8 milligrams of Su Bofu BSU are mixed.The bifenthrin fine powder that 20 milligrams of particles contained granularities is not more than 425mkm mixes, was fused together in 30 minutes with copolymer/surfactant viscosity blend.The composition of gained copolymer/surfactant mixture is Pu Luluoni F127: Su Bofu BSU=4:1:0.53 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 9.5:1.With the melt composition cool to room temperature, obtain white solid matter.Under agitation, 20.5 milligrams of solid pharmaceutical preparations are placed on hydration again in 3.9 ml waters, in 40 minutes, form transparent in fact dispersion.The total concentration of copolymer/surface active agent composition in mixture is about 0.5%.Use the UV spectrophotometry as described in embodiment 1, the content of bifenthrin is about 0.5 mg/ml in the said composition.Little blend is 10.6 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven InstrumentCo.)) to carry out dynamic light scattering, it is 25.6 nanometers that load has the granularity of little blend particle of bifenthrin.At least in 18 hours, this dispersion is stable, and granularity does not change.

Little blend of embodiment 26. bifenthrins and nonionic block copolymer melt

Utilize the Tetronics block copolymer to prepare the little blend of bifenthrin.Tetronics is general formula (IV) four arm block copolymers, by expoxy propane and PEO sequential polymerization are obtained to ethylenediamine.The Tetronics copolymer of amount of calculation is mixed with the bifenthrin fine powder that particles contained granularity is not more than 425mkm, in 30 minutes, be fused together at 85 ℃.Copolymer: the charge ratio of bifenthrin is 9:1.With the melt composition cool to room temperature, then under agitation, in water, carry out hydration.Used Tetronics T908 and the characteristic of T1107 and the composition of final mixture are shown in table 9 in these experiments.

Table 9

Copolymer	Tetronics?T908	Tetronics?T1107
			Molecular weight	25000	15000
HLB	>24	18-23
			The concentration of copolymer (weight %) in the dispersion	0.9	0.9
The content of bifenthrin (amount of calculation, mg/ml)	1	1

After 2 hours, form milky slightly dispersion.For Tetronics T908/BF dispersion and Tetronics T1107 dispersion, it is respectively 119 nanometers and 89 nanometers that load has the granularity of the copolymer pellet of bifenthrin.At least in 22 hours, do not observe visible bifenthrin precipitation.The granulometry of carrying out after 22 hours shows that grain graininess all is increased to about 140-150 nanometers under two kinds of situations, and is stable but dispersion keeps.

Little blend of embodiment 27. bifenthrins and nonionic block copolymer melt

Use the melt of Tetronic and Pu Luluonike block copolymer to prepare the little blend of bifenthrin.Particularly, use four arms (four-arm) the block copolymer Tetronic 90R4 of general formula (Iva) (to contain big molecular range poly(propylene oxide) block in addition, molecular weight is 6,900, HLB1-7) binary mixture with Pu Luluonike F127 (HLB22) prepares composition together with bifenthrin.In vial, under 80 ℃, 84.1 milligrams of Pu Luluonike F127 and 81.2 milligrams of Tetronic 90R4 are mixed.The bifenthrin fine powder that 16.7 milligrams of particles contained granularities is less than or equal to 425mkm mixes with copolymer viscosity blend, is fused together in 30 minutes.The composition of gained copolymer/bifenthrin mixture is F127:Tetronic90R4:BF=1:1:0.2 (weight).The charge ratio of copolymer/bifenthrin is 10:1.With the melt composition cool to room temperature, obtain yellow waxy substance.46.5 milligrams of final compositions are placed on hydration again in 4.65 ml waters, in 2 hours, form the milky dispersion.The total concentration of copolymer component in mixture is about 0.9%.Little blend is 9.2 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, load has the granularity of little blend particle of bifenthrin to be about 87.5 nanometers.At least in 22 hours, this dispersion is stable.The granulometry of carrying out in 22 hours shows that grain graininess is increased to 124 nanometers.Do not observe visible bifenthrin precipitation.

Little blend that the binary mixture of embodiment 28. bifenthrins and nonionic block copolymer and nonionic ethoxylated surfactant forms

Use the melt of the binary mixture of nonionic block copolymer and ethoxylated surfactant to prepare the little blend of bifenthrin.Particularly, tristyrylphenol ethoxylates (Su Bofu BSU, Rhodia) and Tetronic T908 (molecular weight is 25,000, HLB〉24) are used in combination.In vial, under 80 ℃, 210 milligrams of Tetronic T908 and 70.2 milligrams of Su Bofu BSU are mixed.The bifenthrin fine powder that 58.8 milligrams of particles contained granularities is not more than 425mkm mixes, was fused together in 30 minutes with copolymer/surfactant viscosity blend.The composition of gained copolymer/surfactant/bifenthrin mixture is T908: Su Bofu BSU:BF=3:1:0.85 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 5.8:1.With the melt composition cool to room temperature, obtain white solid matter.41.7 milligrams of solid pharmaceutical preparations are placed in 4.17 ml waters hydration again spend the night, form stable opaque dispersion.The total concentration of copolymer/surface active agent composition in mixture is about 0.8%.Little blend is 17.3 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 87.4 nanometers that load has the granularity of little blend particle of bifenthrin.At least in 16 hours, this dispersion is stable, and granularity does not change.After dispersion is at room temperature deposited 20 hours, observed the bifenthrin micro crystal and formed.

Little blend of embodiment 29. bifenthrins and nonionic block copolymer and nonionic ethoxylated surfactant

Use the melt of the mixture of nonionic block copolymer and ethoxylated surfactant to prepare the little blend of bifenthrin.Specifically, with ethoxylized fatty alcohol (Agnique 90C-3, Kening Co.,Ltd) and two kinds of Pu Luluonike copolymers, i.e. Pu Luluonike F127 (PEO ₁₀₀-PPO ₆₅-PEO ₁₀₀) and Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀) be used in combination.In vial, 40.4 milligrams of Pu Luluonike F127 and 40.3 milligrams of Pu Luluonike P123 are mixed with 21.9 milligrams of Agnique 90C-3.The bifenthrin fine powder that 18.6 milligrams of particles contained granularities is not more than 425mkm mixes with copolymer/surfactant viscosity blend, is being fused together in 30 minutes under 80 ℃.The composition of gained copolymer/surfactant mixture is Pu Luluonike F127: Pu Luluonike P123:Agnique 90C-3=2:2:1 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 10:1.8.With the melt composition cool to room temperature.Final preparation is a waxy solid.12.3 milligrams of solid pharmaceutical preparations are mixed with 80 microliter methanol,, add 2.46 ml waters then up to dissolving fully.Form milky slightly dispersion immediately.The total concentration of copolymer/surface active agent composition in mixture is about 0.4%, and the content of methyl alcohol is 3 volume/volume %.The content of bifenthrin is 0.74 mg/ml in little blend.Little blend is 15.3 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 96 nanometers that load has the granularity of the copolymer pellet of bifenthrin.In 32 hours, this little blend is stable.

Little blend of embodiment 30. bifenthrins and nonionic block copolymer and nonionic ethoxylated surfactant

Use the mixture of nonionic block copolymer and ethoxylated surfactant to prepare the little blend of bifenthrin.Specifically, the cocoa alkylamine of ethoxylation (Ethoquad C/25, AkzoNobel company) and Tetronic T908 (molecular weight is 25000, HLB〉24) are used in combination.All components in the blend uses with their 10% liquid storages in acetonitrile.The solution that will comprise 7.6 milligrams of Tetronic copolymers, 0.4 milligram of Ethoquad C/25 and 2 milligrams of bifenthrins adds round-bottomed flask, thoroughly mixes by rotation down in 45 ℃ in water-bath, then rotation evaporating solvent and trace water under vacuum condition.The composition of gained copolymer/surfactant mixture is Tetronic T908:Ethoquad C/25=19:1 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 4:1.Gained solid film hydration again in 4 ml waters (target content of bifenthrin is 0.5 mg/ml) forms milky slightly dispersion immediately.The total concentration of copolymer/surface active agent composition in mixture is about 0.2%.As described in the embodiment 1 with the content of bifenthrin in the little blend of UV spectrophotometry, described content is 0.49 mg/ml.Little blend is 20 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 107 nanometers that load has the granularity of little blend particle of bifenthrin.At least in 23 hours, this dispersion is stable.The granulometry of carrying out in 23 hours shows that grain graininess is increased to 167 nanometers.Do not observe visible bifenthrin precipitation.After at room temperature depositing 42 hours, under the speed of 12000rpm with centrifugal 2 minutes of the little blend of equal portions.In the supernatant content of bifenthrin be 0.13 mg/ml or initial load bifenthrin 26%.

Little blend of embodiment 31. bifenthrins and nonionic block copolymer

Use has the PLURONIC P85 of medium hydrophilic value (HLB 12-18), and (n=26, m=40) block copolymer prepares the bifenthrin blend.8 milligrams of PLURONIC P85s are not more than 425mkm with 2 milligrams of particles contained granularities, are dissolved in 1 milliliter of bifenthrin fine powder in the acetonitrile and mix, in water-bath, thoroughly mix by rotation, then rotation evaporating solvent and trace water under vacuum condition in 45 ℃.Copolymer: the charge ratio of bifenthrin is 4:1.Prepared composition hydration again in 2 ml waters (target content of bifenthrin is 1 mg/ml) forms transparent in fact dispersion immediately.The total concentration of PLURONIC P85 is about 0.4% in the mixture.As described in the embodiment 1 with the content of bifenthrin in the little blend of UV spectrophotometry, described content is 1 mg/ml.Little blend is 20 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 35 nanometers that load has the granularity of the copolymer pellet of bifenthrin.At least in 18 hours, do not observe visible bifenthrin precipitation.The similar dispersion that the target content of bifenthrin prepares when being 0.5 mg/ml was stable at least 26 hours.The granulometry of between storage period dispersion being carried out at room temperature shows that grain graininess increases, and is as shown in table 10.

Table 10

Little blend of embodiment 32. bifenthrins and nonionic block copolymer and nonionic ethoxylated surfactant

Use the mixture of nonionic block copolymer and ethoxylated surfactant to prepare the little blend of bifenthrin.Specifically, the cocoa alkylamine of ethoxylation (Ethoquad C/25, AkzoNobel company) is used in combination with Tetronic T1107 (molecular weight is 15000, HLB 18-23).All components in the blend uses with their 10% liquid storages in acetonitrile.The solution that will comprise 7.6 milligrams of Tetronic copolymers, 0.4 milligram of Ethoquad C/25 and 2 milligrams of bifenthrins adds round-bottomed flask, thoroughly mixes by rotation down in 45 ℃ in water-bath, then rotation evaporating solvent and trace water under vacuum condition.The composition of gained copolymer/surfactant mixture is Tetronic T1107:Ethoquad C/25=19:1 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 4:1.Gained solid film hydration again in 4 ml waters (target content of bifenthrin is 0.5 mg/ml) forms milky slightly dispersion immediately.The total concentration of copolymer/surface active agent composition in mixture is about 0.2%.As described in the embodiment 1 with the content of bifenthrin in the little blend of UV spectrophotometry, described content is 0.48 mg/ml.Little blend is 20 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 43 nanometers that load has the granularity of little blend particle of bifenthrin.At least in 30 hours, this dispersion is stable.The granulometry of carrying out in 30 hours shows that grain graininess is increased to 120 nanometers.Do not observe visible bifenthrin precipitation.After at room temperature depositing 42 hours, under the speed of 12000rpm with centrifugal 2 minutes of the little blend of equal portions.In the supernatant content of bifenthrin be 0.2 mg/ml or initial load bifenthrin 40%.

Little blend that embodiment 33. bifenthrins and nonionic block copolymer and nonionic ethoxylated surfactant mixture form

Use the mixture of nonionic block copolymer and ethoxylated surfactant to prepare the little blend of bifenthrin.Specifically, cocoa alkylamine (the Ethoquad C/25 of ethoxylation, AkzoNobel company) be used in combination with Tetronic T1107, wherein Tetronic T1107 is four copolymers containing hydroxyl and carboxyl groups (molecular weight is 15000, HLB 18-23) of poly(propylene oxide) and PEO.All components in the blend uses with their 10% liquid storages in acetonitrile.The solution that will comprise 7.6 milligrams of Tetronic copolymers, 0.4 milligram of EthoquadC/25 and 2 milligrams of bifenthrins adds round-bottomed flask, thoroughly mixes by rotation down in 45 ℃ in water-bath, then rotation evaporating solvent and trace water under vacuum condition.The composition of gained copolymer/surfactant mixture is T1107:Ethoquad C/25=19:1 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 4:1.Gained solid film hydration again in 4 ml waters (target content of bifenthrin is 0.5 mg/ml) forms milky slightly dispersion immediately.The total concentration of copolymer/surface active agent composition in mixture is about 0.2%.As described in the embodiment 1 with the content of bifenthrin in the little blend of UV spectrophotometry, described content is 0.48 mg/ml.Little blend is 20 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 43 nanometers that load has the granularity of little blend particle of bifenthrin.At least in 30 hours, this dispersion is stable.The granulometry of carrying out in 30 hours shows that grain graininess is increased to 120 nanometers.Do not observe visible bifenthrin precipitation.After at room temperature depositing 42 hours, under the speed of 12000rpm with centrifugal 2 minutes of the little blend of equal portions.In the supernatant content of bifenthrin be 0.2 mg/ml or initial load bifenthrin 40%.

Little blend of embodiment 34. bifenthrins and nonionic block copolymer

Use has the PLURONIC P85 of medium hydrophilic value (HLB 12-18), and (n=26, m=40) block copolymer prepares the bifenthrin blend.8 milligrams of PLURONIC P85s are not more than 425mkm with 2 milligrams of particles contained granularities, are dissolved in 1 milliliter of bifenthrin fine powder in the acetonitrile and mix, in water-bath, thoroughly mix by rotation, then rotation evaporating solvent and trace water under vacuum condition in 45 ℃.Copolymer: the charge ratio of bifenthrin is 4:1.Prepared composition hydration again in 2 ml waters (target content of bifenthrin is 1 mg/ml) forms transparent in fact dispersion immediately.The total concentration of PLURONIC P85 is about 0.4% in the mixture.As described in the embodiment 1 with the content of bifenthrin in the little blend of UV spectrophotometry, described content is 1 mg/ml.Little blend is 20 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 35 nanometers that load has the granularity of the copolymer pellet of bifenthrin.At least in 18 hours, do not observe visible bifenthrin precipitation.The similar dispersion that the target content of bifenthrin prepares when being 0.5 mg/ml was stable at least 26 hours.The granulometry of between storage period dispersion being carried out at room temperature shows that grain graininess increases, and is as shown in table 11.

Table 11

Little blend of embodiment 35. bifenthrins and nonionic block copolymer

Use Pu Luluonike R block copolymer to prepare the little blend of bifenthrin.Pu Luluonike R copolymer has formula (III), by oxirane (EO) and expoxy propane (PO) block according to following structure PO _n-EO _m-PO _nForm this structure and Pu Luluonike inverted configuration.Pu Luluonike 25R4 (PO with amount of calculation ₁₉-EO ₃₃-PO ₁₉, molecular weight is 3600, HLB 8) and copolymer and the particles contained granularity bifenthrin fine powder that is less than or equal to 425mkm is dissolved in respectively in the acetonitrile, prepares 10% solution of each component.The solution that will comprise 8 milligrams of 25R4 copolymers and 2 milligrams of bifenthrins adds round-bottomed flask, thoroughly mixes by rotation in 45 ℃ in water-bath, then rotation evaporating solvent and trace water under vacuum condition.Copolymer: the charge ratio of bifenthrin is 4:1.Prepared composition hydration again in 2 ml waters (target content of bifenthrin is 1 mg/ml) forms transparent in fact dispersion immediately.The total concentration of copolymer component is about 0.4% in the mixture.As described in the embodiment 1 with the content of bifenthrin in the little blend of UV spectrophotometry, described content is about 1 mg/ml.Little blend is 20 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 106 nanometers that load has the granularity of little blend particle of bifenthrin.At least in 24 hours, this dispersion is stable, and the granularity of little blend does not change.

Little blend of embodiment A 36. bifenthrins and nonionic block copolymer and nonionic ethoxylated surfactant

Use the mixture of nonionic Pu Luluonike R block copolymer and ethoxylated surfactant to prepare the little blend of bifenthrin.Specifically, tristyrylphenol ethoxylates (Su Bofu BSU, Rhodia) and Pu Luluonike 25R4 (PO ₁₉-EO ₃₃-PO ₁₉, molecular weight is 3600, HLB 8) and the copolymer in combination use.The bifenthrin fine powder that Pu Luluonike 25R4 copolymer, Su Bofu BSU and the particles contained granularity of amount of calculation is not more than 425mkm is dissolved in respectively in the acetonitrile, prepares 10% solution of each component.To comprise the solution of 7 milligrams of Pu Luluonike 25R4 copolymers, the solution that comprises the solution of 1 milligram of Su Bofu BSU surfactant and comprise 2 milligrams of bifenthrins adds round-bottomed flask, in water-bath, thoroughly mix by rotation, then rotation evaporating solvent and trace water under vacuum condition in 45 ℃.The Propiram Buddhist nun that consists of of copolymer/surfactant mixture restrains 25R4: Su Bofu BSU=7:1 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 4:1.Prepared composition hydration again in 2 ml waters (target content of bifenthrin is 1 mg/ml) forms transparent dispersion immediately.The total concentration of copolymer/surface active agent composition is about 0.4% in the mixture.As described in the embodiment 1 with the content of bifenthrin in the little blend of UV spectrophotometry, described content is about 1 mg/ml.Little blend is 20 w/w % to the load capacity of bifenthrin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 33 nanometers that load has the granularity of little blend particle of bifenthrin.The granulometry of carrying out in 13 hours shows that grain graininess increases to 52 nanometers.After dispersion is at room temperature deposited 24 hours, observe the precipitation of bifenthrin.

The formed little blend of embodiment 37. fungicides and nonionic block copolymer and nonionic ethoxylated surfactant

The mixture of use nonionic Pu Luluonike block copolymer and ethoxylated surfactant prepares little blend of triazole type fungicide Flutriafol (Flutriafol).Specifically, tristyrylphenol ethoxylates (Su Bofu BSU, Rhodia) and Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀, molecular weight is 5750, HLB 8) and the copolymer in combination use.Pu Luluonike P123, the Su Bofu BSU of amount of calculation are dissolved in respectively in the acetonitrile, prepare 10% solution of each component.Flutriafol is dissolved in the acetonitrile, prepares 4% solution.To comprise the solution of 7 milligrams of P123 copolymers, the solution that comprises the solution of 1 milligram of Su Bofu BSU and comprise 2 milligrams of Flutriafols thoroughly mixes, evaporating solvent then.Copolymer/surfactant mixture consist of Pu Luluonike P123: Su Bofu BSU=7:1 (weight).Copolymer/surfactant: the charge ratio of Flutriafol is 4:1.Prepared composition hydration again in 2 ml waters (target content of Flutriafol is 1 mg/ml) forms transparent dispersion immediately.The total concentration of copolymer/surface active agent composition is about 0.4% in the mixture.Little blend is 20 w/w % to the load capacity of Flutriafol.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (BrookhavenInstrument Co.)) to carry out dynamic light scattering, it is 18 nanometers that load has the granularity of little blend particle of Flutriafol.After dispersion is at room temperature deposited 8 hours, observe the precipitation of Flutriafol.

Little blend of embodiment 38. fungicides and nonionic block copolymer and anionic ethoxylated surfactant

Utilize the binary mixture of nonionic block copolymer and anionic ethoxylated surfactant to prepare little blend of triazole type fungicide Flutriafol.Specifically, the HLB triphenyl vinyl phenol (Su Bofu 3D33, Rhodia) that equals 16 phosphorylation ethoxylation is used in combination with Tetronic T1107 (molecular weight is 15000, and HLB 24).The TetronicT1107 and the Flutriafol of amount of calculation are dissolved in the acetonitrile corresponding preparation 10% and 4% solution respectively.The Su Bofu 3D33 solution of preparation 17% in ethanol.As the little blend of preparation as described in the embodiment 36.The composition of final mixture is shown in table 12.

Table 12

Composition	37A	37B
			Tetronic T1107: the composition (weight) of Su Bofu 3D33 mixture	7:1	7:1
Copolymer/surfactant: the charge ratio of Flutriafol	4:1	5.3:1
			Targeted loads amount (%)	20.0	15.8

Prepared composition is hydration again in 2 ml waters, forms transparent dispersion immediately.Load has the granularity (utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering measures) of little blend particle of Flutriafol, the target content of Flutriafol and the stability of dispersion to be shown in table 13.

Table 13

Composition	37A	37B
			The concentration of copolymer/surface active agent composition (weight %)	0.4	0.4
The target content of Flutriafol (mg/ml)	1.0	0.75
			Granularity (nanometer)	43	37
Dispersion stability (hour)	4	7

Little blend of embodiment 39. fungicides and nonionic block copolymer and anionic ethoxylated surfactant

Use the interior little blend of inhaling imines bacterium (Stobilurin) fungicide nitrile Fluoxastrobin (azoxystrobin) of binary mixture preparation of nonionic block copolymer and anionic ethoxylated surfactant.Specifically, the HLB triphenyl vinyl phenol (Su Bofu 3D33, Rhodia) that equals 16 phosphorylation ethoxylation is used in combination with Tetronic T1107 (molecular weight is 15000, and HLB 24).The Tetronic T1107 copolymer of amount of calculation is dissolved in the acetonitrile solution of preparation 10%.The nitrile Fluoxastrobin is dissolved in the acetonitrile solution of preparation 4%.The Su Bofu 3D33 solution of preparation 17% in ethanol.To comprise the solution of 6 milligrams of Tetronic T1107 copolymers, the solution that comprises the solution of 2 milligrams of Su Bofu 3D33 surfactants and comprise 2 milligrams of nitrile Fluoxastrobins thoroughly mixes, evaporating solvent then.Copolymer/surfactant mixture consist of Tetronic T1107: Su Bofu 3D33=3:1 (weight).Copolymer/surfactant: the charge ratio of nitrile Fluoxastrobin is 4:1.Prepared composition hydration again in 2 ml waters (target content of nitrile Fluoxastrobin is 1 mg/ml) forms milky dispersion.The total concentration of copolymer/surface active agent composition is about 0.4% in the mixture.Little blend is 20 w/w % to the load capacity of nitrile Fluoxastrobin.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (BrookhavenInstrument Co.)) to carry out dynamic light scattering, it is 130 nanometers that load has the granularity of little blend particle of nitrile Fluoxastrobin.It is muddy more that dispersion becomes when at room temperature depositing.At least in 4 hours, in dispersion, do not observe visible precipitation.

Little blend of embodiment 40. fungicides and nonionic block copolymer and anionic ethoxylated surfactant

Use the interior little blend of inhaling imines bacterium fungicide nitrile Fluoxastrobin of binary mixture preparation of Tetronic T704 (molecular weight is 5500, and HLB 15) and anionic phosphorylation ethoxylation triphenyl vinyl phenol surfactant Su Bofu 3D33.As the little blend of preparation as described in the embodiment A36.The solution that will comprise Tetronic T704, Su Bofu 3D33 and nitrile Fluoxastrobin in organic solvent thoroughly mixes, then evaporating solvent.The composition of final composition is shown in table 14.

Table 14

Composition	39A	39B
			Tetronic T704: the composition (weight) of Su Bofu 3D33 mixture	3.5:1	4:1
Copolymer/surfactant: the charge ratio of nitrile Fluoxastrobin	9:1	8:1
			Targeted loads amount (%)	10.0	11.0

Prepared composition is hydration again in 2 ml waters.Load has the granularity (utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (BrookhavenInstrument Co.)) to carry out dynamic light scattering measures) of little blend particle of nitrile Fluoxastrobin, the target content of nitrile Fluoxastrobin and the stability of dispersion to be shown in table 15.

Table 15

Composition	39A	39B
			The concentration of copolymer/surface active agent composition (weight %)	0.45	0.4
The target content of nitrile Fluoxastrobin (mg/ml)	1.0	0.75
			The dispersion outward appearance	Transparent	Muddy
Granularity (nanometer)	1l	148
			Dispersion stability (hour)	4	5

Little blend of embodiment 41. fungicides and nonionic block copolymer and nonionic fluorine-containing surfactant

The mixture of use nonionic block copolymer and fluorine-containing surfactant prepares little blend of Flutriafol.Specifically, the ZonylFS300 surfactant (E.I.Du Pont Company) that comprises perfluorinate hydrophobicity tail base and hydrophilic polyethylene oxide headgroup is used in combination with Tetronic T1107 copolymer (molecular weight is 15000, and HLB 24).The preparation of little blend is as described in the embodiment 34.In brief, the solution that will comprise 6 milligrams of Tetronic T1107 copolymers, 2 milligrams of Zonyl FS300 surfactants and 2 milligrams of Flutriafols in organic solvent thoroughly mixes, then evaporating solvent.Copolymer/surfactant mixture consist of Tetronic T1107:Zonyl FS300=3:1 (weight).Copolymer/surfactant: the charge ratio of Flutriafol is 4:1.Prepared composition hydration again in 2 ml waters (target content of Flutriafol is 1 mg/ml) forms transparent in fact dispersion.The total concentration of copolymer/surface active agent composition is about 0.4% in the mixture.Little blend is 20 w/w % to the load capacity of Flutriafol.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 111 nanometers that load has the granularity of little blend particle of Flutriafol.At least in 4 hours, in dispersion, do not observe visible precipitation.

Little blend that the mixture of embodiment 42. fungicides and nonionic block copolymer and nonionic fluorine-containing surfactant forms

The mixture of use nonionic block copolymer and fluorine-containing surfactant prepares little blend of nitrile Fluoxastrobin.Specifically, the ZonylFS300 surfactant (E.I.Du Pont Company) that comprises perfluorinate hydrophobicity tail base and hydrophilic polyethylene oxide headgroup is used in combination with Tetronic T704 copolymer (molecular weight is 5500, and HLB 15).The preparation of little blend is as described in the embodiment 36.In brief, the solution that will comprise 7 milligrams of Tetronic T704,2 milligrams of Zonyl FS300 surfactants and 1 milligram of nitrile Fluoxastrobin in organic solvent thoroughly mixes, then evaporating solvent.Copolymer/surfactant mixture consist of Tetronic T704:Zonyl FS300=3.5:1 (weight).Copolymer/surfactant: the charge ratio of nitrile Fluoxastrobin is 9:1.Prepared composition hydration again in 2 ml waters (target content of nitrile Fluoxastrobin is 0.5 mg/ml) forms muddy dispersion.The total concentration of copolymer/surface active agent composition is about 0.45% in the mixture.Little blend is 10 w/w % to the load capacity of Flutriafol.Measure through utilizing " ZetaPlus " Zeta Potential analyzer (Brooker Hai Wen instrument company (Brookhaven Instrument Co.)) to carry out dynamic light scattering, it is 200 nanometers that load has the granularity of little blend particle of nitrile Fluoxastrobin.At least in 8 hours, in dispersion, do not observe visible precipitation.

Little blend of embodiment 43. various insecticides and nonionic block copolymer and nonionic ethoxylated surfactant mixture

The melt of the mixture of use nonionic block copolymer and ethoxylated surfactant prepares little blend of insecticide.Specifically, tristyrylphenol ethoxylates (Su Bofu BSU, Rhodia) and Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀) be used in combination.250 milligrams of Pu Luluonike P123 copolymers are mixed with 250 milligrams of Su Bofu BSU and 50 milligrams of insecticide fine powders, in 1 hour, be fused together.Copolymer/surfactant mixture consist of P123: Su Bofu=1:1 (weight).Copolymer/surfactant: the charge ratio of insecticide is 10:1.With the composition cools of fusion to room temperature.Final composition is a waxy solid.The jolting 1 hour in 1 ml water of 50 milligrams of compositions is with hydration again.The total concentration of copolymer/surface active agent composition is about 4.6% in the mixture.The target content of insecticide in little blend dispersion is 4.5 mg/ml.Little blend is 9 w/w % to the load capacity of insecticide.2 hours back loadings have the granularity (utilizing " Nanotrac 250 " Particle Size Analyzer (Microtrac Inc.) to carry out dynamic light scattering measures) and the dispersion outward appearance of at room temperature depositing after 24 hours of particle in little blend dispersion of insecticide to be shown in table 16.

Table 16

Insecticide	Granularity (nanometer)	Dispersion outward appearance in 24 hours
			Cypermethrin	14	Clarification
Bifenthrin	14	Clarification
			Profenofos	13	Clarification
Avermectin	13	Clarification
			Fluorine worm nitrile	13	Clarification
Pleocidin	13	Clarification
			Pyridalyl (pyridalyl)	14	Clarification

Little blend of embodiment 44. bifenthrins and nonionic block copolymer and anionic ethoxylated surfactant

Use the melt of the mixture of nonionic block copolymer and ethoxylated surfactant to prepare the bifenthrin composition.Specifically, sulfated ethoxylated triphenyl vinyl phenol (Su Bofu 4D-384, Rhodia) and Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀) be used in combination.Preparation of compositions is described with embodiment 22.In brief, the component (Pu Luluonike P123, Su Bofu 4D-384 and bifenthrin) of ormal weight is mixed, in 30 minutes, be fused together.The composition of copolymer/surfactant mixture is shown in table 17.Copolymer/surfactant: the charge ratio of bifenthrin is 20:1.With the melt composition cool to room temperature.Final composition is a viscous liquid, and does not contain the solvent of adding.50 milligrams of compositions are placed on hydration again in 1 ml water, form transparent dispersion immediately.The target content of bifenthrin in little blend dispersion is 4.5 mg/ml.Measure through utilizing " Nanotrac 250 " Particle Size Analyzer (Microtrac Inc.) to carry out dynamic light scattering, load has the granularity of particle in little blend dispersion of bifenthrin, the dispersion outward appearance of at room temperature depositing after 48 hours to be shown in table 17.

Table 17

Pu Luluonike P123: the composition (weight) of Su Bofu 4D-384 mixture	Granularity (nanometer)	Dispersion outward appearance in 48 hours
			4:6	16	Clarification
7:3	13	Clarification

Little blend that the mixture of embodiment 45. bifenthrins and nonionic block copolymer and nonionic surface active agent forms

Use the melt of the mixture of nonionic block copolymer and nonionic surface active agent to prepare the little blend of bifenthrin.Specifically, with sorbitan trioleate (Kening Co.,Ltd) and Pu Luluonike copolymer, i.e. Pu Luluonike F127 (PEO ₁₀₀-PPO ₆₅-PEO ₁₀₀) and Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀) be used in combination.Preparation of compositions is described with embodiment A 22.In brief, the component (Pu Luluonike P123, Pu Luluonike F127, sorbitan trioleate and bifenthrin) of ormal weight is mixed, in 30 minutes, be fused together.Copolymer/surfactant mixture consist of Pu Luluonike F127: Pu Luluonike P123: surfactant=3:6:1 (weight).Copolymer/surfactant: the charge ratio of bifenthrin is 20:1.With the melt composition cool to room temperature.50 milligrams of compositions are placed on hydration again in 1 ml water, stir the back and form the milky dispersion.The target content of bifenthrin in little blend dispersion is 4.5 mg/ml.Measure through utilizing " Nanotrac250 " Particle Size Analyzer (Microtrac Inc.) to carry out dynamic light scattering, it is 23 nanometers that load has the granularity of particle in little blend dispersion of bifenthrin.At room temperature deposit within least 48 hours, it is stable that dispersion keeps.

Little blend of embodiment 46. bifenthrins and nonionic block copolymer and anionic ethoxylated surfactant

Use the melt of the mixture of nonionic block copolymer and nonionic surface active agent to prepare the little blend of bifenthrin.Specifically, poly-aryl phenol phosphate (Su Bofu 3D33, Rhodia) of ethoxylation and Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀) be used in combination.The bifenthrin fine powder that 500 milligrams of Pu Luluonike P123 and 500 milligrams of Su Bofu 3D33 and 100 milligrams of particles contained granularities are not more than 425mkm mixes, and is fused together at 70 ℃ then, obtains transparent liquid melts, and it contains 9% bifenthrin.Allow composition cools to room temperature, add in 10 ml deionized water 100 milligrams of melts and jolting.After the jolting 10 minutes, form the dispersion of clarification.The target content of bifenthrin in little blend dispersion is 0.9 mg/ml.After 30 minutes, measure through utilizing " Nanotrac 250 " Particle Size Analyzers (MicrotracInc.) to carry out dynamic light scattering, it is 5.3 nanometers that load has the granularity of particle in little blend dispersion of bifenthrin, at room temperature deposits after 24 hours to become 5.8 nanometers.Dispersion kept clarification at least in 5 days, do not observe precipitation.

Little blend of embodiment 47. bifenthrins and phosphorylation block copolymer

Use the little blend of three block PEO-poly(propylene oxide)-polyethylene oxide copolymers (Dispersogen 3618, Clariant company) preparation bifenthrin of phosphate end-blocking.Utilize independent Dispersogen 3618 and it and Pu Luluonike P123 (PEO respectively ₂₀-PPO ₆₉-PEO ₂₀) and/or the combined preparation composition of the poly-aryl phenol surfactant Su Bofu 3D33 of anion ethoxylation.In brief, just the component of ormal weight mixes, and is fused together at 70 ℃.The composition of copolymer and copolymer/surfactant mixture is shown in table 18.

Table 18

Component (w/w %)	7A	7B	7C	7D	7E
						Bifenthrin (technical grade, 95 w/w %)	1.05	1.05	1.05	1.05	1.05
Dispersogen?3618	32.98	19.79	9.89	49.48	98.95
						Pu Luluonike P123	32.98	39.58	44.53	49.47	0
Su Bofu 3D33	32.98	39.58	44.53	0	0

Make the melt composition cool to room temperature, every kind of melts of 500 milligrams are added 25 ml deionized water, jolting.After the jolting 10 minutes, all samples forms the clarification dispersion, contains 0.2 mg/ml bifenthrin.Utilize " Nanotrac 250 " Particle Size Analyzer (Microtrac Inc.) difference constantly (30 minutes, 4 hours and 24 hours) carry out dynamic light scattering and measure, load has the measurement result of grain graininess in little blend dispersion of bifenthrin to be shown in table 19.

Table 19

Time after the dilution (hour)	7A	7B	7C	7D	7E
						0.5	9.0	6.4	8.0	22.1	36.2
4	11.1	7.2	6.3	12.6	43.3
						24	10.4	11.7	N/D	20.1	27.1

All dispersions are at room temperature deposited and are still kept clarification after 24 hours, visible precipitate do not occur.

Little blend of embodiment 48 various weed killer herbicides and nonionic block copolymer and nonionic ethoxylated surfactant

The melt of the mixture of use nonionic block copolymer and ethoxylated surfactant prepares little blend of weed killer herbicide.Specifically, tristyrylphenol ethoxylates (Su Bofu BSU, Rhodia) and Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀) be used in combination.At first, 50 Ke Pululuonike P123 and 50 Ke Subofu BSU are fused together at 70 ℃, form transparent homogeneous phase melt, thereby make the deposit blend of Pu Luluonike P123 and Su Bofu BSU.Copolymer/surfactant mixture consist of Pu Luluonike P123: Su Bofu=1:1 (weight).Some technical grade weed killer herbicides with different logP values are respectively got 0.25 gram, add the rich BSU mixture of Pu Luluonike P123/ Su Bo of 4.75 gram deposits.Each weed killer herbicide and corresponding logP value [referring to the The PesticideManual (insecticide handbook) of C.D.S.Tomlin volume, the 11st edition] thereof are listed in table 18.Heated each mixture 10 minutes at 70 ℃, and jolting.Also shown in table 20, all samples forms transparent homogeneous mixture, still keeps liquid behind the cool to room temperature.

Table 20

Composition	Weed killer herbicide	LogP	The blend outward appearance
				9A	Fluorine ketazolam grass	3.36	Faint yellow supernatant liquid
9B	Lorox	3.00	Faint yellow supernatant liquid
				9C	P DimethenamidP (dimethenamid-P)	2.05	Faint yellow supernatant liquid
9D	Prodiamine	4.10	Orange supernatant liquid
				9E	Pendimethalin	5.18	Brown supernatant liquid
9F	Different Lonster	2.5	Faint yellow supernatant liquid

With the limit jolting limit hydration again in 5 ml waters of every kind of blends of 100 milligrams.All samples all dissolves in less than 10 minutes time.The target content of insecticide in little blend dispersion is 4.5 mg/ml.Little blend is 9 w/w % to the load capacity of insecticide.Load has the granularity (utilizing " Nanotrac 250 " Particle Size Analyzer (Microtrac Inc.) to carry out dynamic light scattering measures) of particle in little blend dispersion of weed killer herbicide and the dispersion outward appearance of at room temperature depositing behind the different time interval to be shown in table 21.

Table 21

Composition	Granularity in 2 hours (nanometer)	Dispersion outward appearance in 2 hours	Granularity in 4 hours (nanometer)	Granularity in 24 hours (nanometer)	Dispersion outward appearance in 24 hours
						9A	14.8	Clarification	12.4	12.9	Clarification
9B	15.6	Clarification	11.6	12.3	Clarification
						9C	15.0	Clarification	11.8	12.1	Clarification
9D	15.0	Clarification	12.6	12.6	Clarification
						9E	15.6	Clarification	12.3	12.5	Traces of precipitated
9F	15.1	Clarification	11.5	12.1	Clarification

Except that the little blend that comprises pendimethalin (composition 9E in the table), all dispersions are at room temperature deposited and are kept stable after 24 hours.Load had little blend dispersion of pendimethalin to observe traces of precipitated in the time of 24 hours.

Little blend of embodiment 49. bifenthrins and poly-aryl phenol ethoxylate

Use poly-aryl phenol ethoxylate (Adsee 775, AKZO Nobel company) and Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀) and the combined preparation bifenthrin blend of Su Bofu 3D33 (the anion ethoxylation gathers the aryl phenol surfactant).In brief, the component of ormal weight is mixed, be fused together at 70 ℃.The composition of copolymer and copolymer/surfactant mixture is shown in table 22.

Table 22

Component (w/w %)	11A	11B	11C
				Bifenthrin (technical grade, 95 w/w %)	1.05	1.05	1.05
Adsee775	5.00	10.00	25.00
				Pu Luluonike P123	46.98	44.48	36.98
Su Bofu 3D33	46.98	44.48	36.98

Allow the melt composition cool to room temperature, every kind of melts of 500 milligrams are added 25 ml deionized water, jolting.After the jolting 10 minutes, all samples forms the clarification dispersion, contains 0.2 mg/ml bifenthrin.Utilize " Nanotrac 250 " Particle Size Analyzer (Microtrac Inc.) difference constantly (30 minutes, 4 hours and 24 hours) carry out dynamic light scattering and measure, load has the measurement result of grain graininess in little blend dispersion of bifenthrin to be shown in table 23.

Table 23

Little blend of embodiment 50. weed killer herbicides and nonionic block copolymer and nonionic ethoxylated surfactant

The melt of the mixture of use nonionic block copolymer and ethoxylated surfactant prepares little blend of weed killer herbicide.Specifically, tristyrylphenol ethoxylates (Su Bofu BSU, Rhodia) and Pu Luluonike P123 (PEO ₂₀-PPO ₆₉-PEO ₂₀) be used in combination.Each weed killer herbicide and corresponding logP value thereof (logP value according to Donovan and Pescatore at J.Chromatography A 2002,952, step measurements described in the 47-61) are listed in table 24.Except that clethodim was measured when the pH=2, all the other all logP all measured when pH=7.At first, 50 Ke Pululuonike P123 and 50 Ke Subofu BSU are fused together at 70 ℃, form transparent homogeneous phase melt, thereby make the deposit blend of Pu Luluonike P123 and Su Bofu BSU.Copolymer/surfactant mixture consist of P123: Su Bofu=1:1 (weight).Some technical grade weed killer herbicides with different logP values are respectively got 0.05 gram, add the rich BSU mixture of Pu Luluonike P123/ Su Bo of 0.95 gram deposit.Heated each mixture 10 minutes at 70 ℃, and jolting.All samples forms transparent homogeneous mixture, still keeps behind the cool to room temperature by liquid (table 24).

Table 24

Composition	Weed killer herbicide	LogP	The blend outward appearance
				10A	Butachlor	4.15	Supernatant liquid
10B	Diflufenican	4.76	Troubled liquor
				10C	Karathane	5.43	Yellow supernatant liquid
10D	Trefanocide	5.08	Orange supernatant liquid
				10E	Fluazifop	4.42	Brown supernatant liquid
10F	Dithiopyr	4.28	Faint yellow supernatant liquid
				10G	Clethodim	4.24*	Supernatant liquid
10H	Ioxynil octanoate	5.60	Supernatant liquid

^*When pH=2, measure

Every kind of blend is got 100 milligrams, limit jolting limit hydration again in 5 ml waters.All samples all dissolves in less than 10 minutes time.The target content of insecticide in little blend dispersion is 5.0 mg/ml.Little blend is 5 w/w % to the load capacity of insecticide.Load has the granularity (utilizing " Nanotrac 250 " Particle Size Analyzer (Microtrac Inc.) to carry out dynamic light scattering measures) of particle in little blend dispersion of weed killer herbicide and the dispersion outward appearance of at room temperature depositing behind the different time interval to be shown in table 25.

Table 25

Composition	Granularity in 2 hours (nanometer)	Dispersion outward appearance in 2 hours	Granularity in 4 hours (nanometer)	Grain granularity (nanometer) in 24 hours	Dispersion outward appearance in 24 hours
						10A	14.1	Clarification	13.46	14.54	Clarification
10B	ND	Precipitation	ND	ND	Precipitation
						10C	12.97	Clarification	10.71	15.33	Clarification
10D	14.68	Clarification	9.96	14.06	Clarification
						10E	14.32	Clarification	12.82	14.02	Clarification
10F	14.2	Clarification	13.01	14.28	Clarification
						10G	14.08	Clarification	13.11	14.57	Clarification
10H	14.90	Clarification	12.64	15.26	Clarification

Except that the little blend that comprises Diflufenican (composition 10B in the table 23), all dispersions are at room temperature deposited and are kept stable after 24 hours.Load had little blend dispersion of Diflufenican to observe traces of precipitated in the time of 2 hours.

The soil animal migration of the little blend of embodiment 51. bifenthrins

Use soil thin layer chromatography (s-TLC) to estimate the soil animal migration of the little blend of bifenthrin of the present invention.Be used for preparing the s-TLC plate with what 250 microns sieve screening was passed through through air dried greenhouse topsoil.Add 30 ml distilled waters to 60 grams through the soil of screening, fully grind the gained mixture, until obtaining slurry smooth, that have medium fluid properties.The soil slurry is spread on the cleaning panes with groove fast and equably.Plate comprises 9 centimetres x1 centimetre groove, and the groove dinting depth is 2 millimeters, 1 centimetre of groove each interval.Allow at room temperature dry 24 hours of plate.Before the soil bone dry, 12.5 centimeters above the plate baseline are passed standardized horizontal line of soil horizon.Utilization is stamped ¹⁴The little blend of bifenthrin that these experiments of the bifenthrin sample preparation of the bifenthrin of C labelled with radioisotope are used is to obtain rational sensitivity.What use in these experiments is that concentration is little blend aqueous dispersion of 10%.Respectively get little blend of the labelled with radioisotope of equal portions, point 1.5 centimeters above the plate baseline.Will ¹⁴The sulfentrazone of C mark (sulfentrazone) and ¹⁴The bifenthrin suspended substance of C mark is as reference sample.

Treated plate is put into Gelman ^TMIn the chromatogram s-TLC chamber, allow the point sample district near elutriant (distilled water) storage pool.The end that the s-TLC chamber is opposite with tank is raised 1 centimetre, makes it to tilt a little.Every passage is siphoned into soil plate with water from storage pool with one section 1 centimetre of wide paper.Allow the front end of water move to 12.5 centimetres of line place, remove siphon paper from storage pool this moment.Then, plate dried overnight at room temperature.

Utilize Packard InstantImager then ^TMTLC plate scanner scanning s-TLC two hours.Utilize following formula (1) to determine R from the gained image _fValue:

R _fThe distance (1) of the distance of=little blend migration/solvent migration

These values are shown in table 26.

Table 26

Little blend component	Component ratio (weight)	Rf
			Pu Luluonike F127, PLURONIC P85	1:1	0.21
Pu Luluonike F127, Pu Luluonike L121	5:1	0.12
			Pu Luluonike F127, Pu Luluonike P123, Pu Luluonike L121	5:4:1	0.35
Tetronic?T908	N/A	0.08
			Tetronic?T1107	N/A	0.10
Tetronic T90R4, Pu Luluonike F127	N/A	0.14
			Tetronic T908, Su Bofu BSU	1:1	0.33
Pu Luluonike F127, Pu Luluonike P123, Agnique 90C-4	2:2:1	0.23
			Tetronic?T908，Ethoquad?C/25	19:1	0.10
PLURONIC P85	N/A	0.07
			Pu Luluonike F127	N/A	0.15
Pu Luluonike P123	N/A	0.25
			Pu Luluonike L121	N/A	0.00
Pu Luluonike P123, PLURONIC P85	1:1	0.33
			Pu Luluonike P123, Pu Luluonike L121	1:1	0.17
Pu Luluonike F127, Pu Luluonike P123, Zonyl FS300	3:3:1	0.46
			The rich 4D 384 of Pu Luluonike P123+ Su Bo	1:1	0.64
The rich BSU of Pu Luluonike P123+ Su Bo	1:1	0.58
			The rich 3D 33 of Pu Luluonike P123+ Su Bo	1:1	0.52
The rich 4D 384 of Pu Luluonike F127+ Su Bo	1:1	0.51
			The rich BSU of Pu Luluonike F127+ Su Bo	1:1	0.42
The rich 3D 33 of Pu Luluonike F127+ Su Bo	1:1	0.40
			Sulfentrazone	N/A	1.0
Bifenthrin	N/A	0.00

Fig. 5 has shown the migration situation of the little blend of several bifenthrins through labelled with radioisotope on the s-TLC plate.The concentration of bifenthrin is represented by the shade depth in the radiation trace.These data show, compare with pure bifenthrin, and the bifenthrin that is added in little blend demonstrates improved soil animal migration.The little blend that preferably contains the hydrophobe that the surfactant of at least a block copolymer and non-polymer and fluorine compounds or aromatic series polycyclic compound form.And, preferably contain little blend of two kinds of block copolymers.

The soil animal migration of the little blend of embodiment 52. bifenthrins

Use soil TLC technical testing to contain the soil animal migration of the little blend of bifenthrin of the different components of polymer/surface active agent composition.Specifically, with aqueous solvent with twice of s-TLC plate development.As described in embodiment 48, utilize ¹⁴The bifenthrin of C mark carries out the experiment of soil animal migration.Use water as solvent and launch s-TLC plate twice, after every expansion once, use Packard InstantImager ^TMTLC plate scanner scanning 2 hours.Determine R from image _fValue is summarized in the table 27.

Table 27

For the second time expansion plate the time, observe the migration of bifenthrin in soil once more.

Embodiment 55. contains the soil animal migration of the little blend of bifenthrin of the component of different proportion

Use soil TLC technical testing to contain animal migration in the soil of little blend of polymer/surface active agent composition of Different Weight ratio.Specifically, the weight ratio that comprises each component in little blend of Pu Luluonike P123 and Su Bofu 4D 384 changes between 10:90 to 90:10.As described in embodiment 50, utilize the bifenthrin of 14C mark to carry out the experiment of soil animal migration.Use water as solvent and launch s-TLC plate twice, use Packard InstantImager then ^TMTLC plate scanner scanning 2 hours.Subsequently, utilize identical step to launch the s-TLC plate once more, drying, scanning once more.The image that obtains after twice expansion is shown in Fig. 6.Determine R from image _fValue is summarized in table 28.

For forming different little blends, observe R _fBe worth comparable soil animal migration, but bifenthrin is significantly different along the distribution of TLC trace.When the content of the second component Su Bofu 4D, 384 anion ethoxylated surfactants when 10% is increased to 50%, the result causes bifenthrin to have significant concentration at s-TLC trace front end.When the content of Su Bofu 4D 384 further when 50% is increased to 90%, the result causes bifenthrin to distribute more equably along the s-TLC trace.For the second time expansion plate the time, observe the migration of bifenthrin in soil once more.Shown in data clearly show that the ratio that changes little blend component is influential to the soil animal migration.

Table 28

Shown in data clearly show that the ratio that changes little blend component is influential to the soil animal migration.

The biological test of 56 pairs of little blends of embodiment

Little blend of top embodiment A 3 preparations is dispersed in the water, removes any visible aggregation by centrifugal.It is 77.3% target bifenthrin that the gained supernatant comprises concentration.This material and commercially available TalstarOne bifenthrin sample (can available from FMC Corp.) be compared, and the latter measures by analysis, and the concentration of target bifenthrin is 81.2%.By following campaign these two samples are launched to estimate:

(A) food dish (diet disk) test: this test determination the reaction of 5 tobacco aphids in the length of time (TBW) preparations that single is provided.Said preparation was estimated to be about 2 hours in the time that its intestines stop.The LD50 value of little blend is 80.4ppm.The LD50 value of Talstar One is 233.9ppm.

At 65 ℃ of fusing preparations (except the lactose WP), fusing sample is moved on to the taring pipe, thereby nanoparticle formulation is carried out secondary sample.Based on example weight, prepare sample again with distilled water, obtain the dilute sample of 1:100.It is 1:100 that all follow-up dilute samples all utilize corresponding blank (not containing bifenthrin) nanoparticle formulation to keep the constant density of block copolymer.All Talstar One dilute samples are all with distilled water preparation, technical grade bifenthrin acetone diluted.Maximum concentration is 750ppm, utilizes the dilution method of 1:3 to be reduced to 9ppm.The concentration of all dilute samples is all used high-performance liquid chromatogram determination, and true concentration is used for probability analysis, calculates LD ₅₀Value and LD ₉₀Value.Dilute sample is finished and is prepared in back 1 hour, is put in the food dish.

Pick out heavy 160 milligrams+/-16 milligram 5 the length of time TBW, be put in the international rearing tray of 32 empty hole CDC.With vinyl cover dish is sealed then, before test, allow jejunitas 90 minutes of TBW.Each data point adopts 8 larvas.

Pour the fusion Stoneville food that is heated to 65 ℃ into 50 milliliters of healthy and free from worry (Corning) plastic centrifuge tubes, at room temperature centrifugal 10 minutes, remove particle matter, thereby cook the food dish that is used on above-mentioned processing with the speed of 4000xg." 0 " number cork card punch (cork borer) is inserted the food of clarification, obtain food core (diet core).With the single-blade razor blade these food cores are sliced into the disk of 4 millimeters x1 millimeters then, just before using sample, they are put on the moistening filter paper of a slice.

During TBW is jejunitas, the diluted formulation samples of 1 microlitre is added to the food panel surface.After jejunitas 90 minutes, treated food dish is offered TBW, enjoy food for their time of 30 minutes.After 30 minutes, the percentage of the food dish that record is not eaten up.And then larva carried out 30 minutes observation, observe it handles outbreak to bifenthrin vomiting reaction.After this viewing duration, the larva branch is put into the international rearing tray of the 32 hole CDC that Stoneville food is housed, put back to again and incubate (28 ℃ of foster devices; Humidity 65%; Light: secretly than 14:10).Write down M ﹠ M every day, connect and remember 3 days.The incidence of disease is determined in the following manner: after larva was turned over, itself can not turn back normal condition in 15 seconds.Utilize XL Stad software will fall ill and dead cohort compile, determine LD ₅₀Value and LD ₉₀Value.

(B) local test: local test measure 5 the length of time TBW to the reaction of the single-dose preparations that is applied directly to the 3rd pereonite dorsal part.At duration of test, make larva continue the contact sample.The LD50 value of little blend is 42.3ppm.The LD50 value of Talstar One is 84.4ppm.

(C) leaf dish test: leaf dish test determination TBW in 2 length of time is placed on the reaction of the preparation on the disk that downcuts from the cotton true leaf to single.

Prepare the series of diluted samples of bifenthrin-polymer complex with deionized water, used identical of " blank " polymeric blends and the above-mentioned compound of preparation.Downcut 1 centimetre of leaf dish from the true leaf of cotton, place it on 24 orifice plates that agar is housed, preparation is used for the sample of 24 dishes/time processing (handling rate).15 microlitre Treatment Solution drops are applied to each cotton leaf dish central authorities, are placed on dry (about 1-2 hours) in the fume hood.2 instar larvaes of 1 TBW are put in each hole.Ventilation plastic foil with adhesive-backet covers this orifice plate, and is placed in about 27 ℃ (80 ℉) environmental chambers.After processing, checked this orifice plate in 24,48,72 and 96 hours, to determine the lethality of larva; The evaluation result of 96 hour records feed after processing.

Claims (22)

1. insecticides, said composition comprises the little blend that contains following component:

(a) first amphoteric compound, this compound contain at least one hydrophobic parts and at least one hydrophilic parts and

(b) second compound is selected from down group:

-hydrophobicity homopolymers or random copolymer;

-contain the amphoteric compound of the part identical with first amphoteric compound, but have the length difference of a hydrophilic segment or hydrophobic part at least, perhaps the configuration difference of hydrophobic parts and/or hydrophilic parts;

-comprise the block copolymer of at least one part of the hydrophilic parts that chemically is different from first amphoteric compound or hydrophobic parts;

-comprise the hydrophobicity block copolymer of at least two different hydrophobic blocks;

-hydrophobicity nonpolymer molecules, its molecular weight is not more than 1000; And

-comprise the molecule of the hydrophobic parts that is connected with hydrophilic polymer.

2. composition as claimed in claim 1 is characterized in that, described second compound is hydrophobicity homopolymers or the random copolymer of hydrophobicity greater than first amphoteric compound.

3. composition as claimed in claim 1 is characterized in that, described first compound and second compound all are the ethylene oxide/propylene oxide block copolymers, and oxirane accounts at least 70% of first compound, and what account for second compound is not more than 30%.

4. composition as claimed in claim 1 is characterized in that, described first compound is the ethylene oxide/propylene oxide copolymer, and described second compound is the ethylene oxide/propylene oxide copolymer, and wherein, ethylene oxide block comprises the terminal phosphate base.

5. composition as claimed in claim 1 is characterized in that, described second compound is fluorine-containing organic surface active agent or has at least two but be less than the aromatic compounds of 20 aromatic rings.

6. composition as claimed in claim 5 is characterized in that, described fluorine-containing organic surface active agent or aromatic compounds also comprise hydrophilic polymer.

7. composition as claimed in claim 6 is characterized in that described hydrophilic polymer is a PEO.

8. as claim 6 or 7 described compositions, it is characterized in that described hydrophilic polymer also comprises ionic group.

9. composition as claimed in claim 8 is characterized in that, described ionic group is sulfo group or phosphate.

10. composition as claimed in claim 1 is characterized in that, described second compound is non-polymeric surfactant, and described second compound accounts at least 10% of composition.

11., it is characterized in that said composition does not contain the water of adding as each described composition among the claim 1-7.

12., it is characterized in that said composition contains following at least a as each described composition among the claim 1-7: (a) water miscibility solvent, or (b) water soluble compound.

13. composition as claimed in claim 8 is characterized in that, described water soluble compound is water-soluble polymeric compounds or oligomeric compound.

14., it is characterized in that the not moisture immiscible solvent of said composition as each described composition among the claim 1-7.

15. as each described composition among the claim 1-7, it is characterized in that, produce the dispersion of granularity behind the described composition dilute with water in the nanoscale scope.

Be subjected to nuisance infringement or may be subjected to the place of nuisance infringement to use among the claim 1-7 each composition 16. a method of preventing and treating nuisance, this method are included in.

17. a method for preparing each insecticides among the claim 1-7, this method comprises: the solution of first amphoteric compound is mixed with the solution of at least a second compound, stir time enough, form little blend.

18. method as claimed in claim 17 is characterized in that, in the place that needs the applying pesticide composition, the solution of first amphoteric compound and the solution of at least a second compound is added in the entry, and two kinds of solution are mixed.

19. little blend as claimed in claim 1 is characterized in that, described first component comprises block copolymer, and described second component is the non-polymer surfactant with hydrophobe of fluorine compounds or the formation of aromatics polycyclic compound.

20. little blend as claimed in claim 1 is characterized in that, each block copolymer naturally of described first component and second component.

21. little blend as claimed in claim 20 is characterized in that, this blend also comprises the non-polymer surfactant with the hydrophobe that contains the fluorocarbon part.

22., it is characterized in that this blend also comprises bifenthrin as each described little blend among the claim 19-21.

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