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EP1976376A1 - Formulation agrochimique a base d'acrylate moleculaire modifie - Google Patents

Formulation agrochimique a base d'acrylate moleculaire modifie

Info

Publication number
EP1976376A1
EP1976376A1 EP07712005A EP07712005A EP1976376A1 EP 1976376 A1 EP1976376 A1 EP 1976376A1 EP 07712005 A EP07712005 A EP 07712005A EP 07712005 A EP07712005 A EP 07712005A EP 1976376 A1 EP1976376 A1 EP 1976376A1
Authority
EP
European Patent Office
Prior art keywords
pesticide
spp
meth
acid
acrylates
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07712005A
Other languages
German (de)
English (en)
Inventor
Oliver BRÜGGEMANN
Volker Braig
Thomas Pfeiffer
Matthias Bratz
Aleksandra Volkmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07712005A priority Critical patent/EP1976376A1/fr
Publication of EP1976376A1 publication Critical patent/EP1976376A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds

Definitions

  • Delayed release formulations circumvent this problem by releasing certain amounts of drug over a period of time. However, it is also desirable in some cases to control the pests or weeds by the direct release of a portion of the total amount of active ingredient used.
  • the present invention thus comprises an agrochemical formulation comprising acrylate polymers which are molecularly imprinted in the presence of at least one pesticide.
  • the abovementioned formulations can be prepared by a process which is characterized in that
  • the acrylate polymer is produced by precipitation polymerization in the presence of the pesticide
  • the molecularly imprinted acrylate polymers are composed of at least one functional monomer and at least one crosslinker.
  • acrylate polymer refers to polymers as well as copolymers made at least on the basis of a monomer selected from the group consisting of acrylic acid, methacrylic acid and monomers derived from acrylic acid or methacrylic acid.
  • At least one functional monomer means that one, two or more of the functional monomers can be used to prepare the molecularly imprinted acrylate in the presence of a pesticide, preferably one or two, more preferably one.
  • crosslinker means that one, two or more crosslinkers can be used to prepare the molecularly imprinted acrylate in the presence of a pesticide, preferably one or two, more preferably one.
  • Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate (Meth) acrylamides such as, for example, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, isopropyl (meth) acrylamide, (meth) acryloylmorpholine, dimethylamino-methyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, dimethylaminopropylphenyl (meth) acrylamide, diethylaminomethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide and derivatives of (meth) acrylamide such as N-methyl acrylamide, N-methylol acrylamide, N-methylol methacrylamide;
  • Alkyl (meth) acrylates such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate,
  • Cyano (alkyl) acrylates such as, for example, cyanoalkyl (meth) acrylates (such as cyanoethyl (meth) acrylates, cyanopropyl (meth) acrylates);
  • Acrylic acid and methacrylic acid with methacrylic acid being particularly preferred.
  • the crosslinker may here preferably be selected from the group consisting of ethylenically unsaturated compounds having at least two (ie two, three or four) vinylic or allylic double bonds which are free-radically polymerizable, for example divinyl esters of aliphatic and aromatic dicarboxylic acids (eg the divinyl esters of Succinic acid or diallyl phthalate), oligoallyl esters (such as, for example, triallyl phosphate or triallyl isocyanurate), divinyl ethers of aliphatic and aromatic diols (for example butanediol-1,4-divinyl ether or diallyl bisphenol A), the reaction products of OH-terminated, oligomeric polybutadienes with maleic acid or (meth ) Acrylic acid, ie oligomeric polybutadienes with activated, photopolymerizable olefinic double bonds, di (meth) acrylates of alkylene glycols or al
  • Triallylphosphate or triallyl-socyanurate, triallyl ether or tri (meth) acrylates of triols such as trimethyloethane, trimethylolpropane or triethanolamine
  • tri- and tetraallyl ethers or tri- and tetra (meth) acrylates of tetraols such as pentaerythritol
  • Oligo (meth) acrylates of polyfunctional phenols having 3 to 4 OH groups such as pyrocatechol
  • ON goacrylates oligo (meth) acrylates, oligoallyl monomers and oligovinyl monomers containing at least three functional groups.
  • the molar ratio of functional monomer to crosslinker is usually 1/2 to 1/10, preferably 1/2 to 1/4.
  • MIA pesticide molecularly imprinted acrylates
  • Nicotinic receptor agonists / antagonists clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, a thiazole compound of the formula ⁇ 1
  • a 1 is CH 3 , Cl, Br, I, X is CH, C-Cl, CF or N, Y 'is F, Cl, or Br, Y "is F, Cl or CF 3
  • B 1 is hydrogen, Cl, Br, I, CN
  • B 2 is Cl, Br, CF 3 , OCH 2 CF 3 or OCF 2 H
  • R B is hydrogen, CH 3 or CH (CH 3 ) 2 and malononitrile compounds as in JP 2002 284608, WO 02/89579, WO 02/90320, WO 02/90321, WO 04/06677, WO 04/20399, or JP 2004 99597.
  • Carboxylic acid anilides Benalaxyl, Benodanil, Boscalid, Carboxin, Mepronil, Fenfuram, Fenhexamid, Flutolanil, Furametpyr, Metalaxyl, Ofurace, Oxadixyl, Oxycarboxin, Penthiopyrad, Thifluzamide, Tiadinil, 4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid - (4'-Bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl -2-methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3
  • Benzoic acid amides flumetover, fluopicolide (picobenzamide), zoxamide;
  • Other carboxamides carpropamide, diclocymet, mandipropamide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methylsulfonylamino 3-methyl-butyramide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl) -ethyl) -2-ethylsulfonyl-amino-3-methyl- butyramide;
  • Triazoles Bitertanol, Bromuconazole, Cyproconazole, Difenoconazole, Diniconazole, Enilconazole, Epoxiconazole, Fenbuconazole, Flusilazole, Fluquinconazole, Flutriafol, Hexaconazole, Imibenconazole, Ipconazole, Metconazole, Myclobutanil, Penconazole, Propiconazole, Prothioconazole, Simeconazole, Tebuconazole, Tetraconazole, Triadimenol, Triadimefon , Triticonazole;
  • - imidazoles cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole;
  • Benzimidazoles benomyl, carbendazim, fuberidazole, thiabendazole;
  • Pyridines fluazinam, pyrifenox, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine;
  • Pyrimidines bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimol, pyrimethanil; - piperazines: triforins;
  • Dicarboximides iprodione, procymidone, vinclozolin;
  • acibenzolar-S-methyl anilazine, captan, captafol, dazomet, diclomezine, fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, octhilinone, probenazole,
  • guanidines dodine, iminoctadine, guazatine
  • Sulfur-containing heterocyclyl compounds isoprothiolanes, dithianone;
  • Organophosphorus compounds edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, pyrazophos, tolclofos-methyl, phosphorous acid and their salts;
  • Organochlorine compounds thiophanates methyl, chlorothalonil, dichlofluanid, toluylfluanid, flusulfamides, phthalides, hexachlorobenzene, pencycuron, quintozene;
  • Nitrophenyl derivatives binapacryl, dinocap, dinobuton;
  • ALS inhibitors such as amidosulfuron, azimsulfuron, bensulfuron, chlorimuron, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethoxysulfuron, flazasulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, lodosulfuron, mesosulfuron, metsulfuron, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, Pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, imazamethabenz, imazamox, imazapic, imazapyr
  • Herbicides such as metflurazon, norflurazon, flufenican, diflufenican, picolinafen, beflubutamide, fluridone, flurochloridone, flurtamone, mesotrione, sulcotrione, isoxachlorotole, isoxaflutole, benzofenap, pyrazolynate, pyrazoxyfen, benzobicyclone, amitrole, cloma- zone, aclonifen, 4- (3 -trifluoromethylphenoxy) - 2- (4-trifluoromethylphenyl) pyrimidine, and 3-heterocyclyl-substituted benzoyl derivatives of the formula (see WO-A-96/26202, WO-A-97/41 116, WO-A-97/411 17 and WO-A-97/41 1 18)
  • R 8 is hydrogen, halogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, Ci-C 6 alkoxy, -C 6 - haloalkoxy, Ci -C 6 alkylthio -alkyl, C 1 -C 6 -alkyl ky I su If i ny I or Ci-C 6 alkylsulfonyl;
  • R 9 represents a heterocyclic radical selected from the group consisting of thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 4,5 - Dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl and 4,5-dihydroisoxazol-5-yl, wherein said radicals may carry one or more substituents, for example, mono-, di-, tri- or tetrasubstituiert by halogen, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, CrC 4 - haloalkyl, Ci-C4-haloalkoxy or Ci-C 4 alkylthio;
  • R 11 hydrogen, halogen or C 1 -C 6 -alkyl
  • R 12 d-Ce-alkyl
  • R 13 hydrogen or C 1 -C 6 -alkyl.
  • EPSP synthase inhibitors such as glyphosate
  • Glutamine synthase inhibitors such as glufosinate and bilanaphos
  • DHP synthase inhibitors such as asulam
  • Mitosis inhibitors such as Benfluralin, Butraline, Dinitramine, Ethalfluralin, Fluchloralin, i-Sopropalin, Methalpropalin, Nitralin, Oryzalin, Pendimethalin, Prodiamine, Profluralin, Trifluralin, Amiprofos-methyl, Butamifos, Dithiopyr, Thiazopyr, Propyzamide, Tebutam, Chlorthal, Carbetamide, Chlorobufam, Chlorpropham and Propham;
  • VLCFA inhibitors such as acetochlor, alachlor, butachlor, butenachlor, delachlor, diethyl, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, prynachlor, terbuchlor, thenylchloride, xylachlor, Allidochlor, CDEA, epronaz, diphenamid, napropamide, naproanilide, pethoxamide, flufenacet, mefenacet, fentrazamide, anilofos, piperophos, cafenstrole, indanofan, and tridiphan; Cellulose biosynthesis inhibitors such as dichlobenil, chlorthiamide, isoxaben and flupoxam;
  • Herbicides such as dinofenate, dinoprop, dinosam, dinoseb, dinoterb, DNOC, etinofen and
  • Auxin herbicides such as Clomeprop, 2,4-D, 2,4,5-T, MCPA, MCPA thioethyl, dichlorprop,
  • Auxin transport inhibitors such as Naptalam, Diflufenzopyr;
  • safener has the following meaning: It is known that in some cases better herbicidal compatibility can be achieved by the combined application of specifically acting herbicides with organic active compounds, which themselves can have a herbicidal action. In these cases, these compounds act as an antidote or antagonist and are referred to as “safeners” due to the fact that they reduce or prevent crop damage.
  • Preferred insecticides are metaflumizones, pyrethroids such as allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta- cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin , prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, flucythrinates, preferably alpha-cypermethrin, c
  • Preferred fungicides are azole fungicides such as triazole fungicides such as bitertanol, bromoconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole , Tebuconazole, Tetraconazole, Triadimenol, Triadimefon, Triticonazole; Imidazole fungicides such as cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole; Benzimidazoles Fungicides such as benomyl, carbend
  • the acrylate polymer is produced by precipitation polymerization in the presence of the pesticide
  • step (1) of the process is well known to those skilled in the art and is described, for example, in Guyot, A. (1989), Comprehensive Polymer Science, Vol. 4: Eastmond, G. C, Ledwith, A., Russo , S., Sigwalt, P. (Eds.). Oxford: Pergamon, pp. 261-273.
  • the molecularly imprinted acrylate polymer according to the invention can be prepared by reacting
  • Solvent was dissolved, which corresponds in a most preferred embodiment, the solvent in which the monomer is dissolved, or
  • a protective colloid may also be added in step a).
  • Suitable protective colloids are surface-active substances.
  • surfactant is defined below.
  • the polymerization can be carried out in a radical, anionic, cationic or coordinative mechanism or according to the principle of a polycondensation or polyaddition. Preferably, it is polymerized via a free-radical mechanism.
  • Various initiators and / or catalysts can be used, if appropriate also in combination with heat supply.
  • cationic polymerizations for example, the following initiators can be used:
  • Protic acids Lewis acids with and without coinitiators, carbonium ions, iodonium ions and / or ionizing radiation
  • the following initiators can be used: bases, Lewis bases, organometallic compounds and / or electron transfer agents, e.g. Alkali metals, alkali metal-aromatic complexes, metal ketyls
  • the following initiators / catalysts can be used:
  • Zeroegler-Natta catalysts Zeroegler-Natta catalysts
  • transition metals e.g. Metallocenes and / or Activated Transition Metal Oxides
  • Initiators suitable for free-radical polymerization include, for example, peroxides or azo compounds, substituted ethanes (e.g., benzopinacols), redox systems with inorganic and organic components, heat, UV light and other high-energy radiation, hydroperoxides, peresters, and persulfates, e.g. the potassium peroxodisulfate, preferably azo compounds
  • Suitable azo compounds are 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4 dimethylvaleronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl 2,2'-azobisisobutyrate, 2- (carbamoylazo) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2,2'-azobis (N, N'-dimethyleneisobutyramidine), as free base or as hydrochloride, 2,2'-azobis (2-amidinopropane), as free base or as hydrochloride,
  • Suitable peroxides are, for example, acetylcyclohexanesulphonic peroxide, diisopropyl peroxydicarbonate, t-amylperneodecanoate, t-butylperneodecanoate, t-butyl perpivalate, t-amyl perpivalate, bis (2,4-dichlorobenzoic acid) peroxide, diisononanoic acid peroxide, di-decanoic acid peroxide and dioctanoic acid peroxide , Dilaurylic acid roxide, bis (2-methylbenzoic acid) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoic acid peroxide, t-butylper-2-ethylhexanoate, bis (4-chlorobenzoic acid) peroxide, t-butylperisobutyrate, t-butylpermaleinate, 1,1
  • Suitable initiators are also redox systems such as e.g. Fe - H2O2, ascorbic acid - H2O2, which are sulfinic acid derivatives such as Brüggemann, z. Disodium 2-dihydroxy-2-sulfinato acetate (e.g., BRUGGOLIT from Brüggemann) and H2O2.
  • the crosslinker can be added in solid, liquid form to the reaction mixture or dissolved or dispersed in a solvent (i.e., emulsified or suspended), preferably added dissolved.
  • a liquid crosslinker or a crosslinker dissolved (or dispersed / mixed) in a solvent is added to the reaction mixture, more preferably a crosslinker dissolved (or dispersed / mixed) in a solvent.
  • the crosslinker is dissolved in the same solvent as the functional monomer or pesticide.
  • solvents which are soluble in the monomers required for the preparation of the particles prepared in step 1 can be used as the solvent.
  • organic solvents are used such as dimethylformamide, ethanol, methanol, isopropanol, chloroform, dichloromethane, toluene, dimethyl sulfoxide, hexane and acetonitrile, preferably toluene and acetonitrile.
  • organic solvent any organic solvent in which the monomers of the particles prepared in the step (1) are soluble can be used.
  • organic solvents are used, such as dimethylformamide, ethanol, methanol, isopropanol, chloroform, dichloromethane, toluene, dimethyl sulfoxide, hexane and acetonitrile, preferably toluene and acetonitrile. It is also possible to use mixtures of the abovementioned solvents.
  • acetic acid or water or mixtures of acetic acid and water can be added to the solvent or the solvent mixtures, up to a proportion of 50% (w / w).
  • step (3) the loading is carried out by active ingredient.
  • the particles prepared in step (1) and washed in step (2) are incubated with a drug solution.
  • the incubation time depends on polymer and active ingredient. For example, it may be incubated for 30 minutes to 24 hours at temperatures of 5 ° C to 30 ° C.
  • the active ingredient may in this case be dissolved in an organic solvent or a mixture of organic solvent or water.
  • the choice of solvent depends on the nature of the active ingredient. It is important that in this case the active ingredient completely, i. molecular disperse dissolved.
  • formulation types which can be prepared on the basis of the MIA are here suspensions (SC, OD, FS), pastes, pastilles, wettable powders, dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which may either be soluble (soluble) or dispersible (wettable) in water, as well as gel formulations for seed treatment (GF).
  • the above formulations may e.g. by stretching the MIA with solvents and / or carriers, if desired using excipients.
  • auxiliaries describes surface-active substances (such as wetting agents, adhesives or dispersants, protective colloids or adjuvants), anti-foaming agents, thickeners, antifreeze agents, bactericides and, if they are seed dressing formulations, if appropriate adhesives and / or if appropriate dyes.
  • Suitable protective colloids are all protective colloids customary for the formulation of agrochemical active compounds, i. in the present case, all water-soluble polymers of amphiphilic character known to the person skilled in the art, such as, for example, proteins, denatured proteins, polysaccharides, hydrophobically modified starches, and synthetic polymers.
  • Suitable thickeners which may be present in the formulations according to the invention are all thickeners customary for the formulation of agrochemical active compounds.
  • thickeners ie compounds which impart a pseudoplastic flow behavior to the formulation, ie high viscosity at rest and low viscosity in the agitated state
  • thickeners are, for example, polysaccharides or organic and inorganic layer minerals such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (RT Vanderbilt) or Attaclay® (Engelhardt).
  • Suitable antifoams which may be present in the formulations according to the invention are all antifoams customary for the formulation of agrochemical active compounds.
  • antifoam agents are silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides can be added to stabilize aqueous formulation types.
  • Suitable bactericides which may be present in the formulations according to the invention are all conventional bactericides for formulating agrochemical active compounds, for example bactericides based on diclorophene and benzyl alcohol hemiformal. Examples of bactericides are Proxel® from the company ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas.
  • Suitable antifreeze agents which may be present in the formulations according to the invention are all antifreeze agents customary for the formulation of agrochemical active compounds. Suitable antifreeze agents are, for example, ethylene glycol, propylene glycol or glycerol, preferably propylene glycol and glycerol.
  • Suitable colorants are all customary for such purposes dyes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, Cl. Pigment Red 1 12 and Cl. Solvent Red 1 known dyes, as well as pigment blue 15: 4, pigment blue 15: 3, pigment blue 15: 2, pigment blue 15: 1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 1 12, pigment red 48: 2, pigment red 48: 1, pigment red 57: 1, pigment red 53: 1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108
  • Suitable adhesives which may be present in the formulations according to the invention are all customary binders which can be used in pickling agents.
  • Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
  • mineral oil fractions of medium to high boiling point such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.
  • mineral oil fractions of medium to high boiling point such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivative
  • the MIA can be ground to a fine suspension of active substance with the addition of dispersing and wetting agents and water or an organic solvent (or solvent / water mixtures).
  • a gelling agent is added to gel formulations (fe. Carrageen (Satiagel ®) Dilution with water gives a stable suspension of the MIA.
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
  • Granules for example coated, impregnated and homogeneous granules, can be prepared by binding the MIA to solid carriers.
  • the formulation types suitable for seed treatment can be diluted or undiluted as needed 2 to 10 times, so that 0.01 to 60% by weight, preferably 0.1 to 40% by weight of the pesticide are present in the formulations to be used for the stain.
  • MIA and all MIA-based formulations are referred to as MIA formulations.
  • the present invention claims methods for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, characterized in that an MIA formulation is applied to the respective pests (ie phytopathogenic fungi and / or unwanted insects or mites) whose habitat or plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat act.
  • an MIA formulation is applied to the respective pests (ie phytopathogenic fungi and / or unwanted insects or mites) whose habitat or plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat act.
  • seed treated with a MIA formulation suitable for seed treatment is also used.
  • the amounts of pesticide are 0.1 g to 10 kg per 100 kg of seed, preferably 1 g to 5 kg per 100 kg of seed, more preferably 1 g to 2.5 kg per 100 kg of seed.
  • seed includes seeds of all kinds, such as grains, seeds, fruits, tubers, cuttings and similar forms.
  • seed preferably describes grains and seeds here.
  • Suitable seeds are cereal crops, strawberry crops, root crops, oilseeds, vegetable seeds, spice seed, ornamental plant seed, e.g. Seeds of durum wheat, wheat, barley, oats, rye, maize (fodder corn and sweetcorn), soya, oilseed, cruciferous vegetables, cotton, sunflowers, bananas, rice, oilseed rape, beet ,, sugarbeet, fodder beetroot, potato, grass, ( Ornamental) lawn, fodder grass, tomato, leek, pumpkin, cabbage, iceberg lettuce, pepper, greens, melons, Brassica spp, melons, beans, peas, garlic, onions, carrots, tubers such as sugar cane, tabbak, grapes, petunia and geranium , Pansy, balsam, prefers wheat, corn, soy and rice.
  • Seed may also be seed of transgenic or plant obtained by conventional breeding methods.
  • seed can be used which is tolerant of herbicides, fungicides or insecticides, e.g. to sulfonylureas, imidazolinones or gluconate or glyphosate (see, for example, EP-A-0242236, EP-A-242246) (WO 92/00377) (EP-A-0257993, U.S. Pat No. 5,013,659) or transgenic plant seeds, e.g. Cotton that produces Bacillus thuringiensis toxin (Bt toxins) and thereby resistant to certain pests (E P-A-0142924, EP-A-0193259).
  • phytopathogenic fungi describes but is not limited to the following species: Alternaria spp. on rice, vegetables, soya beans, oilseed rape, sugarbeet and fruits, Aphanomyces spp. on sugar beet and vegetables, Bipolaris and Drechslera spp. on corn, cereals, rice and ornamental grass, Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental flowers, grapes, Bremia lactucae on lettuce, Cercospora spp. on corn, soybean, and sugarbeet, Cochliobolus spp.
  • Ants for example Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Pogonomyrmex spp and Pheidole megacephala,
  • Flies e.g. Agromyza oryzea, Chrysomia bezziana, Chrysomya hominivorax, Chrysomia macellaria, Contarina sorghicola, Cordylobia anthropophaga, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Fannia canicularis, Gasterophilus intestinalis, Geomyza tri punctata, Glossina morsitans, Haematobia irritants, Haplodiplosis equestris, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Muscina stabulans, Oestrus ovis, Opomyza flo
  • Orthoptera e.g. Acrididae, Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melonoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus;
  • Termites e.g. Calotermes flavicollis, Coptotermes spp, Dalbulus maidis, Leucotermes flavipes, Macrotermes gilvus, Reticulitermes lucifugus, and Termes natalensis;
  • Arachnids for example eg of the families Argasidae, Ixodidae and Sarcoptidae, eg Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp eg Aculus badendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp eg Phytone
  • Nematodes especially plant parasitic nematodes e.g. "root-knot” nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other melodiogynous spp; cyst-forming nematodes, Globodera rostochiensis and other Globodera spp; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera spp; Seed gall nematodes, Anguina spp; Star and foliar nematodes, Aphelenchoides spp; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus spp; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus spp
  • Controlling undesired plant growth means controlling / destroying plants that grow in places where they are undesirable, e.g. from
  • solution 2 Another solution (solution 2) was prepared by dissolving the remaining 3/4 of the initiator, corresponding to 1.594 g, in 250 ml of acetonitrile. The second half of solution 1 and solution 2 were added by means of the two HPLC pumps in the reactor over a period of 18 h. Dosage rates for solution were 1: 0.153 ml / min, and for solution 2: 0.232 ml / min. The subsequent post-reaction time was 6 hours, so the total reaction time thus 24 h. After each full hour, a 1 mL sample was taken from the reaction mixture and, after filtration, subjected to HPLC analysis.
  • Example b A 2-liter HWS reactor was equipped with a condenser, a stirrer motor, an anchor stirrer, a glass fritted nitrogen inlet tube, a Julabo LC 3 laboratory controller with 2 PT-100 thermosensors, an oil bath with immersion heater and magnetic stirrer. The apparatus was purged with nitrogen before the start of the experiment. During the entire experiment, nitrogen was passed through the solution at a flow rate of about 10 L / h. 1000 ml of solvent acetonitrile (AcN) were introduced into the reaction vessel and in this 18 g of fipronil (template), 6.12 g of methacrylic acid (functional monomer) and 76.32 g of trimethylolpropane trimethacrylate dissolved.
  • AcN solvent acetonitrile
  • Example 1 a The mixture obtained from Example 1 a) was filtered, and the residue remaining in the filter was subsequently washed with 100 ml of acetonitrile and then with 100 ml of methanol over a period of 10 min.
  • Example 3 Loading the polymer with a pesticide
  • Example 3 The release behavior of a post-polymerization molecular imprinted polymer (MIP1, prepared according to Example 3) was measured at the rate of release of a post-polymerization loaded non-imprinted control polymer (CP1), the data being collected according to the procedure outlined in Example 4 A).
  • CP1 was synthesized in analogy to the preparation described in Example 1 a, but in the absence of the active ingredient fipronil.
  • the washed polymer was washed with 100 ml each of acetonitrile and methanol in the same way as in Example 2B, the subsequent loading with active ingredient was carried out analogously to Example 3.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne l'utilisation de polymères d'acrylate moléculaire modifiés en présence d'au moins un pesticide pour la fabrication d'une formulation agrochimique à libération contrôlée de la substance active, des formulations comprenant ledit polymère d'acrylate moléculaire modifié en présence d'au moins un pesticide et au moins un pesticide, un procédé de fabrication desdites formulations, ainsi que l'utilisation desdites formulations pour la protection des plantes.
EP07712005A 2006-01-12 2007-01-05 Formulation agrochimique a base d'acrylate moleculaire modifie Withdrawn EP1976376A1 (fr)

Priority Applications (1)

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EP07712005A EP1976376A1 (fr) 2006-01-12 2007-01-05 Formulation agrochimique a base d'acrylate moleculaire modifie

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06100263 2006-01-12
EP07712005A EP1976376A1 (fr) 2006-01-12 2007-01-05 Formulation agrochimique a base d'acrylate moleculaire modifie
PCT/EP2007/050112 WO2007082802A1 (fr) 2006-01-12 2007-01-05 Formulation agrochimique a base d’acrylate moleculaire modifie

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EP1976376A1 true EP1976376A1 (fr) 2008-10-08

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EP (1) EP1976376A1 (fr)
JP (1) JP2009523152A (fr)
CN (1) CN101374411A (fr)
BR (1) BRPI0706626A2 (fr)
CA (1) CA2640305A1 (fr)
IL (1) IL192422A0 (fr)
WO (1) WO2007082802A1 (fr)

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EP2348834B1 (fr) * 2008-09-25 2018-04-18 Vive Crop Protection Inc. Procédés de production de nanoparticules de polymère et formulations d'ingrédients actifs
KR20130059349A (ko) * 2010-04-28 2013-06-05 신젠타 파티서페이션즈 아게 안정화된 농약 조성물
US9686979B2 (en) 2011-08-23 2017-06-27 Vive Crop Protection Inc. Pyrethroid formulations
CN102507820B (zh) * 2011-10-18 2013-10-16 山东农业大学 一种同时检测敌百虫和久效磷的方法
JP6062454B2 (ja) 2011-12-22 2017-01-18 ヴァイヴ クロップ プロテクション インコーポレイテッドＶｉｖｅ Ｃｒｏｐ Ｐｒｏｔｅｃｔｉｏｎ Ｉｎｃ． ストロビルリン配合物
WO2013186695A1 (fr) 2012-06-11 2013-12-19 Vive Crop Protection Inc. Formulations herbicides
EP2864417B1 (fr) * 2012-06-21 2019-01-09 Ligar Limited Partnership Polymère et son procédé d'utilisation
US9392786B2 (en) 2013-02-05 2016-07-19 Vive Crop Protection, Inc. Mectin and milbemycin polyelectrolyte nanoparticle formulations
CN104927862B (zh) * 2015-05-20 2017-02-22 合肥工业大学 一种用于测定杀菌剂福美双的上转换发光纳米探针及其制备方法和应用
EP3672411A4 (fr) 2017-08-25 2021-05-19 Vive Crop Protection Inc. Compositions pesticides à composants multiples appliquées au sol
CN113817100A (zh) * 2021-10-28 2021-12-21 昆明理工大学 一种三唑醇分子印迹聚合物微球的制备方法
CN115684308A (zh) * 2022-10-13 2023-02-03 桂林理工大学 双链dna辅助识别的咪鲜胺分子印迹传感器的制备方法
CN115791942A (zh) * 2022-10-13 2023-03-14 桂林理工大学 基于dna辅助识别的多菌灵分子印迹传感器的制备方法
CN118812763A (zh) * 2023-04-20 2024-10-22 中国石油化工股份有限公司 用于实时质谱分析的分子印迹搅拌磁子及其制备方法和应用
CN117964831B (zh) * 2024-03-29 2024-08-16 广州伽能生物科技有限公司 一种醉椒素温敏分子印迹聚合物的制备方法及应用

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CN101374411A (zh) 2009-02-25
CA2640305A1 (fr) 2007-07-26
BRPI0706626A2 (pt) 2011-04-05
JP2009523152A (ja) 2009-06-18
IL192422A0 (en) 2009-09-22
US20100227761A1 (en) 2010-09-09
WO2007082802A1 (fr) 2007-07-26

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