EP2819511A1 - Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkylamines - Google Patents

Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkylamines

Info

Publication number
EP2819511A1
EP2819511A1 EP13703620.8A EP13703620A EP2819511A1 EP 2819511 A1 EP2819511 A1 EP 2819511A1 EP 13703620 A EP13703620 A EP 13703620A EP 2819511 A1 EP2819511 A1 EP 2819511A1
Authority
EP
European Patent Office
Prior art keywords
formula
carbamate
polymer
composition according
pesticide
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Withdrawn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
EP13703620.8A
Other languages
German (de)
French (fr)
Inventor
Gerhard Schnabel
Roman Benedikt Raether
Mariano Ignacio ETCHEVERRY
Silke ZEYER
Gerd Krämer
Richard Roger Evans
Fabien Jean Brand
Peter Hänggi
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 EP13703620.8A priority Critical patent/EP2819511A1/en
Publication of EP2819511A1 publication Critical patent/EP2819511A1/en
Withdrawn legal-status Critical Current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
    • A01N25/30—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 characterised by the surfactants
    • 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
    • A01N25/02—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 liquids as carriers, diluents or solvents
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Definitions

  • Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkyla- mines are optionally alkoxylated reaction products of glycerol carbonate and alkyla- mines.
  • the present invention relates to a composition
  • a composition comprising a pesticide and an adjuvant selected from a carbamate of the formula (I), a carbamate of the formula (II), or a polymer, which is obtainable by polymerization of at least one alkylene oxide and a carbamate of the formula (I) and/or (II) as defined below.
  • the invention further relates to a method of preparing said compo- sition by bringing the adjuvant and the pesticide into contact; to a polymer, which is obtainable by the polymerization as defined below, and which consists of the compounds of the formula (III) or (IV) as defined below; to a method of preparing said polymer by first reacting a glycerol carbonate and an amine of the formula R-Nhb yielding the carbamate of the formula (I) and/or (II); followed by polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II); to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein said composition is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their
  • Object of the present invention was to overcome the problems of the state of the art.
  • the object was solved by a composition comprising a pesticide and an adjuvant selected from a carbamate of the formula (I), a carbamate of the formula (II), or a polymer, which is obtainable by polymerization of at least one alkylene oxide and a carbamate of the formula (I) and/or (II)
  • R is a saturated or unsaturated, acyclic or cyclic, aliphatic, araliphatic or aromatic residue.
  • the adjuvant may comprise at least one of the carbamate of the formula (I), the carbamate of the formula (II), or a polymer, e.g. one, two or three of said components.
  • the adjuvant may comprise a majority (e.g. at least 80 wt%) of the polymer and a minority (e.g. up to 20 wt%) of the carbamates of the formula (I) and (II).
  • the adjuvant is a carbamate of the formula (I) or a carbamate of the formula (II), or mixtures thereof.
  • the adjuvant is a polymer, which is obtainable by polymerization of at least one alkylene oxide and a carbamate of the formula (I) and/or (II).
  • the residue R is usually a C4-C32 alkyl group, which may optionally contain at least one double and/or triple Carbon-Carbon bond.
  • R contains no, one or two double bonds.
  • the double bonds may be in E or Z configuration.
  • the residue R may be linear, branched, or cyclic alkyl group.
  • R may contain functional groups connected to the alkyl group, such as halogen.
  • R is a hydrocarbon, which is free of functional groups.
  • R is a linear or branched, saturated or unsaturated hydrocarbon.
  • R is a linear or branched C6-C24 alkyl group, in particular a linear or branched C6-C18 hydrocarbon.
  • R are n-octyl, iso-nonyl, n-decyl, 2-propylheptyl, 2-ethylhexyl, n-dodecyl, branched tridecyl, tetradecyl, n-hexadecyl, n-octadecyl, or oleyl.
  • the residue R may be an alkyletheramine, such as R'-O-Chb-Chb-NI-b or R'-O- CH2-CH2-CH2-NH2, wherein R' is C4-C32 alkyl group, which may optionally contain at least one double and/or triple Carbon-Carbon bond.
  • R' contains no, one or two double bonds.
  • the double bonds may be in E or Z configuration.
  • the residue R' may be linear, branched, or cyclic alkyl group.
  • R' may contain functional groups connected to the alkyl group, such as halogen.
  • R' is a hydrocarbon, which is free of functional groups.
  • R' is a linear or branched, saturated or unsaturated hydrocarbon.
  • R' is a linear or branched C6-C24 alkyl group, in particular a linear or branched C6-C18 hydrocarbon.
  • R' are n- octyl, iso-nonyl, n-decyl, 2-propylheptyl, 2-ethylhexyl, n-dodecyl, branched tridecyl, tetradecyl, n-hexadecyl, n-octadecyl, or oleyl.
  • Suitable alkylene oxides are C2-C10 alkylene oxides, such as ethylene oxide, propylene oxide, 1 - butene oxide, 2-butene oxide, isobutene oxide, 1 -pentene oxide, styrene oxide, 1 -hexene oxide, 1 -heptene oxide, 1 -octene.
  • Preferred alkylene oxides comprise C2-C5 alkylene oxides, in particular C2-, C3-, and/or C4- alkylene oxide.
  • the alkylene oxide contains ethylene oxide and/or propylene oxide.
  • the alkylene oxide is a mixture of ethylene oxide and butylene oxide.
  • the polymer may comprise from 1 to 100, preferably from 2 to 30, and in particular from 3 to 20 equivalents of the alkylene oxide (e.g. ethylene oxide and/or propylene oxide) per equivalent of the carbamate.
  • the polymer may comprise from 1 to 50, preferably from 2 to 40, and in particular from 3 to 20 equivalents of ethylene oxide and optionally 1 to 30, preferably from 1 to 10, and in particular from 1 to 5 equivalents of propylene oxide per equivalent of the carbamate.
  • the carbamate of the formula (I) and/or (II) is obtainable (preferably it is obtained) by reacting glycerol carbonate and an amine of the formula R-NH2, where R is as defined above.
  • the carbamate may be present as a compound of the formula (I), of the formula (II), or as a mixture of both.
  • the carbamate comprises a mixture of a compound of the formula (I) and of the formula (II).
  • the mixture of the carbamates may comprise 25 to 75 wt% (preferably 35 to 65 wt%) of each compound of the formula (I) and of the formula (II), wherein they sum up to 100 wt%.
  • the polymer is obtainable (preferably it is obtained) by polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II).
  • the polymers can be prepared by
  • the polymerization takes place as base-initiated polyaddition and/or a (further) base is used during the polymerization.
  • the polyaddition and/or polymerization can also be carried out without using an additional base.
  • Bases suiable for polymerization processes are known to the person skilled in the art, for example alkali metals, alkali metal hydrides, alkali metal hydroxides, alkali metal al- coholates or alkaline earth metals, alkaline earth metal hydrides, alkaline earth metal hydroxides or alkaline earth metal alcoholates, and also tertiary and heteroaromatic amines can be used for this purpose.
  • bases are KO(t-Bu) (where t-Bu is the radical tertiary-butyl), KOEt, KOH or NaOH, and mixtures thereof.
  • the base is preferably used in amounts of from 0.05% by weight to 20% by weight, the base preferably being used in an amount of from 0.1 to 10% by weight, in particular from 0.1 to 1 % by weight (in each case based on the amount of polymer (product)).
  • the present invention further relates to a method of preparing the polymer by first reacting a glycerol carbonate and an amine of the formula R-NH2 yielding the carbamate of the formula (I) and/or (II); followed by polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II).
  • the polymer may be a homopolymer, a random copolymer, a block copolymer, or a gradient copolymer.
  • the polymer is a homopolymer (e.g. based on ethylene oxide) or a block copolymer (e.g. based on ethylene oxide and propylene oxide).
  • the polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II) may result in a poly(alkyleneglycol) polymer chain, which is terminated by a hydroxy group. Said hydroxy group by further be modified to arrive at other terminal groups.
  • Suitable terminal groups of the polymerized alkylene oxide are -OR 1 , where
  • R 1 is an H, d-C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, -S0 3 R a , -P(0)OR b OR c , -CH 2 C0 2 R d , or - C(0)R e ,
  • R a and R d independently of one another are an H, inorganic or organic cations
  • R b and R c independently of one another are an H, inorganic or organic cations, Ci-C6-alkyl, C 2 -C6-alkenyl or C 2 -C6-alkynyl,
  • R e is Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 2 -C 22 -alkynyl, C 6 -C 22 -aryl, C 7 -C 22 -alkylaryl, or or -OR d .
  • R a and R d are independently of one another H, or inorganic or organic cations, which may be singly or multiply positively charged. Examples of inorganic cations are cations of ammonium, Na + , K + , Mg 2+ , Ca 2+ , or Zn 2+ .
  • R a and R d independently of one another are H or inorganic cations. If an inorganic or organic cation is present, then the associated anionic group would be formed by the corresponding functional group (e.g., -SO3 " , - ⁇ (0) ⁇ " , or -CH 2 C0 2 " ) on R 6 .
  • R b and R° are preferably, independently of one another, H, inorganic or organic cations. Suitable inorganic or organic cations are those specified under R a .
  • R 1 is preferably an H or Ci-C6-alkyl, more preferably an H or methyl, especially H.
  • the polymer comprises the compound of the formula (III) and/or (IV)
  • R is a saturated or unsaturated, acyclic or cyclic, aliphatic, araliphatic or aromatic residue (preferably a saturated or unsaturated C4-C32 alkyl group),
  • R 1 is an H, d-C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, -S0 3 R a , -P(0)OR b OR c , -CH 2 C0 2 R d , or -C(0)R e ,
  • R a and R d independently of one another are an H, inorganic or organic cations
  • R b and R c independently of one another are an H, inorganic or organic cations, Ci-C6-alkyl, C 2 -C6-alkenyl or C 2 -C6-alkynyl,
  • R e is Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 2 -C 22 -alkynyl, C 6 -C 22 -aryl or C 7 -C 22 -alkylaryl,
  • R 2 is ethylene, propylene, butylene (1 -, 2-, or iso-) or a mixture thereof,
  • n, m have independently a value of from 0 to 20, and the sum of n and m is from 1 to 30.
  • R 2 is most preferably ethylene, or ethylene and propylene.
  • n, m have independently a value of from 0 to 30, and the sum of n and m is from 1 to 50.
  • n, m have independently a value of from 0 to 20, and the sum of n and m is from 1 to 25.
  • the values of n and m are normally average values as they mostly arise upon the alkoxylation with alkoxides. Therefore, n and m can not only be integers, but also all values between the integers.
  • the polymer may be present as a compound of the formula (III), of the formula (IV), or as a mixture of both.
  • the polymer comprises a mixture of a compound of the formula (III) and of the formula (IV).
  • the mixture of the polymers may comprise 25 to 75 wt% (preferably 35 to 65 wt%) of each compound of the formula (III) and of the formula (IV), wherein they sum up to 100 wt%.
  • the compounds of the formula (III) and/or (IV) are obtainable by polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II).
  • the polymer comprises at least 60 wt%, preferably at least 75 wt%, and in particular at least 90 wt% of the compound of the formula (III) and/or (IV).
  • the present invention further relates to a polymer, which is obtainable by the polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II), wherein the polymer consists of the compounds of the formula (III) or (IV).
  • the composition may contain at least 0,1 wt%, preferably at least 1 wt% of the adjuvant (e.g. the polymer).
  • the composition according to the invention may be present as an agrochemical composition type and comprises from 1 to 80% by weight of the polymer, preferably from 2 to 50% by weight and in particular from 5 to 30% by weight.
  • pesticide refers to at least one active substance selected from the group of the fungicides, insecticides, nematicides, herbicides, safeners, molluscicides, rodenticides and/or growth regulators.
  • Preferred pesticides are fungicides, insecticides, herbicides and growth regulators.
  • Especially preferred pesticides are herbicides and growth regulators.
  • Mixtures of pesticides from two or more of the abovementioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London.
  • the pesticides may also comprise salts, esters, optical isomers or tautomers.
  • Suitable pesticides are (groups A) to M) are fungicides): A) Respiration inhibitors
  • Inhibitors of complex III at Q 0 site e.g. strobilurins: azoxystrobin, coumethoxystrobin,
  • coumoxystrobin dimoxystrobin, enestroburin, fenaminstrobin, fenoxy- strobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5- dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-di- chlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl- acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
  • - inhibitors of complex II e. g. carboxamides: benodanil, bixafen, boscalid, carboxin, fen- furam, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'- trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide, N-(2- (1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide, N-[9- (dichloromethylene)-l ,2,3,4-tetrahydro-1 ,4-methanonaphthalen-5-yl]-3-(
  • respiration inhibitors e.g. complex I, uncouplers: diflumetorim, (5,8-difluoroquinazolin- 4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ -amine; nitrophenyl deri- vates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthi- ofam;
  • complex I uncouplers
  • DMI fungicides triazoles: azaconazole, bitertanol, bromucona- zole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbu- conazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triti- conazole, uniconazole,
  • Delta14-reductase inhibitors aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
  • phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
  • hymexazole hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p- tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
  • tubulin inhibitors such as benzimidazoles, thiophanates: benomyl, carbendazim, fuber- idazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methyl- piperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine
  • cell division inhibitors diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
  • - methionine synthesis inhibitors anilino-pyrimidines: cyprodinil, mepanipyrim, pyrimethanil; - protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
  • MAP / histidine kinase inhibitors fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
  • - Phospholipid biosynthesis inhibitors edifenphos, iprobenfos, pyrazophos, isoprothiolane;
  • lipid peroxidation dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
  • phospholipid biosynthesis and cell wall deposition dimethomorph, flumorph, mandipropa- mid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1 -(1 -(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
  • fatty acid amide hydrolase inhibitors 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]- 2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1 H-pyrazol-1 -yl]ethanone;
  • organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles: anilazine, chloro- thalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachloroben- zene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N- ethyl-4-methyl-benzenesulfonamide;
  • organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles: anilazine, chloro- thalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachloroben- zene, pentachlorphenole and its salts, phthalide, toly
  • guanidine dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyl- 1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
  • glucan synthesis validamycin, polyoxin B; melanin synthesis inhibitors: pyroqui- lon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
  • Antifungal biocontrol agents plant bioactivators: Ampelomyces quisqualis (e.g. AQ 10 ® from Intrachem Bio GmbH & Co. KG, Germany), Aspergillus flavus (e.g. AFLAGUARD ® from Syngenta, CH), Aureobasidium pullulans (e.g. BOTECTOR ® from bio-ferm GmbH, Germany), Bacillus pumilus (e.g. NRRL Accession No.
  • Ampelomyces quisqualis e.g. AQ 10 ® from Intrachem Bio GmbH & Co. KG, Germany
  • Aspergillus flavus e.g. AFLAGUARD ® from Syngenta, CH
  • Aureobasidium pullulans e.g. BOTECTOR ® from bio-ferm GmbH, Germany
  • Bacillus pumilus e.g. NRRL Accession No.
  • Bacillus subtilis e.g. isolate NRRL-Nr. B-21661 in RHAPSODY ® , SERENADE ® MAX and SERENADE ® ASO from AgraQuest Inc., USA
  • Bacillus subtilis var. amyloliquefaciens FZB24 e.g. TAEGRO ® from Novozyme Biologicals, Inc., USA
  • Candida oleophila I-82 e.g. ASPIRE ® from Ecogen Inc., USA
  • Candida saitoana e.g.
  • BIO- CURE ® in mixture with lysozyme
  • BIOCOAT ® from Micro Flo Company, USA (BASF SE) and Arysta
  • Chitosan e.g. ARMOUR-ZEN from BotriZen Ltd., NZ
  • Clonostachys rosea f. catenulata also named Gliocladium catenulatum (e.g. isolate J 1446: PRESTOP ® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS ® from Prophyta, Germany), Cryphonectria parasitica (e.g. Endothia parasitica from CNICM, France), Cryptococcus albi- dus (e.g.
  • YIELD PLUS ® from Anchor Bio-Technologies, South Africa
  • Fusarium oxysporum e.g. BIOFOX ® from S.I.A.P.A., Italy, FUSACLEAN ® from Natural Plant Protection, France
  • Metschnikowia fructicola e.g. SHEMER ® from Agrogreen, Israel
  • Microdochium dimerum e.g. ANTIBOT ® from Agrauxine, France
  • Phlebiopsis gigantea e.g. ROTSOP ® from
  • Pseudozyma flocculosa e.g. SPORODEX ® from Plant Products Co. Ltd., Canada
  • Pythium oligandrum DV74 e.g. POLYVERSUM ® from Remeslo SSRO, Bio- preparaty, Czech Rep.
  • Reynoutria sachlinensis e.g. REGALIA ® from Marrone Biolnnova- tions, USA
  • Talaromyces flavus V1 17b e.g. PROTUS ® from Prophyta, Germany
  • Tricho- derma asperellum SKT-1 e.g. ECO-HOPE ® from Kumiai Chemical Industry Co., Ltd., Japan
  • Atroviride LC52 e.g. SENTINEL ® from Agrimm Technologies Ltd, NZ
  • T. harzianum T-22 e.g. PLANTSHIELD ® der Firma BioWorks Inc., USA
  • T. harzianum JH 35 e.g. ROOT PRO ® from Mycontrol Ltd., Israel
  • T. harzianum T-39 e.g. TRICHODEX ® and TRICHO-
  • T. harzianum and T. viride e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ
  • T. harzianum ICC012 and T. viride ICC080 e.g. REMEDIER ® WP from Isagro Ricerca, Italy
  • T. polysporum and T. harzi- anum e.g. BINAB ® from BINAB Bio-Innovation AB, Sweden
  • T. stromaticum e.g. TRICO- VAB ® from C.E.P.L.A.C., Brazil
  • T. virens GL-21 e.g.
  • T. viride e.g. TRIECO ® from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE ® F from T. Stanes & Co. Ltd., Indien
  • T. viride TV1 e.g. T. viride TV1 from Agribiotec srl, Italy
  • Ulo- cladium oudemansii HRU3 e.g. BOTRY-ZEN ® from Botry-Zen Ltd, NZ
  • BOTRY-ZEN from Botry-Zen Ltd, NZ
  • abscisic acid amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, di- methipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadi- one (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phos- phorotrithioate, 2,3,
  • acetochlor alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefe- nacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
  • EPTC esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thio- bencarb, triallate;
  • acifluorfen acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, ox- yfluorfen;
  • - phenoxy acetic acids clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlor- prop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
  • - pyridines aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;
  • - sulfonyl ureas amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfu- ron, triflusulfuron, trito
  • ureas chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
  • acetolactate synthase inhibitors bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrim- isulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
  • organo(thio)phosphates acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyri- fos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethi- on, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phentho- ate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
  • - carbamates alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosul- fan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodi- carb, triazamate;
  • - pyrethroids 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, profluthrin, dimefluthrin;
  • - insect growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cy- ramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juve- noids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
  • - nicotinic receptor agonists/antagonists compounds clothianidin, dinotefuran, flupyradifurone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1 -2-chloro-thiazol-5- ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane;
  • GABA antagonist compounds endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyri- prole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1 H-pyrazole-3-carbothioic acid amide;
  • - macrocyclic lactone insecticides abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram;
  • acaricides fenazaquin, pyridaben, tebu- fenpyrad, tolfenpyrad, flufenerim;
  • oxidative phosphorylation inhibitors cyhexatin, diafenthiuron, fenbutatin oxide, propargite;
  • cryomazine cryomazine
  • safeners are benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, di- cyclonon, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1 -oxa-4- azaspiro[4.5]decane (CAS 71526-07-3) and 2,2,5-trimethyl-3-(dichloroacetyl)-1 ,3-oxazolidine (CAS 52836-31 -4).
  • Preferred pesticides comprise at least one pesticide with at least one H-acidic group (such as carboxylic acid group, phosphonic acid group, phosphinic acid group) or the anionic salts thereof (e.g., mono, di or tri salts). These anionic salts of the pesticides with an H-acidic group are also suitable as anionic pesticides in group A-. Preferred pesticides with an H-acidic group are herbicides with an H-acidic group.
  • H-acidic group such as carboxylic acid group, phosphonic acid group, phosphinic acid group
  • anionic salts thereof e.g., mono, di or tri salts.
  • herbicides with an H-acidic group are amino acid analogs (such as glyphosate or glufosinate) or imidazolinones (such as imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr).
  • pesticides with an H-acidic group are glyphosate and glufosinate.
  • pesticides with an H-acidic group are imidazolinones.
  • the pesticide comprises a pesticide with an H-acidic group and one further pesticide.
  • the pesticide comprises mixtures of at least two pesti- cides with an H-acidic group, and optionally further pesticides (such as at least one fungicide, herbicide, insecticide, and/or safener, with fungicides and/or herbicides being preferred).
  • the pesticide comprises glyphosate (for example as the free acid, sodium salt, sesquisodium salt, potassium salt, dipotassium salt, ammonium salt, diam- monium salt, dimethylammonium salt, trimesium salt or isopropylamine sale) or glufosinate (for example as the ammonium salt).
  • the pesticide comprises glyphosate (for example as the potassium salt, ammonium salt or isopropylamine salt).
  • the pesticide comprises glyphosate or glufosinate, and additionally a further herbicide.
  • the pesticide comprises glyphosate or glufosinate, and additionally a further pesticide (such as at least one fungicide, herbicide, insecticide and/or safener, with fungicides and/or herbicides being preferred).
  • the pesticide comprises glyphosate and at least one further herbicide selected from the following list:
  • composition according to the invention may also be present in form of an agrochemical compositions comprising the pesticide, the adjuvant( e.g. the polymer), and optionally an auxiliary.
  • An agrochemical composition comprises a pesticidally effective amount of a pesticide.
  • effective amount denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful pests on or around cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific pesti- cide used.
  • Suitable, customary types of agrochemical compositions are e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Tech- nical Monograph No. 2, 6 th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, further adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
  • suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, further adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, al- kylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalene, al-
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.
  • Suitable further adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the pesticide on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are:
  • 10-60 wt% of the pesticide and 5-15 wt% wetting agent e.g. alcohol alkoxylates
  • a water-soluble solvent e.g. alcohols
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e.g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20-40 wt% water-insoluble organic solvent e.g. aromatic hydrocarbon
  • wt% of the pesticide are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • 0,1 -2 wt% thickener e.g. xanthan gum
  • 50-80 wt% of the pesticide are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • 50-80 wt% of the pesticide are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
  • 1 -5 wt% dispersants e.g. sodium lignosulfonate
  • 1 -3 wt% wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • wt% of the pesticide are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -5 wt% thickener e.g. carboxymethylcellulose
  • 5-20 wt% of the pesticide are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethyl- amide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
  • organic solvent blend e.g. fatty acid dimethyl- amide and cyclohexanone
  • surfactant blend e.g. alkohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of the pesticide, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of the pesticide, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g.
  • diphenylmethene-4,4'-diisocyanatae are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol).
  • a protective colloid e.g. polyvinyl alcohol.
  • the addition of a polyamine results in the formation of a polyurea microcapsules.
  • the monomers amount to 1 -10 wt%.
  • the wt% relate to the total CS composition.
  • Dustable powders (DP, DS)
  • 1 -10 wt% of the pesticide are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
  • 0.5-30 wt% of the pesticide is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
  • solid carrier e.g. silicate
  • compositions types i) to xi) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1 -1 wt% anti-foaming agents, and 0,1 -1 wt% col- orants.
  • Preferred composition type is a water-soluble concentrates (SL).
  • the composition according to the invention comprises at least 10 wt% of the pesticide (e.g. glyphosate), at least 1 wt% of the adjuvant, and up to 100 wt% water.
  • the composition according to the invention comprises at least 30 wt% of the pes- ticide (e.g. glyphosate), at least 5 wt% of the adjuvant, and up to 100 wt% water.
  • the composition according to the invention comprises 10 to 70 wt% of the pesticide (e.g. glyphosate), 3 to 60 wt% of the adjuvant (e.g. the polymer), and up to 100 wt% water.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance (i.e. pesticide).
  • active substance i.e. pesticide
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.
  • Application can be carried out before or during sowing.
  • Methods for applying or treating the pesticide and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • the pesticide or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant prop- agation material (preferably seed) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • concentration of the adjuvant (e.g. the polymer) in the ready-to-use preparation e.g. the tank mix
  • the concentration of the adjuvant e.g. the polymer
  • the ready-to-use preparation e.g. the tank mix
  • the concentration of water in the ready-to-use preparation is in most cases at least 60 wt%, preferably at least 75 wt%, and in particular at least 90 wt%.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired applica- tion concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • composition according to the in- vention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components, e. g. components comprising the pesticide and/or the adjuvant can be applied jointly (e.g. after tank mix) or consecutively.
  • the present invention furthermore relates to a method of preparing the composition according to the invention by bringing the adjuvant and the pesticide into contact, e.g. by mixing. The contacting may be done between 5 to 95 °C.
  • a tankmix or a agrochemical composition may be prepared.
  • the present invention furthermore relates to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the composition according to the invention or the adjuvant is allowed to act on the respective pests, their environment or the crop plants to be protected from the re- spective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
  • the application rate of the adjuvant is in most cases in the range of from 10 to 3000 g/ha, pref- erably from 10 to 1000 g/ha, especially preferably from 80 to 750 g/ha and specifically from 100 to 400 g/ha.
  • the application rate is at least 1000 g/ha adjuvant (e.g. polymer), preferably at least 1500 g/ha.
  • suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for ex- ample cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tangerines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avocados, cinnamon or camphor; energy
  • crop plants also includes those plants which have been modified by breeding, mutagenesis or recombinant methods, including the biotechnological agricultural products which are on the market or in the process of being developed.
  • Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by hybridizing, mutations or natural recombination (i.e. recombination of the genetic material).
  • one or more genes will, as a rule, be integrated into the genetic material of the plant in order to improve the plant's properties.
  • Such recombinant modifications also comprise posttranslational modifications of proteins, oligo- or polypeptides, for example by means of gly- cosylation or binding polymers such as, for example, prenylated, acetylated or farnesylated residues or PEG residues.
  • plants which, as the result of plant-breeding and recombinant measures, have acquired a tolerance for certain classes of herbicides, such as hy- droxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors such as, for example, sulfonylureas (EP-A 257 993, US 5,013,659) or imidazolinones (for ex- ample US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526,
  • HPPD hy- droxyphenylpyruvate dioxygenase
  • ALS acetolactate synthase
  • sulfonylureas EP-A 257 993, US 5,013,659
  • imidazolinones for ex- ample US 6,222,100, WO 01/82685, WO 00/263
  • EPSPS enolpyruvylshikimate 3-phosphate synthase
  • EPSPS enolpyruvylshikimate 3-phosphate synthase
  • GS glutamine synthetase
  • glufosinate see, for example, EP-A 242 236, EP-A 242 246) or oxynil herbicides (see, for example, US 5,559,024).
  • toxins for example those from the bacterial strain Bacillus.
  • Toxins which are produced by such genetically modified plants comprise, for example, insecticidal proteins of Bacillus spp., in particular from B.
  • thuringiensis such as the endotoxins CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 , Cry9c, Cry34Ab1 or Cry35Ab1 ; or vegetable insecticidal proteins (VIPs), for example VIP1 , VIP2, VIP3, or VIP3A; insecticidal proteins from nematode-colonizing bacteria, for example Photorhabdus spp.
  • VIPs vegetable insecticidal proteins
  • toxins from animal organisms for example wasp, spider or scorpion toxins
  • fungal toxins for example from Streptomycetes
  • plant lectins for example from pea or barley
  • agglutinins proteinase inhibitors, for example trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins RIPs
  • steroid- metabolizing enzymes for example 3-hydroxysteroid oxidase, ecdysteroid I DP glycosyl transferase, cholesterol oxidase, ecdysone inhibitors or HMG CoA-reductase
  • ion channel blockers for example inhibitors of sodium or calcium channels
  • juvenile hormone esterase for the diuretic hormone (helicokinin receptors)
  • toxins can also be produced, in the plants, in the form of pretoxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are distinguished by a novel combination of different protein domains (see, for example, WO 2002/015701 ).
  • Further examples of such toxins or genetically modified plants which produce these toxins are disclosed in EP-A 374 753, WO 93/07278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 and WO 03/52073.
  • the methods for generating these genetically modified plants are known to the skilled worker and explained, for example, in the abovementioned publications.
  • a large number of the abovementioned toxins impart to the plants which produce them a tolerance for pests from all taxonomic classes of the arthropods, in particular beetles (Coeleropta), dipterans (Diptera) and lepidopterans (Lepidoptera) and nematodes (Nematoda).
  • plants which, with the aid of recombinant measures, produce one or more proteins which bring about an increased resistance to, or ability to withstand, bacterial, viral or fungal pathogens such as, for example, so-called pathogenesis-related proteins (PR proteins, see EP-A 0 392 225), resistance proteins (for example potato varieties which produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum) or T4 lysozyme (for example potato varieties which, as the result of the production of this protein, are resistant to bacteria such as Erwinia amylvora).
  • PR proteins pathogenesis-related proteins
  • resistance proteins for example potato varieties which produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum
  • T4 lysozyme for example potato varieties which, as the result of the production of this protein, are resistant to bacteria such as Erwinia amylvora.
  • yield potential for example biomass, grain yield, starch content, oil content or protein content
  • tolerance for drought, salt or other limiting environmental factors for example by increasing the yield potential (for example biomass, grain yield, starch content, oil content or protein content), the tolerance for drought, salt or other limiting environmental factors, or the resistance to pests and fungal, bacterial and viral pathogens.
  • plants whose constituents, in particular for improving human or animal nutrition, have been modified with the aid of recombinant methods, for example by oil plants producing health-promoting long-chain omega-3-fatty acids or monounsaturated omega-9-fatty acids (for example Nexera ® oilseed rape, DOW Agro Sciences, Canada).
  • the present invention also relates to seed (such as seeds or other plant propagation materials) comprising the composition according to the invention.
  • Plant propagation materials can be treated preventively with the composition according to the invention at the point of or even be- fore sowing or at the point of or even before transplanting.
  • seed such as seeds or other plant propagation materials
  • Plant propagation materials can be treated preventively with the composition according to the invention at the point of or even be- fore sowing or at the point of or even before transplanting.
  • For the treatment of seed one will generally use water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF).
  • LS water-soluble concentrates
  • FS suspensions
  • dusts DS
  • WS, SS water-dispersible and water-soluble powders
  • ES emulsions
  • EC emulsifiable concentrate
  • the composition in question can be diluted 2- to 10-fold, so that from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, of active substance is present in the compositions used for the seed dressing.
  • the application may be effected before or during sowing.
  • the treatment of plant propagation material, in particular the treatment of seed is known to the skilled worker and carried out by dusting, coating, pelleting, dipping or soaking the plant propagation material, the treatment preferably being carried out by pelleting, coating and dusting or by in-furrow treatment so that, for example, untimely early germination of the seed is prevented. It is preferred to use suspensions for the treatment of seed.
  • compositions comprise from 1 to 800 g/l of active substance, from 1 to 200 g/l of surfactants, from 0 to 200 g/l of antifreeze agents, from 0 to 400 g/l of binders, from 0 to 200 g/l of colorants and solvent, preferably water.
  • the advantages of the invention are high stability of the formulation and of the spray mixture, little wind-caused drift in the case of spray applications, good adhesion of the formulation on the surface of the treated plants, increased solubility of the pesticides in the formulation, increased permeation of the pesticides into the plant, or more rapid and enhanced activity.
  • An important advantage is the low toxicity of the adjuvant.
  • Another advantage is the low harmful effect against crop plants, i.e. low phytotoxic effects.
  • Another advantage is that no phase separation and no salt precipitation occurs in compositions with a high salt content, such as over 400 g/l glyphosate.
  • Octylamin was diluted in 200ml_ ethyl acetate.
  • the solution of 75.4g glycerine carbonate in 100ml_ ethyl acetate was added and proceeded as in Example 1 .
  • a white solid (105g, 71 % yield, mp 60-63°C) was obtainedd and the structure was further confirmed with IR and 1 H NMR.
  • aqueous formulation (SL type) was prepared by dissolving 52.3 wt% potassium glyphosate in water.
  • As adjuvant the ethoxylated (10 equivalents) carbamate from Example 1 was added and dissolved in the resulting SL formulation.
  • This SL formulation was diluted with water to prepare a tank mix, which contained 0,8 g/l of the adjuvant, 0,75 g/l of the potassium glyphosate (or as alternative tank mix 0,37 g/l).
  • This tankmix may be applied at 375 l/ha (corresponding to 300 g/ha adjuvant and 280 g/ha glyphosate (or 140 g/ha as alternative).
  • Genamine® T1510 from Clariant was used, which is a tallow fatty amine eth- oxylate comprising 15 mole ethylene oxide per mol tallow fatty amine.
  • soybean soybean (cultivar Delta P.), rapeseed) was sown or potted in loamy sandy soil to a depth of 1 -2 cm.
  • the spray mixtures were applied to the plants in a spraying cabin.
  • the tank mix prepared in Example 7 was applied at a application rate of 375 l/ha (140 or 280 g of glyphosate/ha and 300 g of adjuvant/ha).
  • the temperatures in the experimental period which lasted for 3 to 4 weeks, were between 18-35°C.
  • the experimental plants re- ceived optimum watering, with nutrients being supplied via the water used for watering.
  • the herbicidal activity was evaluated by awarding scores to the treated plants in comparison to the untreated control plants (Table 1 and 2).
  • the evaluation scale ranges from 0% to 100% activity.
  • 100% activity means the complete death at least of those parts of the plant that are above ground.
  • 0% activity means that there were no differences between treated and untreated plants.
  • the results demonstrated the increased activity of the active substance as a result of addition of the adjuvant.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to a composition comprising a pesticide and an adjuvant selected from a carbamate of the formula (I), a carbamate of the formula (II), or a polymer, which is obtainable by polymerization of at least one alkylene oxide and a carbamate of the formula (I) and/or (II) as defined below. The invention further relates to a method of preparing said composition by bringing the adjuvant and the pesticide into contact; to a polymer, which is obtainable by the polymerization as defined below, and which consists of the compounds of the formula (III) or (IV) as defined below; to a method of preparing said polymer by first reacting a glycerol carbonate and an amine of the formula R-NH2 yielding the carbamate of the formula (I) and/or (II); followed by polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II); to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein said composition is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment; and to seed containing said composition.

Description

Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkyla- mines
Description
The present invention relates to a composition comprising a pesticide and an adjuvant selected from a carbamate of the formula (I), a carbamate of the formula (II), or a polymer, which is obtainable by polymerization of at least one alkylene oxide and a carbamate of the formula (I) and/or (II) as defined below. The invention further relates to a method of preparing said compo- sition by bringing the adjuvant and the pesticide into contact; to a polymer, which is obtainable by the polymerization as defined below, and which consists of the compounds of the formula (III) or (IV) as defined below; to a method of preparing said polymer by first reacting a glycerol carbonate and an amine of the formula R-Nhb yielding the carbamate of the formula (I) and/or (II); followed by polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II); to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein said composition is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment; and to seed containing said composition. The preferred em- bodiments of the invention mentioned herein below have to be understood as being preferred either independently from each other or in combination with one another.
Polymers based on alkylene oxide, glycerol carbonate and an amine are known from
WO2012/1 13617.
Object of the present invention was to overcome the problems of the state of the art. The object was solved by a composition comprising a pesticide and an adjuvant selected from a carbamate of the formula (I), a carbamate of the formula (II), or a polymer, which is obtainable by polymerization of at least one alkylene oxide and a carbamate of the formula (I) and/or (II)
where R is a saturated or unsaturated, acyclic or cyclic, aliphatic, araliphatic or aromatic residue.
The adjuvant may comprise at least one of the carbamate of the formula (I), the carbamate of the formula (II), or a polymer, e.g. one, two or three of said components. For example, the adjuvant may comprise a majority (e.g. at least 80 wt%) of the polymer and a minority (e.g. up to 20 wt%) of the carbamates of the formula (I) and (II). In a preferred form, the adjuvant is a carbamate of the formula (I) or a carbamate of the formula (II), or mixtures thereof.
In more preferred form, the adjuvant is a polymer, which is obtainable by polymerization of at least one alkylene oxide and a carbamate of the formula (I) and/or (II).
The residue R is usually a C4-C32 alkyl group, which may optionally contain at least one double and/or triple Carbon-Carbon bond. Preferably, R contains no, one or two double bonds. The double bonds may be in E or Z configuration. The residue R may be linear, branched, or cyclic alkyl group. R may contain functional groups connected to the alkyl group, such as halogen. Preferably, R is a hydrocarbon, which is free of functional groups. Preferably, R is a linear or branched, saturated or unsaturated hydrocarbon.
More preferably, R is a linear or branched C6-C24 alkyl group, in particular a linear or branched C6-C18 hydrocarbon. Examples for R are n-octyl, iso-nonyl, n-decyl, 2-propylheptyl, 2-ethylhexyl, n-dodecyl, branched tridecyl, tetradecyl, n-hexadecyl, n-octadecyl, or oleyl.
In another form, the residue R may be an alkyletheramine, such as R'-O-Chb-Chb-NI-b or R'-O- CH2-CH2-CH2-NH2, wherein R' is C4-C32 alkyl group, which may optionally contain at least one double and/or triple Carbon-Carbon bond. Preferably, R' contains no, one or two double bonds. The double bonds may be in E or Z configuration. The residue R' may be linear, branched, or cyclic alkyl group. R' may contain functional groups connected to the alkyl group, such as halogen. Preferably, R' is a hydrocarbon, which is free of functional groups. Preferably, R' is a linear or branched, saturated or unsaturated hydrocarbon. More preferably, R' is a linear or branched C6-C24 alkyl group, in particular a linear or branched C6-C18 hydrocarbon. Examples for R' are n- octyl, iso-nonyl, n-decyl, 2-propylheptyl, 2-ethylhexyl, n-dodecyl, branched tridecyl, tetradecyl, n-hexadecyl, n-octadecyl, or oleyl.
Suitable alkylene oxides are C2-C10 alkylene oxides, such as ethylene oxide, propylene oxide, 1 - butene oxide, 2-butene oxide, isobutene oxide, 1 -pentene oxide, styrene oxide, 1 -hexene oxide, 1 -heptene oxide, 1 -octene. Preferred alkylene oxides comprise C2-C5 alkylene oxides, in particular C2-, C3-, and/or C4- alkylene oxide. In one particular form, the alkylene oxide contains ethylene oxide and/or propylene oxide. In another particular form, the alkylene oxide is a mixture of ethylene oxide and butylene oxide.
The polymer may comprise from 1 to 100, preferably from 2 to 30, and in particular from 3 to 20 equivalents of the alkylene oxide (e.g. ethylene oxide and/or propylene oxide) per equivalent of the carbamate. In another form, the polymer may comprise from 1 to 50, preferably from 2 to 40, and in particular from 3 to 20 equivalents of ethylene oxide and optionally 1 to 30, preferably from 1 to 10, and in particular from 1 to 5 equivalents of propylene oxide per equivalent of the carbamate. The carbamate of the formula (I) and/or (II) is obtainable (preferably it is obtained) by reacting glycerol carbonate and an amine of the formula R-NH2, where R is as defined above. Such a reaction is known from Rousseau, Tetrahedron 2009, 65, 8571 -8581. The carbamate may be present as a compound of the formula (I), of the formula (II), or as a mixture of both. Preferably, the carbamate comprises a mixture of a compound of the formula (I) and of the formula (II). The mixture of the carbamates may comprise 25 to 75 wt% (preferably 35 to 65 wt%) of each compound of the formula (I) and of the formula (II), wherein they sum up to 100 wt%.
The polymer is obtainable (preferably it is obtained) by polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II). The polymers can be prepared by
polymerization processes known to the person skilled in the art. Preferably, the polymerization takes place as base-initiated polyaddition and/or a (further) base is used during the polymerization. However, the polyaddition and/or polymerization can also be carried out without using an additional base. Bases suiable for polymerization processes are known to the person skilled in the art, for example alkali metals, alkali metal hydrides, alkali metal hydroxides, alkali metal al- coholates or alkaline earth metals, alkaline earth metal hydrides, alkaline earth metal hydroxides or alkaline earth metal alcoholates, and also tertiary and heteroaromatic amines can be used for this purpose. Particularly preferred bases are KO(t-Bu) (where t-Bu is the radical tertiary-butyl), KOEt, KOH or NaOH, and mixtures thereof. The base is preferably used in amounts of from 0.05% by weight to 20% by weight, the base preferably being used in an amount of from 0.1 to 10% by weight, in particular from 0.1 to 1 % by weight (in each case based on the amount of polymer (product)).
The present invention further relates to a method of preparing the polymer by first reacting a glycerol carbonate and an amine of the formula R-NH2 yielding the carbamate of the formula (I) and/or (II); followed by polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II).
The polymer may be a homopolymer, a random copolymer, a block copolymer, or a gradient copolymer. Preferably, the polymer is a homopolymer (e.g. based on ethylene oxide) or a block copolymer (e.g. based on ethylene oxide and propylene oxide).
The polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II) may result in a poly(alkyleneglycol) polymer chain, which is terminated by a hydroxy group. Said hydroxy group by further be modified to arrive at other terminal groups. Suitable terminal groups of the polymerized alkylene oxide are -OR1, where
R1 is an H, d-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, -S03Ra, -P(0)ORbORc, -CH2C02Rd, or - C(0)Re,
Ra and Rd independently of one another are an H, inorganic or organic cations,
Rb and Rc independently of one another are an H, inorganic or organic cations, Ci-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl,
Re is Ci-C22-alkyl, C2-C22-alkenyl, C2-C22-alkynyl, C6-C22-aryl, C7-C22-alkylaryl, or or -ORd. Ra and Rd are independently of one another H, or inorganic or organic cations, which may be singly or multiply positively charged. Examples of inorganic cations are cations of ammonium, Na+, K+, Mg2+, Ca2+, or Zn2+. Examples of organic cations are methylammonium, dime- thylammonium, trimethylammonium, tetramethylammonium, (2-hydroxyethyl)ammonium, bis(2- hydroxyethyl)ammonium, tris(2-hydroxyethyl)ammonium, tetra(2-hydroxyethyl)ammonium. Preferably, Ra and Rd independently of one another are H or inorganic cations. If an inorganic or organic cation is present, then the associated anionic group would be formed by the corresponding functional group (e.g., -SO3", -Ρ(0)ΟΌ", or -CH2C02 ") on R6. Rb and R° are preferably, independently of one another, H, inorganic or organic cations. Suitable inorganic or organic cations are those specified under Ra.
R1 is preferably an H or Ci-C6-alkyl, more preferably an H or methyl, especially H.
In another preferred form, the polymer comprises the compound of the formula (III) and/or (IV)
wherein
R is a saturated or unsaturated, acyclic or cyclic, aliphatic, araliphatic or aromatic residue (preferably a saturated or unsaturated C4-C32 alkyl group),
R1 is an H, d-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, -S03Ra, -P(0)ORbORc, -CH2C02Rd, or -C(0)Re,
Ra and Rd independently of one another are an H, inorganic or organic cations,
Rb and Rc independently of one another are an H, inorganic or organic cations, Ci-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl,
Re is Ci-C22-alkyl, C2-C22-alkenyl, C2-C22-alkynyl, C6-C22-aryl or C7-C22-alkylaryl,
R2 is ethylene, propylene, butylene (1 -, 2-, or iso-) or a mixture thereof,
n, m have independently a value of from 0 to 20, and the sum of n and m is from 1 to 30.
R2 is most preferably ethylene, or ethylene and propylene. Usually, n, m have independently a value of from 0 to 30, and the sum of n and m is from 1 to 50. Preferably, n, m have independently a value of from 0 to 20, and the sum of n and m is from 1 to 25. The values of n and m are normally average values as they mostly arise upon the alkoxylation with alkoxides. Therefore, n and m can not only be integers, but also all values between the integers. The polymer may be present as a compound of the formula (III), of the formula (IV), or as a mixture of both. Preferably, the polymer comprises a mixture of a compound of the formula (III) and of the formula (IV). The mixture of the polymers may comprise 25 to 75 wt% (preferably 35 to 65 wt%) of each compound of the formula (III) and of the formula (IV), wherein they sum up to 100 wt%.
The compounds of the formula (III) and/or (IV) are obtainable by polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II). Typically, the polymer comprises at least 60 wt%, preferably at least 75 wt%, and in particular at least 90 wt% of the compound of the formula (III) and/or (IV).
The present invention further relates to a polymer, which is obtainable by the polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II), wherein the polymer consists of the compounds of the formula (III) or (IV).
The composition may contain at least 0,1 wt%, preferably at least 1 wt% of the adjuvant (e.g. the polymer). The composition according to the invention may be present as an agrochemical composition type and comprises from 1 to 80% by weight of the polymer, preferably from 2 to 50% by weight and in particular from 5 to 30% by weight.
The term pesticide refers to at least one active substance selected from the group of the fungicides, insecticides, nematicides, herbicides, safeners, molluscicides, rodenticides and/or growth regulators. Preferred pesticides are fungicides, insecticides, herbicides and growth regulators. Especially preferred pesticides are herbicides and growth regulators. Mixtures of pesticides from two or more of the abovementioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London. The pesticides may also comprise salts, esters, optical isomers or tautomers. Suitable pesticides are (groups A) to M) are fungicides): A) Respiration inhibitors
- Inhibitors of complex III at Q0 site (e.g. strobilurins): azoxystrobin, coumethoxystrobin,
coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxy- strobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, 2-[2-(2,5- dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-(2-(3-(2,6-di- chlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl- acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
- inhibitors of complex III at Q, site: cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8-benzyl-3-[(3- acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine- 2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate,
[(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]- 6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3- (1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]am
1 ,5-dioxonan-7-yl] 2-methylpropanoate; (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2- pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2- methylpropanoate;
- inhibitors of complex II (e. g. carboxamides): benodanil, bixafen, boscalid, carboxin, fen- furam, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'- trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide, N-(2- (1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide, N-[9- (dichloromethylene)-l ,2,3,4-tetrahydro-1 ,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1 - methyl-1 H-pyrazole-4-carboxamide;
- other respiration inhibitors (e.g. complex I, uncouplers): diflumetorim, (5,8-difluoroquinazolin- 4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl deri- vates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthi- ofam;
B) Sterol biosynthesis inhibitors (SBI fungicides)
- C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole, bitertanol, bromucona- zole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbu- conazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triti- conazole, uniconazole,
1 -[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H- [1 ,2,4]triazole, 2-[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]- 2H-[1 ,2,4]triazole-3-thiol; imidazoles: imazalil, pefurazoate, prochloraz, triflumizol; pyrim- idines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine;
- Delta14-reductase inhibitors: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
- Inhibitors of 3-keto reductase: fenhexamid;
C) Nucleic acid synthesis inhibitors
- phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
- others: hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p- tolylmethoxy)pyrimidin-4-amine, 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
D) Inhibitors of cell division and cytoskeleton
- tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl, carbendazim, fuber- idazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methyl- piperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine
- other cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil, mepanipyrim, pyrimethanil; - protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F) Signal transduction inhibitors
- MAP / histidine kinase inhibitors: fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
- G protein inhibitors: quinoxyfen;
G) Lipid and membrane synthesis inhibitors
- Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane;
- lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
- phospholipid biosynthesis and cell wall deposition: dimethomorph, flumorph, mandipropa- mid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and N-(1 -(1 -(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
- compounds affecting cell membrane permeability and fatty acides: propamocarb, propamo- carb-hydrochlorid
- fatty acid amide hydrolase inhibitors: 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]- 2-thiazolyl]-1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1 H-pyrazol-1 -yl]ethanone;
H) Inhibitors with Multi Site Action
- inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;
- organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chloro- thalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachloroben- zene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N- ethyl-4-methyl-benzenesulfonamide;
- guanidines and others: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyl- 1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
I) Cell wall synthesis inhibitors
- inhibitors of glucan synthesis: validamycin, polyoxin B; melanin synthesis inhibitors: pyroqui- lon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
J) Plant defence inducers
- acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
K) Unknown mode of action
- bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difen- zoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N- methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine, 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazole-1 -yl)- acetyl]-piperidin-4-yl}-thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1 -yl)- amide, 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]-piperidin-4-yl}-thiazole-4- carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide,
1 - [4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1 -piperidinyl]-
2- [5-methyl-3-(trifluoromethyl)-1 H-pyrazol-1 -yl]ethanone, methoxy-acetic acid
6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, A/-Methyl-2-{1 -[(5-methyl-3-trifluoro- methyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-A/-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4- thiazolecarboxamide, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4- chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole), N-(6-methoxy-pyridin-
3- yl) cyclopropanecarboxylic acid amide, 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl- 1 H-benzoimidazole,
2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide; Antifungal biocontrol agents, plant bioactivators: Ampelomyces quisqualis (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Aspergillus flavus (e.g. AFLAGUARD® from Syngenta, CH), Aureobasidium pullulans (e.g. BOTECTOR® from bio-ferm GmbH, Germany), Bacillus pumilus (e.g. NRRL Accession No. B-30087 in SONATA® and BALLAD® Plus from AgraQuest Inc., USA), Bacillus subtilis (e.g. isolate NRRL-Nr. B-21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest Inc., USA), Bacillus subtilis var. amyloliquefaciens FZB24 (e.g. TAEGRO® from Novozyme Biologicals, Inc., USA), Candida oleophila I-82 (e.g. ASPIRE® from Ecogen Inc., USA), Candida saitoana (e.g. BIO- CURE® (in mixture with lysozyme) and BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., NZ), Clonostachys rosea f. catenulata, also named Gliocladium catenulatum (e.g. isolate J 1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS® from Prophyta, Germany), Cryphonectria parasitica (e.g. Endothia parasitica from CNICM, France), Cryptococcus albi- dus (e.g. YIELD PLUS® from Anchor Bio-Technologies, South Africa), Fusarium oxysporum (e.g. BIOFOX® from S.I.A.P.A., Italy, FUSACLEAN® from Natural Plant Protection, France), Metschnikowia fructicola (e.g. SHEMER® from Agrogreen, Israel), Microdochium dimerum (e.g. ANTIBOT® from Agrauxine, France), Phlebiopsis gigantea (e.g. ROTSOP® from
Verdera, Finland), Pseudozyma flocculosa (e.g. SPORODEX® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (e.g. POLYVERSUM® from Remeslo SSRO, Bio- preparaty, Czech Rep.), Reynoutria sachlinensis (e.g. REGALIA® from Marrone Biolnnova- tions, USA), Talaromyces flavus V1 17b (e.g. PROTUS® from Prophyta, Germany), Tricho- derma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL® from Agrimm Technologies Ltd, NZ), T. harzianum T-22 (e.g. PLANTSHIELD® der Firma BioWorks Inc., USA), T. harzianum JH 35 (e.g. ROOT PRO® from Mycontrol Ltd., Israel), T. harzianum T-39 (e.g. TRICHODEX® and TRICHO-
DERMA 2000® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride (e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum ICC012 and T. viride ICC080 (e.g. REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T. harzi- anum (e.g. BINAB® from BINAB Bio-Innovation AB, Sweden), T. stromaticum (e.g. TRICO- VAB® from C.E.P.L.A.C., Brazil), T. virens GL-21 (e.g. SOILGARD® from Certis LLC, USA), T. viride (e.g. TRIECO® from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE® F from T. Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1 from Agribiotec srl, Italy), Ulo- cladium oudemansii HRU3 (e.g. BOTRY-ZEN® from Botry-Zen Ltd, NZ);
M) Growth regulators
abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, di- methipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadi- one (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phos- phorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole;
N) Herbicides
- acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefe- nacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
- amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
- aryloxyphenoxypropionat.es: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
- Bipyridyls: diquat, paraquat;
- (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam
(EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thio- bencarb, triallate;
- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepralox- ydim, tralkoxydim;
- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;
- diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, ox- yfluorfen;
- hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;
- imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;
- phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlor- prop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
- pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
- pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr;
- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfu- ron, triflusulfuron, tritosulfuron, 1 -((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3- (4,6-dimethoxy-pyrimidin-2-yl)urea; - triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;
- ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrim- isulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarba- zone,benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone, bromacil, bromo- butide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl, chlorthal, cinme- thylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl ar- sonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, py- raclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H- pyrimidin-1 -yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2- cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl- phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2- carboxylic acid methyl ester.
O) Insecticides
- organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyri- fos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethi- on, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl- parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phentho- ate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosul- fan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodi- carb, triazamate;
- pyrethroids: 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, profluthrin, dimefluthrin;
- insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cy- ramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juve- noids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
- nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, flupyradifurone, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1 -2-chloro-thiazol-5- ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane;
- GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyri- prole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1 H-pyrazole-3-carbothioic acid amide;
- macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram;
- mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebu- fenpyrad, tolfenpyrad, flufenerim;
- METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon;
- Uncouplers: chlorfenapyr;
- oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite;
- moulting disruptor compounds: cryomazine;
- mixed function oxidase inhibitors: piperonyl butoxide;
- sodium channel blockers: indoxacarb, metaflumizone;
- others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquinazon.
Examples of safeners are benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, di- cyclonon, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1 -oxa-4- azaspiro[4.5]decane (CAS 71526-07-3) and 2,2,5-trimethyl-3-(dichloroacetyl)-1 ,3-oxazolidine (CAS 52836-31 -4). Preferred pesticides comprise at least one pesticide with at least one H-acidic group (such as carboxylic acid group, phosphonic acid group, phosphinic acid group) or the anionic salts thereof (e.g., mono, di or tri salts). These anionic salts of the pesticides with an H-acidic group are also suitable as anionic pesticides in group A-. Preferred pesticides with an H-acidic group are herbicides with an H-acidic group. Examples of herbicides with an H-acidic group are amino acid analogs (such as glyphosate or glufosinate) or imidazolinones (such as imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr).
Particularly preferred pesticides with an H-acidic group are glyphosate and glufosinate. In another preferred embodiment, pesticides with an H-acidic group are imidazolinones.
Especially preferably, the pesticide comprises a pesticide with an H-acidic group and one further pesticide. In another embodiment the pesticide comprises mixtures of at least two pesti- cides with an H-acidic group, and optionally further pesticides (such as at least one fungicide, herbicide, insecticide, and/or safener, with fungicides and/or herbicides being preferred).
In a further preferred embodiment, the pesticide comprises glyphosate (for example as the free acid, sodium salt, sesquisodium salt, potassium salt, dipotassium salt, ammonium salt, diam- monium salt, dimethylammonium salt, trimesium salt or isopropylamine sale) or glufosinate (for example as the ammonium salt). With particular preference the pesticide comprises glyphosate (for example as the potassium salt, ammonium salt or isopropylamine salt). With particular preference the pesticide comprises glyphosate or glufosinate, and additionally a further herbicide. In another preferred embodiment the pesticide comprises glyphosate or glufosinate, and additionally a further pesticide (such as at least one fungicide, herbicide, insecticide and/or safener, with fungicides and/or herbicides being preferred).
Specifically preferably, the pesticide comprises glyphosate and at least one further herbicide selected from the following list:
acetochlor,acifluorofen, aclonifen, acrolein, alachlor, ametryn, amidosulfuron, amitrole, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benfluralin, benfuresate, bensulfuron- methyl, bensulide, bentazon, benzofenap, bialaphos, bifenox, bromacil, bromobutide, bromo- fenoxim, bromoxynil, butachlor, butamifos, butralin, butroxydim, butylate, cafenstrole, carbeta- mide, carfentrazone-ethyl, chlomethoxyfen, chloroamben, chlorobromuron, chloroidazon, chlo- roimuron-ethyl, chloronitrofen, chloroacetic acid, chlorotoluron, chloropropham, chlorosulfuron, chlorothal-dimethyl, chlorothiamid, cinmethylin, cinosulfuron, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam-methyl, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D,2,4-DB, daimuron, dalapon, desmedipham, desmetryn, di- camba, dichlobenil, dichloroprop, diclofop-methyl, difenzoquat, diflufenican, dimefuron, dimepi- perate, dimethachlor, dimethametryn, dimethenamid, dinitramine, dinoterb, diphenamid, diquat, dithiopyr, diuron, endothall, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofume- sate, ethoxysulfuron, etobenzanid, fenac, fenoxaprop, fenoxaprop-ethyl, fenuron, flamprop, flamprop-methyl, flazasulfuron, fluazifop-butyl, fluchloralin, flumetsulam, flumiclorac, flumiclorac- pentyl, flumioxazin, fluometuron, fluorochloridone, fluoroglycofen, fluoroglycofen-ethyl, flupo- xam, flupropanate, flurenol, fluridone, fluroxypyr-1- methylheptyl, flurtamone, fluthiacet-methyl, fomesafen, fosamine, glufosinate, halosulfuron, haloxyfop-methyl, hexazinone, imazameth, i- mazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, in- danofan, ioxynil, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPB, mecoprop, mefenacet, mesotrione, metamitron, metazachlor, metha- benzthiazuron, methylarsonic acid, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monolinuron, naproanilide, napro- pamide, naptalam, neburon, nicosulfuron, nonanoic acid, norflurazon, orbencarb, oryzalin, o- xadiargyl, oxadiazon, oxasulfuron, oxyfluorfen, paraquat, pebulate, pendimethalin, pentanoch- lor, pentoxazone, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodiamine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen-ethyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyributicarb, pyridate, pyriminobac-methyl, quinclorac, quinmerac, quizalofop- ethyl, rimsulfuron, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfamic acid, sulfentra- zone, sulfometuron, sulfosulfuron, TCA, tebutam, tebuthiuron, terbacil, terbumeton, terbuthyla- zine, terbutryn, thenylchlor, thiazopyr, thifensulfuron, thiobencarb, tiocarbazil, tralkoxydim, trial- late, triasulfuron, tribenuron, 2,3,6-trichlorobenzoic acid, triclopyr, trietazine, trifluralin, triflusulfu- ron, vernolate.
The composition according to the invention may also be present in form of an agrochemical compositions comprising the pesticide, the adjuvant( e.g. the polymer), and optionally an auxiliary. An agrochemical composition comprises a pesticidally effective amount of a pesticide. The term "effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful pests on or around cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific pesti- cide used.
Suitable, customary types of agrochemical compositions are e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Tech- nical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, further adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, al- kylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof. Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines. Suitable further adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the pesticide on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of the pesticide and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of the pesticide and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion. iii) Emulsifiable concentrates (EC)
15-70 wt% of the pesticide and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of the pesticide and 1 -10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of the pesticide are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added,
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of the pesticide are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of the pesticide are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of the pesticide are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
iv) Microemulsion (ME)
5-20 wt% of the pesticide are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethyl- amide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
iv) Microcapsules (CS)
An oil phase comprising 5-50 wt% of the pesticide, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of the pesticide, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenedi- amine) results in the formation of a polyurea microcapsules. The monomers amount to 1 -10 wt%. The wt% relate to the total CS composition.
ix) Dustable powders (DP, DS)
1 -10 wt% of the pesticide are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
x) Granules (GR, FG)
0.5-30 wt% of the pesticide is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
xi) Ultra-low volume liquids (UL)
1 -50 wt% of the pesticide are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydro- The compositions types i) to xi) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1 -1 wt% anti-foaming agents, and 0,1 -1 wt% col- orants. Preferred composition type is a water-soluble concentrates (SL).
In a preferred form, the composition according to the invention comprises at least 10 wt% of the pesticide (e.g. glyphosate), at least 1 wt% of the adjuvant, and up to 100 wt% water. In a very preferred form, the composition according to the invention comprises at least 30 wt% of the pes- ticide (e.g. glyphosate), at least 5 wt% of the adjuvant, and up to 100 wt% water. In an especially preferred form, the composition according to the invention comprises 10 to 70 wt% of the pesticide (e.g. glyphosate), 3 to 60 wt% of the adjuvant (e.g. the polymer), and up to 100 wt% water. The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance (i.e. pesticide). The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating the pesticide and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, the pesticide or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant prop- agation material (preferably seed) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1. The concentration of the adjuvant (e.g. the polymer) in the ready-to-use preparation (e.g. the tank mix) is in most cases in the range of from 0.01 to 50 g/l, preferably 0.08 to 10 g/l and in particular 0.5 to 8 g/l.
The concentration of water in the ready-to-use preparation (e.g. the tank mix) is in most cases at least 60 wt%, preferably at least 75 wt%, and in particular at least 90 wt%.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired applica- tion concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the in- vention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising the pesticide and the adjuvant, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate. In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising the pesticide and/or the adjuvant can be applied jointly (e.g. after tank mix) or consecutively. The present invention furthermore relates to a method of preparing the composition according to the invention by bringing the adjuvant and the pesticide into contact, e.g. by mixing. The contacting may be done between 5 to 95 °C. Thus, a tankmix or a agrochemical composition may be prepared. The present invention furthermore relates to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the composition according to the invention or the adjuvant is allowed to act on the respective pests, their environment or the crop plants to be protected from the re- spective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
The application rate of the adjuvant is in most cases in the range of from 10 to 3000 g/ha, pref- erably from 10 to 1000 g/ha, especially preferably from 80 to 750 g/ha and specifically from 100 to 400 g/ha. In another form, the application rate is at least 1000 g/ha adjuvant (e.g. polymer), preferably at least 1500 g/ha.
Examples of suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for ex- ample cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tangerines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avocados, cinnamon or camphor; energy crops and industrial feedstock crops, for example maize, soybeans, wheat, oilseed rape, sugar cane or oil palm; maize; tobacco; nuts; coffee; tea; bana- nas; wine (dessert grapes and grapes for vinification); hops; grass, for example turf; sweetleaf (Stevia rebaudania); rubber plants and forest plants, for example flowers, shrubs, deciduous trees and coniferous trees, and propagation material, for example seeds, and harvested produce of these plants. The term crop plants also includes those plants which have been modified by breeding, mutagenesis or recombinant methods, including the biotechnological agricultural products which are on the market or in the process of being developed. Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by hybridizing, mutations or natural recombination (i.e. recombination of the genetic material). Here, one or more genes will, as a rule, be integrated into the genetic material of the plant in order to improve the plant's properties. Such recombinant modifications also comprise posttranslational modifications of proteins, oligo- or polypeptides, for example by means of gly- cosylation or binding polymers such as, for example, prenylated, acetylated or farnesylated residues or PEG residues.
Examples which may be mentioned are plants which, as the result of plant-breeding and recombinant measures, have acquired a tolerance for certain classes of herbicides, such as hy- droxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors such as, for example, sulfonylureas (EP-A 257 993, US 5,013,659) or imidazolinones (for ex- ample US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526,
WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073), enolpyruvylshikimate 3-phosphate synthase (EPSPS) inhibitors such as, for example, glyphosate (see, for example, WO 92/00377), glutamine synthetase (GS) inhibitors such as, for example, glufosinate (see, for example, EP-A 242 236, EP-A 242 246) or oxynil herbicides (see, for example, US 5,559,024). For example, breeding and mutagenesis have given rise to Clearfield® oilseed rape (BASF SE, Germany), which features tolerance for imidaz- olinones, for example imazamox. With the aid of recombinant methods, crop plants such as soybeans, cotton, maize, beet and oilseed rape have been generated which are resistant to glyphosate or glufosinate, and these are available by the brand names RoundupReady® (glyphosate-resistant, Monsanto, U.S.A.) and Liberty Link® (glufosinate-resistant, Bayer Crop- Science, Germany). Also comprised are plants which, with the aid of recombinant measures, produce one or more toxins, for example those from the bacterial strain Bacillus. Toxins which are produced by such genetically modified plants comprise, for example, insecticidal proteins of Bacillus spp., in particular from B. thuringiensis, such as the endotoxins CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 , Cry9c, Cry34Ab1 or Cry35Ab1 ; or vegetable insecticidal proteins (VIPs), for example VIP1 , VIP2, VIP3, or VIP3A; insecticidal proteins from nematode-colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp.; toxins from animal organisms, for example wasp, spider or scorpion toxins; fungal toxins, for example from Streptomycetes; plant lectins, for example from pea or barley; agglutinins; proteinase inhibitors, for example trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIPs), for example ricin, maize RIP, abrin, luffin, saporin or bryodin; steroid- metabolizing enzymes, for example 3-hydroxysteroid oxidase, ecdysteroid I DP glycosyl transferase, cholesterol oxidase, ecdysone inhibitors or HMG CoA-reductase; ion channel blockers, for example inhibitors of sodium or calcium channels; juvenile hormone esterase; receptors for the diuretic hormone (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases and glucanases. These toxins can also be produced, in the plants, in the form of pretoxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are distinguished by a novel combination of different protein domains (see, for example, WO 2002/015701 ). Further examples of such toxins or genetically modified plants which produce these toxins are disclosed in EP-A 374 753, WO 93/07278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 and WO 03/52073. The methods for generating these genetically modified plants are known to the skilled worker and explained, for example, in the abovementioned publications. A large number of the abovementioned toxins impart to the plants which produce them a tolerance for pests from all taxonomic classes of the arthropods, in particular beetles (Coeleropta), dipterans (Diptera) and lepidopterans (Lepidoptera) and nematodes (Nematoda). Genetically modified plants which produce one or more genes which code for insecticidal toxins are described for example in the abovementioned publications and are in some cases commercially available such as, for example, YieldGard® (maize varieties which produce the toxin CrylAb), YieldGard® Plus (maize varieties which produce the toxins CrylAb and Cry3Bb1 ), Starlink® (maize varieties which produce the toxin Cry9c), Herculex® RW (maize varieties which produce the toxins Cry34Ab1 , Cry35Ab1 and the enzyme phosphinothricin N-acetyltransferase [PAT]); NuCOTN® 33B (cotton varieties which produce the toxin CrylAc), Bollgard® I (cotton varieties which produce the toxin CrylAc), Bollgard® II (cotton varieties which produce the toxins CrylAc and Cry2Ab2); VIPCOT® (cotton varieties which produce a VIP toxin); NewLeaf® (potato varieties which produce the toxin Cry3A); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt1 1 (for example Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (maize varieties which produce the toxin CrylAb and the PAT enzyme), MIR604 from Syngenta Seeds SAS, France (maize varieties which produce a modified version of the toxin Cry3A, see in this context WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (maize varieties which produce the toxin Cry3Bb1 ), IPC 531 from Monsanto Europe S.A., Belgium (cotton varieties which produce a modified version of the toxin CrylAc) and 1507 from Pioneer Overseas Corporation, Belgium (maize varieties which produce the toxin Cry1 F and the PAT enzyme).
Also comprised are plants which, with the aid of recombinant measures, produce one or more proteins which bring about an increased resistance to, or ability to withstand, bacterial, viral or fungal pathogens such as, for example, so-called pathogenesis-related proteins (PR proteins, see EP-A 0 392 225), resistance proteins (for example potato varieties which produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum) or T4 lysozyme (for example potato varieties which, as the result of the production of this protein, are resistant to bacteria such as Erwinia amylvora).
Also comprised are plants whose productivity has been improved with the aid of recombinant methods, for example by increasing the yield potential (for example biomass, grain yield, starch content, oil content or protein content), the tolerance for drought, salt or other limiting environmental factors, or the resistance to pests and fungal, bacterial and viral pathogens.
Also comprised are plants whose constituents, in particular for improving human or animal nutrition, have been modified with the aid of recombinant methods, for example by oil plants producing health-promoting long-chain omega-3-fatty acids or monounsaturated omega-9-fatty acids (for example Nexera® oilseed rape, DOW Agro Sciences, Canada).
The present invention also relates to seed (such as seeds or other plant propagation materials) comprising the composition according to the invention. Plant propagation materials can be treated preventively with the composition according to the invention at the point of or even be- fore sowing or at the point of or even before transplanting. For the treatment of seed, one will generally use water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible and water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF). These compositions can be applied to the propagation materials, in particular seed, in undiluted form or, preferably, in diluted form. Here, the composition in question can be diluted 2- to 10-fold, so that from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, of active substance is present in the compositions used for the seed dressing. The application may be effected before or during sowing. The treatment of plant propagation material, in particular the treatment of seed, is known to the skilled worker and carried out by dusting, coating, pelleting, dipping or soaking the plant propagation material, the treatment preferably being carried out by pelleting, coating and dusting or by in-furrow treatment so that, for example, untimely early germination of the seed is prevented. It is preferred to use suspensions for the treatment of seed. Usually, such compositions comprise from 1 to 800 g/l of active substance, from 1 to 200 g/l of surfactants, from 0 to 200 g/l of antifreeze agents, from 0 to 400 g/l of binders, from 0 to 200 g/l of colorants and solvent, preferably water.
The advantages of the invention are high stability of the formulation and of the spray mixture, little wind-caused drift in the case of spray applications, good adhesion of the formulation on the surface of the treated plants, increased solubility of the pesticides in the formulation, increased permeation of the pesticides into the plant, or more rapid and enhanced activity. An important advantage is the low toxicity of the adjuvant. Another advantage is the low harmful effect against crop plants, i.e. low phytotoxic effects. Another advantage is that no phase separation and no salt precipitation occurs in compositions with a high salt content, such as over 400 g/l glyphosate.
The examples which follow illustrate the invention without imposing any limitation. Example 1 - Carbamate synthesis
18.7g Dodecylamine were diluted in 10ml_ ethyl acetate. The solution of 12.0g glycerine carbonate in 10ml_ ethyl acetate was added at room temperature, then stirred for 1 hour, and heated for two hours to 60 °C. Hexane was added to the reaction mixture resulting in a clear solution which turns into a white suspension by cooling down to 10°C. The suspension is filtered and a white solid (21.3g, yield 70%, mp 67-71 °C) was obtained corresponding to the two isomers as confirmed with 1 H-NMR.
Example 2 - Carbamate synthesis
77.6g Octylamin was diluted in 200ml_ ethyl acetate. The solution of 75.4g glycerine carbonate in 100ml_ ethyl acetate was added and proceeded as in Example 1 .A white solid (105g, 71 % yield, mp 60-63°C) was obtined and the structure was further confirmed with IR and 1 H NMR.
Example 3 - Carbamate synthesis
1 19.6g tridecylamine in 200ml_ ethyl acetate and 75.4g glycerine carbonate in 100ml_ ethyl acetate were reacted as in Example 1. The resulting light yellow oil (1 12g, 59% yield) was the analogous carbamate reaction product as was confirmed with IR and 1 H NMR. xample 4 - Carbamate synthesis H
98.6g Cetylamine in 200mL ethyl acetate and 50.2g glycerine carbonate in 100ml_ ethyl acetate were reacted as in Example 1 . The resulting white solid (124g, 86% yield, mp 78-80°C) was the analogous carbamate reaction product as was confirmed with IR and 1 H NMR.
Example 5 - Carbamate synthesis
Oleylamine was reacted with glycerine carbonate analoguously to Example 1.
Example 6 - Alkoxylation of carbamates
17 g of the carbamate from example 2 and 0,44 g potassium methoxide were filled into a dry autoclave, which was preheated to 60°C. The mixture was stirred, heated to 100 °C and a vac- uum of 20 mbar was applied for two hours to remove methanol. After complete removal of methanol, nitrogen was led into the vessel, the reaction mixture heated up to a temperature of 120 °C and 30,2 g ethylene oxide dosed into the reactor within 10 hours. After complete addition of ethylene oxide, the reaction mixture was stirred for another 6 hours at 120 °C. The mixture was cooled down to 100 °C and a vacuum of 20 mbar was applied for 30 minutes. The mix- ture is then further cooled to 80 °C and filled into a storage vessel. The product was obtained in quantitative yield and is a brownish, viscous liquid.
The free hydroxy groups of the carbamates synthesized in Examples 1 -5 were ethoxylated accordingly with 5, 10 or 15 equivalents of gaseous ethylene oxide. The resulting polymers were obtained in quantitative yield.
Example 7 - Preparation of SL formulation and tankmix
An aqueous formulation (SL type) was prepared by dissolving 52.3 wt% potassium glyphosate in water. As adjuvant the ethoxylated (10 equivalents) carbamate from Example 1 was added and dissolved in the resulting SL formulation. This SL formulation was diluted with water to prepare a tank mix, which contained 0,8 g/l of the adjuvant, 0,75 g/l of the potassium glyphosate (or as alternative tank mix 0,37 g/l). This tankmix may be applied at 375 l/ha (corresponding to 300 g/ha adjuvant and 280 g/ha glyphosate (or 140 g/ha as alternative). For comparison, Genamine® T1510 from Clariant was used, which is a tallow fatty amine eth- oxylate comprising 15 mole ethylene oxide per mol tallow fatty amine. Example 8 - Biological Testing
For the greenhouse tests, various crops (winter wheat (cultivar Cubus), maize (cultivar
Amadeo), soybean (cultivar Delta P.), rapeseed) was sown or potted in loamy sandy soil to a depth of 1 -2 cm. When the plants had reached a growth height of 10 to 25 cm (i.e., around 10 to 21 days after sowing), the spray mixtures were applied to the plants in a spraying cabin.
The tank mix prepared in Example 7 was applied at a application rate of 375 l/ha (140 or 280 g of glyphosate/ha and 300 g of adjuvant/ha). The temperatures in the experimental period, which lasted for 3 to 4 weeks, were between 18-35°C. During this time, the experimental plants re- ceived optimum watering, with nutrients being supplied via the water used for watering.
The herbicidal activity was evaluated by awarding scores to the treated plants in comparison to the untreated control plants (Table 1 and 2). The evaluation scale ranges from 0% to 100% activity. 100% activity means the complete death at least of those parts of the plant that are above ground. Conversely, 0% activity means that there were no differences between treated and untreated plants. The results demonstrated the increased activity of the active substance as a result of addition of the adjuvant.
Table 1 : Activity [%] after 21 days DAT (280 g/ha application rate)
a) Comparative experiment, not inventive.
Table 2: Activity [%] after 21 days DAT (140 g/ha application rate)
a) Comparative experiment, not inventive.

Claims

Claims
1 . A composition comprising a pesticide and an adjuvant selected from a carbamate of the formula (I), a carbamate of the formula (II), or a polymer, which is obtainable by polymerization of at least one alkylene oxide and a carbamate of the formula (I) and/or (II)
where R is a saturated or unsaturated, acyclic or cyclic, aliphatic, araliphatic or aromatic residue.
The composition according to claim 1 , wherein the alkylene oxide is C2-, C3-, and/or C4- alkylene oxide.
The composition according to claim 1 or 2, wherein the polymer comprises from 3 to 30 equivalents of the alkylene oxide per equivalent of the carbamate.
The composition according to any of claims 1 to 3, wherein the polymer comprises from 3 to 20 equivalents of the ethylene oxide and optionally 1 to 10 equivalents of propylen oxide per equivalent of the carbamate.
The composition according to any of claims 1 to 4, wherein R is a linear or branched C6-C24 alkyl group.
The composition according to any of claims 1 to 5, wherein R is selected from n-octyl, decyl, n-dodecyl, branched tridecyl, tetradecyl, cetyl, or oleyl.
The composition according to any of claims 1 to 6, wherein the terminal groups of the polymerized alkylene oxide are -OR1, where
R1 is an H, Ci-Ce-alkyI, C2-C6-alkenyl, C2-C6-alkynyl, -S03Ra, -P(0)ORbORc, -CH2C02Rd, or -C(0)Re,
Ra and Rd independently of one another are an H, inorganic or organic cations,
Rb and Rc independently of one another are an H, inorganic or organic cations, Ci-C6-alkyl,
C2-C6-alkenyl or C2-C6-alkynyl,
Re is Ci-C22-alkyl, C2-C22-alkenyl, C2-C22-alkynyl, C6-C22-aryl, C7-C22-alkylaryl, or -ORd.
The composition according to any of claims 1 to 7, wherein the pesticide contains glypho- sate. The composition according to any of claims 1 to 8, wherein the carbamate of the formula (I) and/or formula (II) is obtainable by reacting glycerol carbonate and an amine of the formula R-NH2, where R is a saturated or unsaturated C4-C32 alkyl group.
10 A method of preparing the composition according to any of claims 1 to 9, by bringing the adjuvant and the pesticide into contact. 1 1 A polymer, which is obtainable by the polymerization as defined in any of claims 1 to 9, which consists of the compounds of the formula (III) or (IV)
wherein
R is a saturated or unsaturated, acyclic or cyclic, aliphatic, araliphatic or aromatic residue, R1 is an H, d-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, -S03Ra, -P(0)ORbORc, -CH2C02Rd, or -C(0)Re,
Ra and Rd independently of one another are an H, inorganic or organic cations,
Rb and Rc independently of one another are an H, inorganic or organic cations, Ci-C6-alkyl,
C2-C6-alkenyl or C2-C6-alkynyl,
Re is Ci-C22-alkyl, C2-C22-alkenyl, C2-C22-alkynyl, C6-C22-aryl or C7-C22-alkylaryl,
R2 is ethylene, propylene, butylene or a mixture thereof,
n, m have independently a value of from 0 to 20, and the sum of n and m is from 1 to 30.
12. The polymer according to claim 1 1 , wherein R is a saturated or unsaturated C4-C32 alkyl group. 13. The polymer according to claim 1 1 or 12, wherein R1 is H or Ci-C6-alkyl. 14. A method of preparing the polymer as defined in claims 1 to 9 or according to claims 1 1 to 13 by first reacting a glycerol carbonate and an amine of the formula R-NH2 yielding the carbamate of the formula (I) and/or (II); followed by polymerization of at least one alkylene oxide and the carbamate of the formula (I) and/or (II).
15. A method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the composition according to any of claims 1 to 9 or the polymer as defined in any of claims 1 to 9 or the polymer according to claimsl 1 to 13 is allowed to act on the respective pests, their envi- ronment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
16. The method according to claim 15, wherein the application rate is at least 1000 g/ha poly- mer.
17. Seed containing the composition according to any of claims 1 to 9 or the polymer as defined in any of claims 1 to 9 or the polymer according to claims 1 1 to 13.
EP13703620.8A 2012-03-01 2013-02-13 Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkylamines Withdrawn EP2819511A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13703620.8A EP2819511A1 (en) 2012-03-01 2013-02-13 Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkylamines

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201261605254P 2012-03-01 2012-03-01
EP12157770 2012-03-01
PCT/EP2013/052831 WO2013127629A1 (en) 2012-03-01 2013-02-13 Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkylamines
EP13703620.8A EP2819511A1 (en) 2012-03-01 2013-02-13 Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkylamines

Publications (1)

Publication Number Publication Date
EP2819511A1 true EP2819511A1 (en) 2015-01-07

Family

ID=49081666

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13703620.8A Withdrawn EP2819511A1 (en) 2012-03-01 2013-02-13 Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkylamines

Country Status (3)

Country Link
EP (1) EP2819511A1 (en)
BR (1) BR112014021199A2 (en)
WO (1) WO2013127629A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150126365A (en) 2013-03-13 2015-11-11 빈터샬 홀딩 게엠베하 Process for the preparation of substituted tris(2-hydroxyphenyl)methane
CN106198470A (en) * 2016-06-30 2016-12-07 江苏莱芙时代生物科技有限公司 A kind of fungal detection fluorescence staining liquid and application

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5304732A (en) 1984-03-06 1994-04-19 Mgi Pharma, Inc. Herbicide resistance in plants
BR8600161A (en) 1985-01-18 1986-09-23 Plant Genetic Systems Nv CHEMICAL GENE, HYBRID, INTERMEDIATE PLASMIDIO VECTORS, PROCESS TO CONTROL INSECTS IN AGRICULTURE OR HORTICULTURE, INSECTICIDE COMPOSITION, PROCESS TO TRANSFORM PLANT CELLS TO EXPRESS A PLANTINIDE TOXIN, PRODUCED BY CULTURES, UNITED BY BACILLA
DE3765449D1 (en) 1986-03-11 1990-11-15 Plant Genetic Systems Nv PLANT CELLS RESISTED BY GENE TECHNOLOGY AND RESISTANT TO GLUTAMINE SYNTHETASE INHIBITORS.
IL83348A (en) 1986-08-26 1995-12-08 Du Pont Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
US5013659A (en) 1987-07-27 1991-05-07 E. I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
FR2629098B1 (en) 1988-03-23 1990-08-10 Rhone Poulenc Agrochimie CHEMICAL GENE OF HERBICIDE RESISTANCE
CA2005658A1 (en) 1988-12-19 1990-06-19 Eliahu Zlotkin Insecticidal toxins, genes encoding these toxins, antibodies binding to them and transgenic plant cells and plants expressing these toxins
DK0392225T3 (en) 1989-03-24 2003-09-22 Syngenta Participations Ag Disease resistant transgenic plants
ES2074547T3 (en) 1989-11-07 1995-09-16 Pioneer Hi Bred Int LARVICID LECTINES, AND INDUCED RESISTANCE OF PLANTS TO INSECTS.
CA2083948C (en) 1990-06-25 2001-05-15 Ganesh M. Kishore Glyphosate tolerant plants
UA48104C2 (en) 1991-10-04 2002-08-15 Новартіс Аг Dna fragment including sequence that codes an insecticide protein with optimization for corn, dna fragment providing directed preferable for the stem core expression of the structural gene of the plant related to it, dna fragment providing specific for the pollen expression of related to it structural gene in the plant, recombinant dna molecule, method for obtaining a coding sequence of the insecticide protein optimized for corn, method of corn plants protection at least against one pest insect
US5530195A (en) 1994-06-10 1996-06-25 Ciba-Geigy Corporation Bacillus thuringiensis gene encoding a toxin active against insects
US5773704A (en) 1996-04-29 1998-06-30 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Herbicide resistant rice
US5773702A (en) 1996-07-17 1998-06-30 Board Of Trustees Operating Michigan State University Imidazolinone herbicide resistant sugar beet plants
WO1998002527A1 (en) 1996-07-17 1998-01-22 Michigan State University Imidazolinone herbicide resistant sugar beet plants
US6348643B1 (en) 1998-10-29 2002-02-19 American Cyanamid Company DNA sequences encoding the arabidopsis acetohydroxy-acid synthase small subunit and methods of use
CA2407396C (en) 2000-04-28 2013-12-31 Basf Aktiengesellschaft Use of the maize x112 mutant ahas 2 gene and imidazolinone herbicides for selection of transgenic monocots
JP2004506432A (en) 2000-08-25 2004-03-04 シンジェンタ・パティシペーションズ・アクチェンゲゼルシャフト Novel insecticidal toxin derived from Bacillus thuringiensis insecticidal crystal protein
DE10118109A1 (en) * 2001-04-11 2002-10-17 Cognis Deutschland Gmbh Production of glycerol carbamate esters useful as thickeners in detergent, cosmetic and pharmaceutical compositions, comprises reacting a glycerol, diglycerol or polyglycerol carbonate with an amine
CA2808328C (en) 2001-08-09 2019-08-06 Northwest Plant Breeding Company Wheat plants having increased resistance to imidazolinone herbicides
UA104990C2 (en) 2001-08-09 2014-04-10 Юніверсіті Оф Саскачеван Wheat plant with increased resistance towards imidazolinone herbicides
BR0211808A (en) 2001-08-09 2004-09-08 Univ Saskatchewan Wheat plants having increased resistance to imidazoline herbicides
US7230167B2 (en) 2001-08-31 2007-06-12 Syngenta Participations Ag Modified Cry3A toxins and nucleic acid sequences coding therefor
AU2002361696A1 (en) 2001-12-17 2003-06-30 Syngenta Participations Ag Novel corn event
CA2492167C (en) 2002-07-10 2015-06-16 The Department Of Agriculture, Western Australia Wheat plants having increased resistance to imidazolinone herbicides
ES2389767T3 (en) 2003-05-28 2012-10-31 Basf Se Wheat plants that have higher tolerance to imidazolinone herbicides
EP1659855B1 (en) 2003-08-29 2011-11-02 Instituto Nacional de Tecnologia Agropecuaria Rice plants having increased tolerance to imidazolinone herbicides
WO2008154639A2 (en) * 2007-06-12 2008-12-18 Neose Technologies, Inc. Improved process for the production of nucleotide sugars
EP2103211A1 (en) * 2008-03-20 2009-09-23 Cognis IP Management GmbH Adjuvant compositions
ES2391913T3 (en) * 2008-06-13 2012-12-03 Clariant Finance (Bvi) Limited Cosmetic or pharmaceutical compositions comprising polysiloxanes modified with at least one carbamate group
ES2764485T3 (en) * 2009-05-07 2020-06-03 Huntsman Corporation Australia Pty Ltd Dispersants in solutions with high electrolytic content
CN103384691B (en) 2011-02-22 2015-09-30 巴斯夫欧洲公司 Based on the polymkeric substance of carbonic acid glyceride and amine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013127629A1 *

Also Published As

Publication number Publication date
WO2013127629A1 (en) 2013-09-06
BR112014021199A2 (en) 2018-05-08

Similar Documents

Publication Publication Date Title
EP2680692B1 (en) Composition comprising a pesticide, an alkoxylate of 2-propylheptylamine and a further surfactant
US10390528B2 (en) Solid agroformulations for preparing near micro-emulsion aqueous pesticides
JP2015525233A (en) Adjuvants containing 2-propylheptylamine alkoxylates, sugar-based surfactants and drift control agents and / or wetting agents
EP3068220B1 (en) A composition comprising an active and a graft copolymer made of n-vinyllactam, vinyl ester, and an alcohol alkoxylate
US20180235211A1 (en) Solid agroformulations prepared from a melt of pesticide and polyalkoxylate, optionally containing liquid adjuvant complexed with polycarboxylate
WO2021043642A1 (en) Polymers for spray drift control of pesticide spray
AU2016206295B2 (en) Emulsifiable granule obtainable by mixing an pesticidal emulsion with solid dispersant and extruding the resulting paste
WO2013075977A1 (en) Adjuvant containing fatty acid ester and silicone surfactant
EP2819511A1 (en) Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkylamines
US20220332660A1 (en) Stable Aqueous Compositions of Fertilizer and Agriculturally Active Compound
US20150072856A1 (en) Adjuvants based on optionally alkoxylated reaction products of glycerol carbonate and alkylamines
NZ613701B2 (en) Composition comprising a pesticide, a surfactant and an alkoxylate of 2-propylheptylamine

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20141001

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20151022

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160509

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20160920