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EP3500098A1 - Composition herbicide comprenant du clomazone et utilisation associée - Google Patents

Composition herbicide comprenant du clomazone et utilisation associée

Info

Publication number
EP3500098A1
EP3500098A1 EP16913149.7A EP16913149A EP3500098A1 EP 3500098 A1 EP3500098 A1 EP 3500098A1 EP 16913149 A EP16913149 A EP 16913149A EP 3500098 A1 EP3500098 A1 EP 3500098A1
Authority
EP
European Patent Office
Prior art keywords
water
composition according
epoxy resin
diisocyanate
organic phase
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Withdrawn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
EP16913149.7A
Other languages
German (de)
English (en)
Other versions
EP3500098A4 (fr
Inventor
Yifan Wu
James Timothy Bristow
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.)
Jiangsu Rotam Chemical Co Ltd
Original Assignee
Jiangsu Rotam Chemical Co Ltd
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 Jiangsu Rotam Chemical Co Ltd filed Critical Jiangsu Rotam Chemical Co Ltd
Publication of EP3500098A1 publication Critical patent/EP3500098A1/fr
Publication of EP3500098A4 publication Critical patent/EP3500098A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—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 in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/22—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom rings with more than six members
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • the present invention concerns an improved microcapsules having epoxy resin incorporated in the polyurea shell wall.
  • the material to be encapsulated is water-immiscible material or high volatile material.
  • the capsule can be dispersed in an aqueous phase.
  • the capsules may be produced to any desired size, for example, of the order of 1 micron up to 100 microns or larger, preferably the size of the microcapsules will range from about 1 to about 50 microns in diameter.
  • Matson U.S. Pat. No. 3,516,941 discloses in-situ polymerization reactions in which the material to be encapsulated is dissolved in an organic, hydrophobic oil phase which is dispersed in an aqueous phase.
  • the aqueous phase has dissolved resin precursors, particularly aminoplast resin precursors, which upon polymerization will form the wall of the microcapsule.
  • a dispersion of fine oil droplets is prepared using high shear agitation. The degree of shear has a major effect on the droplet size and may serve to keep the capsule size small.
  • Addition of an acid catalyst initiates the polycondensation of the aminoplast precursors within the aqueous phase, resulting in the formation of an aminoplast polymer which is insoluble in both phases.
  • the aminoplast polymer separates from the aqueous phase and deposits on the surface of the dispersed droplets of the oil phase to form a capsule shell at the interface of the two phases, thus encapsulating the fill materials. This process produces the microcapsules.
  • Polymerizations that involve amines and aldehydes, such as those described herein, are also known as aminoplast encapsulations. Urea-formaldehyde (UF) , urea-resorcinol-formaldehyde (URF) , urea-melamine-formaldehyde (UMF) , and melamine-formaldehyde (MF) , capsule formations proceed in this manner.
  • the materials to form the capsule wall are in separate phases, one in an aqueous phase and the other in a fill phase. Polymerization occurs at the phase boundary. Thus, a polymeric capsule shell wall forms at the interface of the two phases thereby encapsulating the fill materials. Wall formation of polyester, polyamide, and polyurea capsules proceeds via interfacial polymerization.
  • Solubilized inorganic materials have been used to modify the surface of particles to be encapsulated.
  • Ugro U.S. Pat. No. 4,879,175, encapsulated inorganic pigment particles in microcapsules prepared by in-situ polymerization (such as aminoplast polymerization) , interfacial polymerization, and coacervation. Because the pigment particles were insoluble in both the oil and water phases, Ugro used surface modifying agents to control the relative wettability of the solids by the organic and aqueous phases. Surface modifying agents such as titanates and silanes were used to modify the surface of the pigment, render it oleophilic, and thus encapsulable in the capsule fill (oil phase) .
  • Control of the relative wettability enabled the deposition of smooth, relatively fault free shells and could be used to control the location of the pigments within the microcapsule structure.
  • Pigments such as metal oxides, carbon black, phthalocyanines, and particularly oil and water insoluble cosmetic colorants were successfully encapsulated by this method.
  • the present invention provides an improved herbicide composition comprising water-immiscible material or high volatile material contained within an encapsulating polymer skin material comprising a polyurea cross-linked by epoxy resin.
  • the microcapsules of the present invention have a polymer wall of a polyurea cross-linked by epoxy resin polymer.
  • the polyurea cross-linked by epoxy resin polymer is formed interfacial polymerization occurring at the interface of a dispersed organic phase and a continuous aqueous phase.
  • the polyurea cross-linked by epoxy resin polymer is preferably formed by the reaction of an isocyanate, in particular a polyfunctional isocyanate, an epoxy and a polyfunctional amine.
  • the microcapsules are formed by interfacial polymerization reaction.
  • a water immiscible organic phase is provided comprising water-immiscible material or high volatile material, one or more polyfunctional isocyanates and an epoxy resin polymer.
  • An aqueous phase is provided comprising one or polyfunctional amines.
  • the organic phase is dispersed in known manner in the aqueous phase, as a result of which formation of the polyurea cross-linked by epoxy resin polymer occurs at the interface of the dispersed organic phase and the aqueous phase. It is an advantage of the present invention that the mixture of components, once dispersed, does not need to be heated to induce the interfacial polymerization reactions.
  • One or more surfactants and/or stabilizers may be included in the mixture, as required, as described hereinafter.
  • the present invention provides a method of preparing a microencapsulated composition, the method comprising:
  • an epoxy resin such as amine-terminated diglycidyl ether of biphenyl-A (DGEBA) prepolymers
  • DGEBA diglycidyl ether of biphenyl-A
  • the process comprises the steps of:
  • an active ingredient to be encapsulated such as clomazone
  • the microcapsules of the present invention are formed by the reaction of a polyfunctional isocyanate.
  • Suitable polyfunctional isocyanates have two or more isocyanate groups. Examples of compounds providing reactive isocyanate groups include para-phenylene diisocyanate, meta-phenylene diisocyanate, naphthalene-1, 5-diisocyanate, tetrachloro-m-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4, 4-diphenyl diisocyanate, the dichloro diphenyl methane diisocyanates, bibenzyl diisocyanate, bitolylene diisocyanate, the diphenyl ether diisocyanates, the dimethyldiphenyl diisocyanates, the polymethylene polyphenyl isocyanates, triphenylmethane-4, 4', 4"-triisocyanate, isopropylbenzen
  • the microcapsules of the present invention are further formed from a polyfunctional amine.
  • Suitable amines for use have two or amine groups.
  • suitable amines for use in the present invention are diamine and higher polyamine reactants, including ethylene diamine, phenylene diamine, toluene diamine, hexamethylene diamine, diethylene triamine, triethylenetetramine, piperazine, 1, 3, 5-benzenetriamine trihydrochloride, 2, 4, 6-triaminotoluene trihydrochloride, tetraethylene pentamine, pentaethylene hexamine, polyethylene imine, 1, 3, 6-triaminonaphthlene, 3, 4, 5-triamino-1, 2, 4-triazole, melamine, and 1, 4, 5, 8-tetraminoanthraquinone.
  • the microcapsules of the present invention are formed to have a shell of a cross-linked polymer, in particular a polyurea cross-linked by epoxy resin polymer.
  • the cross linking agent is a surfaced modified epoxy resin.
  • Epoxy resin can be selected from diglycidyl ether of biphenyl-A (DGEBA) and its derivative.
  • Surface-modified means that the epoxy resin surface has been (chemically) modified so as to have cross-linkable, reactive functional groups.
  • the surface of the epoxy resin may be modified using modifying agents selected from a wide variety of chemicals.
  • epoxide compounds are particularly suitable for the process according to the invention: epoxidised diolefins, dienes or cyclic dienes, such as butadiene dioxide, 1, 2, 5, 6-diepoxyhexane and 1, 2, 4, 5-diepoxycyclohexane; epoxidised diolefinically unsaturated carboxylic acid esters, such as methyl 9, 10, 12, 13-diepoxystearate; the dimethyl ester of 6, 7, 10, 11-diepoxyhexadecane-1, 16-dicarboxylic acid; and epoxidised compounds containing two cyclohexenyl radicals, such as diethylene glycol bis- (3, 4-epoxycyclohexanecarboxylate) and 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate.
  • epoxidised diolefins dienes or cyclic dienes, such as butadiene dioxide, 1, 2, 5, 6-diepoxyhex
  • polyesters such as are accessible by reacting a dicarboxylic acid with epichlorohydrin or dichlorohydrin in the presence of alkali.
  • Such polyesters can be derived from aliphatic dicarboxylic acids, such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and especially from aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 2, 6-naphthylene-dicarboxylic acid, diphenyl-o, o'-dicarboxylic acid, ethylene glycol bis- (p-carboxyphenyl) ether and others.
  • polyglycidyl ethers such as are accessible by etherification of a dihydric or polyhydric alcohol or diphenol or polyphenol with epichlorohydrin or dichlorohydrin in the presence of alkali.
  • These compounds can be derived from glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, pentane-1, 5-diol, hexane-1, 6-diol, hexane-2, 4, 6-triol and glycerol, and especially from diphenols or polyphenols, phenol novolacs or cresol novolacs, resorcinol, pyrocatechol, hydroquinone, 1, 4-dihydroxynaphthalene, phenol/formaldehyde condensation products, bis- (4-hydroxyphenyl) -methane (bisphenol F) , bis (4-hydroxyphenyl) -methyl
  • epoxy resins for example, of the average formula:
  • Z is a small number and is an integer or fraction, for example between 0 and 25.
  • diglycidyl ethers of bisphenol A to be used in accordance with the present invention are diglycidyl ethers having the formula:
  • z represents 0 or a positive number having a value of 0 to about 25.
  • Diglycidyl ether of biphenyl-A (DGEBA) prepolymers are prepared by reaction of epichlorohydrin with 2, 2-bis (p-hydroxyphenyl) propane (bisphenol-A) in the presence of an alkali metal hydroxide, characterized by:
  • the epichlorohydrin/bisphenol-A molar ratio should not exceed 15: 1. Values of the said ratio which are less than 10: 1 do not give epoxy resins with the desired characteristics, especially as regards the values of the viscosity and the hydrolyzable chlorine content. On the other hand no appreciable improvements are obtained by using epichlorohydrin/bisphenol-A molar ratios greater than 15: 1.
  • the aqueous solution of alkali metal hydroxide is fed in until the ratio between the moles of alkali metal hydroxide and the number of phenolic hydroxyl groups is from 1: 1 to 1.05: 1, so as not to enhance those secondary reactions which give rise to the formation of undesirable by-products.
  • a large excess of alkali metal hydroxide typically an excess of 10-20%) , with the object of reducing the hydrolyzable chlorine content in the epoxy resin, with consequent diminutions in yield and formation of undesirable by-products.
  • a concentrated aqueous solution of alkali metal hydroxide is used, for example a solution containing from 40 to 50 wt. %of the said hydroxide.
  • the hydroxide is preferably sodium or potassium hydroxide.
  • the fundamental feature of the process of this invention consists in keeping an amount of water of from 0.1%to 0.7%by weight and a pH value between 7 and 9 in the reaction medium, during the addition of alkali metal hydroxide.
  • the water is continuously removed from the reaction medium in the form of an azeotropic mixture with epichlorohydrin; the vapors thus produced are condensed with separation into two layers, the aqueous layer being discharged and the epichlorohydrin layer being recycled into the reaction medium.
  • the feed rate of the aqueous solution and the rate of evaporation of the water are adjusted so as to maintain the water content and pH of the reaction mass within the ranges of values defined above.
  • the addition of the aqueous alkali metal hydroxide is generally effected in a period of from 3 to 6 hours.
  • reaction mass may be circulated continuously through a self-cleaning filter or a centrifuge, placed outside the reaction zone.
  • a self-cleaning filter or a centrifuge placed outside the reaction zone.
  • liquid epoxy resin is recovered from the reaction products by conventional methods.
  • water can be added to the reaction products to wash out the alkali metal chloride.
  • the aqueous phase is then separated from the organic phase consisting of a solution of the liquid epoxy resin in epichlorohydrin. Obviously this operation may not be necessary when the alkali metal chloride is removed in the course of the reaction.
  • the unreacted epichlorohydrin is then distilled off, and it is generally convenient to filter off the distillation residue so as to remove any inorganic compound present.
  • reaction yields based on the converted epichlorohydrin are in each case 95%or more, whereas in known methods in which an excess of sodium hydroxide of 10-20%over the stoichiometric value is used, these yields are of the order of 85-90%.
  • J is --C (O) R 1 , --C (O) NHR 2 , --C (O) NR 2 R 3 , --CHR 4 OR 5 , or --SiR 1 R 2 R 3 , and R 1 , R 2 , R 3 , R 4 , and R 5 are substituted or unsubstituted alkyl, aryl or cycloalkyl groups such as: --CH 3 --CH 2 Cl, --CH 2 OCH 3 , --CH 2 CH 3 , --CH (CH 3 ) 2 , --C 4 H 9 --n, --C 5 H 11 --n, --C 8 H 17 --n, --CH (C 2 H 5 ) 2 , --C 6 H 11 --c, --CH 2 CH 2 C 6 H 5 , --CH 2 CH (C 6 H 5 ) 2 , --CH 2 OCH 2 C 6 H 5 , --CH 2 CH 2 C 6 H 3 (3, 4--OCH 3 ) , --CH 2 CO 2 C 2 H 5 , --C 6 H 5 , --
  • a polymer derived from bisphenol-A and epichlorohydrin is considered to be "substantially free of free hydroxyl groups" when at least 50%of the polymer units derived from epichlorohydrin do not contain free hydroxyl groups. Preferably, at least 75%of such units, and more preferably at least 95%of such units, will have their free hydroxyl groups blocked.
  • Examples of particular polymers of the invention according to the above formula include E-1 through E-19, which are obtained by blocking the free hydroxyl groups of PKHH Phenoxy Resin:
  • the polymers of the invention give improved stability as compared to the non-functionalized polymer containing free hydroxyl groups, and compared to bisphenol-A polycarbonate.
  • the multi-phase reaction mixture used to prepare the microcapsules in the present invention comprises a polyfunctional isocyanate and a polyfunctional amine, in addition to the cross-linking agent.
  • the degree of cross-linking of the polymer wall may be controlled, inter alia, by selection of the polyfunctional reactants.
  • Sufficient polyfunctional reactant is provided in the reaction mixture to produce microcapsules wherein the polyurea cross-linked by epoxy resin capsule wall is from 3 to 60%cross-linked, more preferably 3 to 30%cross-linked, that is, from 3 to 60%, more preferably from 3 to 30%of the polymer is part of a three dimensional polymer network.
  • the polyurea cross-linked by epoxy resin capsule wall is from 3 to 30%cross-linked.
  • the microcapsules may have any suitable particle size.
  • the average particle size of the microcapsules will generally range from about 1 to about 130 microns, preferably from 1 to 100 microns, more preferably from 1 to 50 microns, with a preferred average particle size of about 1 to 50 microns. Such relatively fine particles are advantageous to prevent plugging of orifices in the spraying equipment used for field application of the pesticide compositions.
  • the wall thickness of the microcapsules may be selected according to the intended use of the composition.
  • the wall thickness of the polyurea cross-linked by epoxy resin capsule preferably ranges from about 0.01 micron to 4 microns, with from about 0.01 to 1 microns thickness preferred.
  • the thickness of the capsule wall, as well as the degree of crosslinking of the polymer constituting same, will affect the rate of diffusion of the active ingredient therethrough, and thereby influence the performance of the composition in the field.
  • the microcapsule size may be controlled during the manufacturing process by controlling the degree of dispersion of the material to be encapsulated and the water-immiscible phase in the aqueous phase.
  • microcapsule wall thickness may be further controlled by the quantity of the reactive intermediate present in the water-immiscible phase to be encapsulated.
  • the multi-phase reaction mixture may contain other components, as required, for example to provide microcapsules of the required size and/or to facilitate other aspects of the process.
  • the aqueous phase may comprise one or more surfactants.
  • Suitable surface active agents are known in the art and include the sodium salt of alkylnaphthalene sulfonic acid, the potassium salt of alkylnaphthalene sulfonic acid, salts of polystyrenesulfonic acid, in particular, the alkali metal, alkaline earth metal and ammonium salts thereof, and salts of condensates of naphthalenesulfonic acids, and mixtures thereof.
  • the dispersant system for the microencapsulation process may also optionally contain one or more non-ionic surfactant, non-ionic protective colloid, or a cationic component.
  • Lignosulfonates are a particularly preferred surfactant for use in the process, in particular sodium lignosulfonate.
  • compositions of the present invention may include one or more emulsifiers.
  • the emulsifiers can be cationic, anionic or nonionic, but are more preferably anionic or nonionic.
  • particularly suitable anionic surfactants for this purpose are sulfonates such as calcium dodecyl benzenesulfonate.
  • particularly suitable nonionic surfactants are polyoxyethylated (POE) sorbitan esters such as POE (20) sorbitan trioleate and polyoxyethylated (POE) sorbitol esters such as POE (40) sorbitol hexaoleate.
  • POE polyoxyethylated
  • POE polyoxyethylated
  • sorbitol esters such as POE (40) sorbitol hexaoleate.
  • Suitable emulsifiers are known in the art and are commercially available.
  • Polyvinyl alcohol ( 203) POE (20) sorbitan trioleate is commercially available under the tradename TWEEN 85 marketed by Uniqema.
  • POE (40) sorbitol hexaoleate is commercially available under the tradenames ATLAS G1086 and CIRRASOL G1086 marketed by Uniqema.
  • a POE sorbitan ester with a POE sorbitol ester allows the HLB (hydrophilic-lipophilic balance) value of the surfactant to be optimized, so as to obtain the highest quality emulsion (smallest suspended droplets) when the composition is added to water.
  • High quality emulsions typically lead to optimal herbicidal performance.
  • composition of the present invention comprising one or more nonionic surfactants selected from polyoxyethylated (POE) sorbitan esters such as POE (20) sorbitan trioleate and polyoxyethylated (POE) sorbitol esters such as POE (40) sorbitol hexaoleate and mixtures thereof.
  • POE polyoxyethylated
  • the mixture may also comprise an antifoam agent.
  • suitable antifoam agent are known in the art.
  • One preferred agent is a polydimethyl siloxane antifoam agent (Dow 1500) .
  • the mixture may also comprise one or more antifreezing agent.
  • suitable antifreezing agents are known in the art.
  • One preferred agent is Propylene Glycol.
  • Suitable stabilizers include calcium chloride, sodium nitrate.
  • a neutralizing agent in particular to control the pH and prevent the formation of acidic conditions which may arise as a result of the condensation reactions.
  • Suitable neutralizing agents are known in the art and include hydrochloric acid.
  • An exemplary recipe for preparing the cross-linked polyurea cross-linked by epoxy polymer encapsulating polymer wall for clomazone is as follows:
  • polyfunctional isocyanate such as polymethylene polyphenylisocyanate known as "PAPI”
  • PAPI polymethylene polyphenylisocyanate
  • difunctional amine such as ethylene diamine
  • n-y moles where n equals 1 to 3;
  • hydrochloride acid 1 –x moles to neutralize the reaction system to be pH 6-9.
  • Excess amine may be present in the reaction mixture.
  • the water-immiscible phase may comprise a solvent.
  • the active ingredient in particular clomazone, acts as a water-insoluble organic solvent for the components to be present in the organic phase, in particular the cross-linking agent and the isocyanate.
  • the water-immiscible phase is dispersed in water and the amine is charged to the reaction as an aqueous solution.
  • the procedure of US 3,577,515 may then be employed to produce the microencapsulated product.
  • the weight ratio of the active ingredient to the polymer in the microencapsulated composition may be any suitable ratio.
  • the weight ratio of the active ingredient, in particular clomazone, to the polymer in the microcapsules is in the range of from about 2: 1 to 50: 1, more preferably from 3: 1 to 8: 1, still more preferably 4: 1 to 7: 1, with a ratio of about 5: 1 being particularly preferred.
  • microcapsules once prepared may be formulated in any suitable manner. Suitable formulations and formulating techniques for such microcapsules are known in the art. A suspension or slurry of the microcapsules in a suitable diluent, most preferably water, is one preferred embodiment for shipping, storing, and ultimately dispensing the composition to the area to be treated. Conventional spraying apparatus is used for application of these formulations.
  • the formulation may be applied directly to the target area.
  • the composition may be further diluted, prior art application.
  • a convenient water dispersion, suspension or slurry for shipping and storage will consist of from about 10 to 30%by weight of microcapsules, more preferably about 25%, of the pesticide-containing microcapsules, which will be diluted with water to about 1%by weight for spraying.
  • compositions of the present invention may be used to control unwanted plant growth at a locus.
  • the present invention provides a method of controlling plant growth at a locus, the method comprising applying to the locus a composition as described hereinbefore.
  • the present invention further provides the use of the compositions described hereinbefore in the control of plant growth.
  • compositions may be applied to the area where control of plant growth is desired, prior to or after emergence of the target plants, for example by spraying onto the surface of the soil or onto the foliage of the plants.
  • the user may, if desired, blend the formulation into the upper layer of soil by cultivation.
  • compositions of the present invention are particularly suitable for the formulation of water immiscible material and high volatile material, such as clomazone, abamectin, pendimethalin, lambda cyhalothrin, spinosad, emamectin benzoate, deltamethrin, cypermethrin, acetochlor, alachlor, metolachlor and their mixture.
  • the active ingredient to be encapsulated can be dissolved in aromatic solvent.
  • aromatic solvent is SOLVESSO (EXXON MOBIL) .
  • One uses an apparatus comprising a reaction vessel (flask) , mechanical agitator, electric heater, distillation column, a condenser, a separator for the epichlorohydrin-water distillate fitted with a siphon for recycling the epichlorohydrin, and a system for regulating the pressure in the reaction vessel.
  • a reaction vessel flask
  • mechanical agitator electric heater
  • distillation column distillation column
  • condenser a separator for the epichlorohydrin-water distillate fitted with a siphon for recycling the epichlorohydrin
  • a separator for the epichlorohydrin-water distillate fitted with a siphon for recycling the epichlorohydrin
  • the pressure in the apparatus is regulated to the desired value and the mass is gradually heated to boiling point.
  • the water is removed from the boiling mass in the form of an azeotropic mixture with epichlorohydrin.
  • the resultant vapors are condensed, the denser epichlorohydrin layer is recycled and the aqueous layer is discharged.
  • the conditions are so regulated as to maintain the water content of the reacting mass at the desired value.
  • the mass After the addition of the sodium hydroxide the mass is kept boiling for a further 15 minutes. Then about 500 parts by weight of water are added, the mass is agitated for 20 minutes and the aqueous phase removed by decantation, operating at about 50°C.
  • the organic phase is distilled, working first at atmospheric pressure and then at subatmospheric pressure (about 10 mmHg) in order to remove the unreacted epichlorohydrin completely.
  • the distillation residue is finally filtered to remove any residual inorganic salts, using diatomaceous earth as a filter aid.
  • the liquid epoxy resin thus obtained is tested to determine its properties, and the results are recorded in the Table.
  • Example I is for comparison in that the water content in the reacting mass is less than the minimum value.
  • Examples 9 to 13 are also for comparison in that the said water content is greater than the maximum limit.
  • Example 1 is repeated, using a 5%excess molar amount of sodium hydroxide with respect to the number of phenolic hydroxyl groups in the bisphenol-A feed.
  • a liquid epoxy resin is obtained with a hydrolyzable chlorine content of 0.3%by weight, whilst the other characteristics of the said resin remain practically unchanged.
  • Examples 2 to 8 are repeated using a 5%excess molar amount of sodium hydroxide with respect to the number of phenolic hydroxyl groups in the bisphenol-A feed.
  • Liquid epoxy resins are obtained with a hydrolyzable chlorine content of from 0.02 to 0.09%by weight, whilst the other characteristics remain practically unchanged.
  • Examples 9 to 13 are repeated using a 5%excess molar amount of sodium hydroxide with respect to the number of phenolic hydroxyl groups in the bisphenol-A feed.
  • Liquid epoxy resins are obtained with a hydrolyzable chlorine content of 0.1-0.4%by weight whilst the other characteristics remain practically unchanged.
  • the Hazen colour of the liquid epoxy resin is of the order of 200; in Examples 15-21 the Hazen colour is of the order of 80-120.
  • the pressure in the apparatus is regulated to 160 mm Hg and the mixture is heated to boiling point.
  • the sodium chloride is formed as a by-product of the reaction, is removed by circulating the reaction mass continuously through a centrifuge placed outside the reactor.
  • the epoxy resin is represented by Formula (I) with "n” equal to 0.014.
  • Example 27 is repeated, 420 parts by weight of an aqueous 49%by weight solution of sodium hydroxide being fed in.
  • the epoxy resin thus obtained has a hydrolyzable chlorine content equal to 0.06%by weight whilst the other characteristics are practically unchanged.
  • tetraoctylammonium bromide 1.5 g was mixed with 100 ml of dry toluene and the mixture was sonicated for 30 min, under a flow of dry Ar. 100 ml of DEGBA resin was added via a gas-tight syringe and sonication was continued for 30 min allowing entry into the micelles.
  • Alkylamine-terminated DEGBA resin with three different alkyl chain lengths were obtained in the reactions of degassed allylamine (2.7 g) , hex-5-en-1-amine (2.4 g) and undec-10-en-1-amine (4.4 g) to each flask with hydrogen-terminated DEGBA resin under Ar, in the presence of 40 ml of 0.05 M H 2 PtCl 6 catalyst.
  • 6-Bromo-1-hexene (5 ml; 0.04 mol) was dissolved in 50 ml DMF. After addition of NaN 3 (0.20 mol) the mixture was stirred at 35 °C for 24 hours. Cold water was added and 6-azido-hex-1-ene was extracted with petroleum ether (PE 40/60) and washed 3 times with brine. Pure 6-azido-hex-1-ene has been obtained with 75%yield.
  • 11-Bromoundecene-1-ene (10 ml; 0.05 mol) was dissolved in 50 ml of DMF. After addition of NaN 3 (0.20 mol) the mixture was stirred at 90°C for 24 hours. Cold water was added and 11-azidoundec-1-ene was extracted with petroleum ether (PE 40/60) and washed 3 times with brine. Pure 11-azidoundec-1-ene has been obtained with 90.3%yield.
  • a water-immiscible organic phase prepared just prior to use having the following components:
  • 0.28g amine terminated DEGBA resin crosslinker (from example 29) was dispersed in 1.47g SOLVESSO (EXXON MOBIL) . The mixture was mixed well at high speed in a high-shear mixer. 0.77g isocyanate (Suprasec-5005) was then added and the mixture was stirred for 10min. 9.36g clomazone was finally added.
  • SOLVESSO EXXON MOBIL
  • Water-immiscible organic phase was added dropwise into aqueous phase. After mixing by high-shear mixer, oil in water dispersion was formed.
  • the oil in water dispersion was transferred into an Erlenmeyer flask. 0.77g diethylenetriamine aqueous solution (0.77g diethylenetriamine in 1.73g water) was added dropwise with stirring. The dispersion was heated and maintained at about 50°C for 4 hours.
  • Adjuvant such as stabilizers (1.69g calcium chloride, 0.70g sodium nitrate) , thickening agent (2%Xanthan gum, 0.67g) , antifreeze agent (1.60g propylene glycol) was added when the temperature was cooled down to about 30°C. pH adjustor (hydrochloric acid 36-38%) was added to keep pH at 6-9.
  • a water-immiscible organic phase prepared just prior to use having the following composition:
  • 0.28g amine terminated DEGBA resin crosslinker (from example 29) was dispersed in 1.47g SOLVESSO (EXXON MOBIL) . The mixture was mixed well at high speed in a high-shear mixer. 0.46g isocyanate (Suprasec-5005) was then added and the mixture was stirred for 10min. 9.36g Clomazone was finally added.
  • Water-immiscible organic phase was added dropwise into aqueous phase. After mixing by high-shear mixer, oil in water dispersion was formed.
  • the oil in water dispersion was transferred into an Erlenmeyer flask. 0.46g diethylenetriamine aqueous solution (0.46g diethylenetriamine in 2.04g water) was added dropwise with stirring. The dispersion was heated and maintained at about 50°C for 4 hours.
  • Adjuvant such as stabilizers (1.69g calcium chloride, 0.70g sodium nitrate) , thickening agent (2%Xanthan gum, 0.67g) , antifreeze agent (1.60g propylene glycol) was added when the temperature was cooled down to about 30°C. pH adjustor (hydrochloric acid 36-38%) was added to keep pH at 6-9.
  • a water-immiscible organic phase prepared just prior to use having the following composition:
  • 0.28g amine terminated DEGBA resin crosslinker from example 29
  • 1.6g POE (20) sorbitan trioleate 0.16g lignosulfonic acid, sodium salt (Reax 88B)
  • 0.16g sulfonated aromatic polymer 0.16g sulfonated aromatic polymer
  • sodium salt MORWET D-425 POWDER
  • 0.03g antifoam 0.03g antifoam (Dow 1500) was added in 6.18g water to be aqueous phase.
  • Water-immiscible organic phase was added dropwise into aqueous phase. After mixing by high-shear mixer, oil in water dispersion was formed.
  • the oil in water dispersion was transferred into an Erlenmeyer flask. 0.77g diethylenetriamine aqueous solution (0.77g diethylenetriamine in 1.73g water) was added dropwise with stirring. The dispersion was heated and maintained at about 50°C for 4 hours.
  • Adjuvant such as stabilizers (1.69g calcium chloride, 0.70g sodium nitrate) , thickening agent (2%Xanthan gum, 0.67g) , antifreeze agent (1.60g propylene glycol) was added when the temperature was cooled down to about 30°C. pH adjustor (hydrochloric acid 36-38%) was added to keep pH at 6-9.
  • a water-immiscible organic phase prepared just prior to use having the following composition:
  • Water-immiscible organic phase was added dropwise into aqueous phase. After mixing by high-shear mixer, oil in water dispersion was formed.
  • the oil in water dispersion was transferred into an Erlenmeyer flask. 0.77g diethylenetriamine aqueous solution (0.77g diethylenetriamine in 1.73g water) was added dropwise with stirring. The dispersion was heated and maintained at about 50°C for 4 hours.
  • Adjuvant such as stabilizers (1.69g calcium chloride, 0.70g sodium nitrate) , thickening agent (2%Xanthan gum, 0.67g) , antifreeze agent (1.60g propylene glycol) was added when the temperature was cooled down to about 30°C.
  • PH adjustor hydroochloric acid 36-38%) was added to keep pH at 6-9.
  • Example 2 was repeated for the mixture of clomazone and any one of acetochlor, alachlor and metolachlor.
  • Example 2 were repeated for the following active ingredients: abamectin, pendimethalin, lambda cyhalothrin, spinosad, emamectin benzoate, Deltamethrin and cypermethrin.

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

Abstract

La présente invention concerne une composition comprenant une matière non miscible dans l'eau ou une matière hautement volatile encapsulée à l'intérieur d'une microcapsule, les microcapsules ayant une enveloppe comprenant une polyurée réticulée par un polymère de résine époxy. L'invention concerne également le procédé de préparation de ladite composition herbicide, et l'utilisation de celle-ci dans la lutte contre la croissance de plantes indésirables.
EP16913149.7A 2016-08-17 2016-08-17 Composition herbicide comprenant du clomazone et utilisation associée Withdrawn EP3500098A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2016/095621 WO2018032389A1 (fr) 2016-08-17 2016-08-17 Composition herbicide comprenant du clomazone et utilisation associée

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EP3500098A1 true EP3500098A1 (fr) 2019-06-26
EP3500098A4 EP3500098A4 (fr) 2020-01-15

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EP4125384A4 (fr) 2020-03-27 2024-02-07 Dow Global Technologies LLC Formulations pesticides à base de fosthiazate
CN111909646B (zh) * 2020-08-07 2021-12-17 湖南福湘木业有限责任公司 一种大豆基胶粘剂防霉改性的方法

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Publication number Priority date Publication date Assignee Title
JPS5813212B2 (ja) * 1973-07-17 1983-03-12 富士写真フイルム株式会社 マイクロカプセル ノ セイゾウホウ
JPS59148066A (ja) * 1983-02-14 1984-08-24 Konishiroku Photo Ind Co Ltd マイクロカプセル型トナ−
JPS60222870A (ja) * 1984-04-20 1985-11-07 Konishiroku Photo Ind Co Ltd マイクロカプセル型トナ−
US4785048A (en) 1988-02-08 1988-11-15 Moore Business Forms, Inc. Polyurea and polyurea-epoxy microcapsules
MXPA05006365A (es) * 2002-12-13 2005-08-29 Monsanto Technology Llc Microcapsulas con velocidad de liberacion ajustada con aminas.
AU2011271403B2 (en) * 2010-06-07 2016-12-22 Syngenta Crop Protection Ag Stabilized chemical composition
GB2483050B (en) * 2010-08-17 2012-12-19 Rotam Agrochem Int Co Ltd Herbicidal compositions
CN103331133B (zh) * 2013-06-07 2015-06-24 深圳大学 一种以聚脲为壁材的环氧微胶囊及其制备方法
GB2509430B (en) * 2014-03-26 2016-09-14 Rotam Agrochem Int Co Ltd Herbicidal composition, a method for its preparation and the use thereof
CN105833811B (zh) * 2016-03-27 2018-06-22 华南理工大学 一种双胶囊自修复环氧涂层及其制备方法

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WO2018032389A1 (fr) 2018-02-22
CN109640651A (zh) 2019-04-16
GB201901591D0 (en) 2019-03-27
GB2567099B (en) 2022-04-06
EP3500098A4 (fr) 2020-01-15
CN109640651B (zh) 2022-10-11

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