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EP3500361A1 - Composition herbicide comprenant du clomazone et son utilisation - Google Patents

Composition herbicide comprenant du clomazone et son utilisation

Info

Publication number
EP3500361A1
EP3500361A1 EP16913147.1A EP16913147A EP3500361A1 EP 3500361 A1 EP3500361 A1 EP 3500361A1 EP 16913147 A EP16913147 A EP 16913147A EP 3500361 A1 EP3500361 A1 EP 3500361A1
Authority
EP
European Patent Office
Prior art keywords
microcapsules
diisocyanate
wall material
water
polyols
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Withdrawn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
EP16913147.1A
Other languages
German (de)
English (en)
Other versions
EP3500361A4 (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 EP3500361A1 publication Critical patent/EP3500361A1/fr
Publication of EP3500361A4 publication Critical patent/EP3500361A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • 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
    • A01N37/22—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 the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • 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
    • A01N43/72—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2310/00—Agricultural use or equipment

Definitions

  • This invention concerns an improved microcapsules polymer wall material consisting of crosslinked polyurethane-polyurea copolymer and its preparation and use.
  • Capsules of this character have a variety of uses, as for encapsulating dyes, chemical reagents, pharmaceuticals, flavoring materials, pesticides (for example, herbicides, insecticides and fungicides) and the like.
  • the liquid or other forms is preserved until it is released by means or instrumentalities that break, crush, melt, dissolve, or remove the capsule wall or until release by diffusion under suitable conditions.
  • the process of the invention is particularly suitable for the production of water-immiscible material inside microcapsules which are of very small in particle size, and suspended in an aqueous solution.
  • Producing of aqueous dispersions of microcapsules having water-immiscible materials are particularly useful in formulating controlled release of water-immiscible material formulations. It is because they can be diluted with water or liquid fertilizer and then sprayed using conventional equipment to produce uniform coverage of the water-immiscible material in fields. Additives, such as film forming agents, can be added directly to the finished formulation to improve the adhesion of microcapsules to foliage. Reduced toxicity and extended activity of the encapsulated water-immiscible material have been reported.
  • British Pat. No. 1,371,179 discloses a process which consists of dispersing an organic pesticide phase containing a polymethylene polyphenylisocyanate or toluene diisocyanate monomer into an aqueous phase.
  • the wall-forming reaction is initiated by elevating temperature to the point which the isocyanate monomers are hydrolyzed at the interface to form amines, which in turn react with unhydrolyzed isocyanate monomers to form the polyurea wall.
  • One difficulty of this technique is the possibility of continued reaction of monomer after packaging. Unless all monomers are reacted during the preparation, there will be continued hydrolysis of the isocyanate monomer together with the evolution of carbon dioxide that will result building up pressure after packaging.
  • the present invention provides a new and improved encapsulation process which is rapid and effective and avoids the necessity of separation of the encapsulated material from a continuous phase.
  • the present invention also eliminates the necessity of the use of a strong solvent in an organic phase resulting in saving energy, packaging and equipment.
  • direct combination of water-based pesticide formulations are possible with other water-based pesticides.
  • compositions of the present invention are particularly suitable for formulating water immiscible and/or highly volatile material, such as clomazone, abamectin, pendimethalin, lambda cyhalothrin, spinosad, emamectin benzoate, deltamethrin, cypermethrin, acetochlor, alachlor, metolachlor and combinations thereof.
  • water immiscible and/or highly volatile material such as clomazone, abamectin, pendimethalin, lambda cyhalothrin, spinosad, emamectin benzoate, deltamethrin, cypermethrin, acetochlor, alachlor, metolachlor and combinations thereof.
  • microcapsules must be separated from the aqueous solution and resuspended in water before they can be sprayed in by conventional agricultural spraying apparatus.
  • This invention provides a process to encapsulate more than 480 grams of water immiscible material in a polyurethane-polyurea copolymer wall of microcapsules and to suspend the microcapsules in the original aqueous solution.
  • the suspended microcapsules can be stored for an extended period of time and can be exposed for short-terms of elevated temperatures without the occurrence of agglomeration or solidification of the aqueous, capsule mass or herbicide crystal growth.
  • This invention also provides a method of controlling plant growth at a locus, comprising applying the composition to the locus.
  • This invention also provides the use of the composition in the control of unwanted plant growth.
  • This invention concerns an improved microcapsules polymer wall material consisting of crosslinked polyurethane-polyurea copolymer.
  • the invention comprises an isocyanate-terminated polyurethane prepolymers.
  • Preferred isocyanate includes polymethylene polyphenyl isocyanates (PMPPI) .
  • PMPPI polymethylene polyphenyl isocyanates
  • the prepolymer then forms polyurethane-polyurea copolymer when it is added to a polyfunctional amine.
  • Preferred polyfunctional amine is 1, 6-hexamethylene diamine.
  • a water-immiscible (organic) phase which consists of a water-immiscible material (the material to be encapsulated) and isocyanate-terminated polyurethane prepolymers, is added to an aqueous phase, with agitation, to form a dispersion of small droplets of water-immiscible phase within the aqueous phase.
  • the polyfunctional amine preferably 1, 6-hexamethylene diamine, is added, with continued agitation, to the dispersion.
  • the polyfunctional amine reacts with isocyanate-terminated polyurethane prepolymers to form a capsular polyurethane-polyurea copolymer wall containing the water-immiscible material.
  • the water-immiscible material which is the material to be encapsulated, can be clomazone, abamectin, pendimethalin, lambda cyhalothrin, spinosad, emamectin benzoate, deltamethrin, cypermethrin, acetochlor, alachlor, metolachlor and the mixture thereof.
  • the material to be encapsulated can be a combination of two or more various types of water-immiscible materials.
  • the combination can be a herbicide with another herbicide; a herbicide with an insecticide; a herbicide with a fungicide; or a herbicide with a nematicide.
  • the combination can also be any pesticides (for example herbicide) with an inactive ingredient (for example, a solvent or adjuvant) .
  • the organic solvents can be xylene and chlorobenzene.
  • the isocyanate-terminated polyurethane prepolymers can be prepared by reacting a molar excess of organic polyisocyanate with one or more polyols.
  • the organic polyisocyanate can be either aliphatic, cycloaliphatic, araliphatic or aromatic.
  • Suitable organic polyisocyanates include meta-phenylene diisocyanate, paraphenylene diisocyanate, 2, 4'-diphenylmethane diisocyanate, benzidine diisocyanate, naphthalene-1, 5-diisocyanate, hexamethylene diisocyanate, 4, 4'4"-triphenylmethane triisocyanate, decamethylene diisocyanate, poly phenylmethylene polyisocyanates that are produced by phosgenation of aniline/formaldehyde condensation products, dianisidine diisocyanate, xylylene diisocyanate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) cyclohex-4-ene-1, 2-dicarboxylate, bis (2-isocyanatoe
  • one or more polyhydroxy compounds or polyols can be employed in the reaction with the organic polyisocyanate.
  • Illustrative polyhydroxy compounds include the following classes of compounds:
  • polyester polyols and alkylene oxide adducts thereof;
  • hydroxyl-terminated extended lactone polyesters prepared by phosgenation of a lactone polyester with a polyol such as bisphenol A (BPA) , and the like.
  • alkylene oxide includes, for example, ethylene oxide, 1, 2-epoxypropane, 1, 2-epoxybutane, 2, 3-epoxybutane, isobutylene oxide, epichlorohydrin, and the like, and mixtures thereof.
  • Lactone polyols are prepared by reacting a lactone, such as epsilon-caprolactone or a mixture of epsilon-caprolactone and an alkylene oxide, with a polyfunctional initiator, such as polyhydric alcohol.
  • lactone polyols also includes various "copolymers” , such as lactone copolyesters, lactone polyester/polycarbonates, lactone polyester/polyethers, lactone polyester/polyether/polycarbonates, and the like.
  • Polyester polyols are esterification products which range from liquids to non-crosslinked solids, i.e., solids which are insoluble in many of the more common inert normally liquid organic media, and which are prepared by the reaction of monocarboxylic acids and/or polycarboxylic acids, their anhydrides, their esters, or their halides, with a stoichiometric excess of a polyol.
  • polycarboxylic acids which can be employed to prepare the polyester polyols preferably included dicarboxylic acids and tricarboxylic acids, such as maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, chlorendic acid, 1, 2, 4-butanetricarboxylic acid, phthalic acid, and the like.
  • dicarboxylic acids and tricarboxylic acids such as maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, chlorendic acid, 1, 2, 4-butanetricarboxylic acid, phthalic acid, and the like.
  • Polyoxyalkyene polyols include alkylene oxide adducts of, for example, water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, gycerol, 1, 2, 6-hexanetriol, 1, 1, 1-trimethylol ethane or propane pentaerythritol, sorbitol, sucrose, lactose, alpha-methylglucoside, alpha-hydroxyalkylgluocoside, and the like.
  • Alkylene oxides employed in producing polyoxyalkylene polyols normally have from 2 to 4 carbon atoms. Ethylene oxide, propylene oxide and mixtures of propylene oxide with ethylene oxide are preferred. Such polyalkylene polyols are well known in the art.
  • sucrose the alkyl glucosides such as methylglucoside, ethyl glucoside, and the like
  • polyol glucosides such as ethylene glycol glucoside, propylene glycol glucoside, glycerol glucoside, 1, 2, 6-hexanetriol glucoside, and the like
  • alkylene oxide adducts thereof sucrose, the alkyl glucosides such as methylglucoside, ethyl glucoside, and the like
  • polyol glucosides such as ethylene glycol glucoside, propylene glycol glucoside, glycerol glucoside, 1, 2, 6-hexanetriol glucoside, and the like
  • alkylene oxide adducts thereof such as ethylene glycol glucoside, propylene glycol glucoside, glycerol glucoside, 1, 2, 6-hexanetriol glucoside, and the like
  • Alkylene oxide adducts of polyphenols include those in which the polyphenol can be bisphenol A (BPA) ; bisphenol F (BPF) ; the condensation products of phenol and formaldehyde, more particularly the novolac resins; the condensation products of various phenolic compounds and acrolein, the simplest members of this class being the 1, 1, 3-tris (hydrophenyl) propanes; the condensation products of various phenolic compounds and glyoxal, glutaraldehyde, and other dialdehydes, the simplest members of this class being the 1, 1, 2, 2-tetrabis (hydroxyphenyl) ethanes, and the like.
  • BPA bisphenol A
  • BPF bisphenol F
  • the condensation products of phenol and formaldehyde more particularly the novolac resins
  • the condensation products of various phenolic compounds and acrolein the simplest members of this class being the 1, 1, 3-tris (hydrophenyl) propanes
  • polystyrene resin Another useful class of polyols is the polytetramethylene glycols, which are prepared by polymerizing tetrahydrofuran in the presence of the acidic catalyst. Also, useful are castor oil and alkylene oxide adducts of castor oil.
  • Suitable polyhydroxy polysulfide polymers have the formula:
  • R and R’ are divalent aliphatic radicals
  • n is an integer having a value of from 1 to 100, which can be prepared by reacting a dihalo-organic compound such as Cl--R’ --Cl, a chlorohydrin such as Cl—R’ --OH and an inorganic polysulfide.
  • the polyol or polyol mixture employed can have hydroxyl numbers which vary over a wide range.
  • the hydroxyl numbers of the polyols employed in the invention can range from about 20, and lower, to about 1000, and higher, preferably, from about 30 to about 800, and more preferably from about 35 to about 700.
  • the hydroxyl number is defined as the number of milligrams of potassium hydroxide required for the complete neutralization of the hydrolysis product of the fully acetylated derivative prepared from 1 gram of polyol.
  • the hydroxyl number can also be defined by the equation:
  • OH is the hydroxy number of the polyol
  • f is the average functionality, this is average number of hydroxyl groups per molecule of polyol
  • M.W. is the average molecular weight of the polyol.
  • the most preferred polyisocyanates are alkylene diisocyanates and aromatic diisocyanates, especially polymethylene polyphenyl isocyanates (PMPPI) , while the most preferred polyols are the diols of polyalkylene glycols and the diols of polycaprolactones.
  • PMPPI polymethylene polyphenyl isocyanates
  • G represents the residue on removal of the terminal OH groups from the hydroxy terminal polyol employed; wherein W represents a divalent hydrocarbon radical and wherein m is an integer of at least one.
  • W represents a divalent hydrocarbon radical and wherein m is an integer of at least one.
  • useful isocyanate-terminated polyurethanes will have a molecular weight that is governed by their intended end use.
  • the polymers should not be too viscous and generally have a molecular weight from 2,000 to about 20,000, preferably from about 4,000 to about 14,000.
  • viscosity problems can be avoided and molecular weights of the polymers greater than 20,000 can be used provided there is a sufficient concentration of hydrolyzable end groups to form a three-dimensional, cross-linked network upon curing.
  • a solvent it should be inert with respect to the polymer and volatile under the curing conditions.
  • the polyfunctional amines suitable for use in the present invention are those amines which are capable of reacting with isocyanate-terminated polyurethane prepolymers to form polyurethane-polyurea copolymer wall.
  • the polyfunctional amines should be water-soluble per se or in water soluble salt form.
  • the usable polyfunctional amines can be selected from a wide range of such materials.
  • Suitable examples of polyfunctional amines which may be used in this invention include, but are by no means limited to the following: ethylenediamine, propylenediamine, isopropylenediamine, hexamethylenediamine, toluenediamine, ethenediamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, diethylenetriamine, bis-hexamethylenetriamine and the like.
  • the amines may be used alone or in combination with each other, preferably in combination with 1, 6-hexamethylenediamine (HMDA) . 1, 6-hexamethylenediamine is preferred for use in the process of the present invention.
  • HMDA 1, 6-hexamethylenediamine
  • Isocyanate-terminated polyurethane prepolymers and the polyfunctional amine form the wall which ultimately encapsulates the water-immiscible material.
  • the wall content of the capsules formed by the present process may vary from about 5%to about 30%, preferably 8%to 20%and more particularly, 10%by weight, of the water-immiscible material.
  • the amount of isocyanate-terminated polyurethane prepolymers and polyfunctional amine used in the process is determined by the percent wall content produced. Generally, there will be present in the reaction, from about 3.5%to about 21.0%isocyanate-terminated polyurethane prepolymers and from about 1.5%to about 9.0%amine, relative to the weight of the water-immiscible material. Preferably, there will be from about 5.6%to about 13.9%isocyanate-terminated polyurethane prepolymers and from about 2.4%to about 6.1%amine and more particularly, 7.0%isocyanate-terminated polyurethane prepolymers and 3.0%amine relative to the weight of the water-immiscible material, present in the reaction.
  • emulsifying agents being generally referred to herein as emulsifiers, which are critical for use in the practice of the present invention are the salts of lignin sulfonate, e.g., sodium, potassium, magnesium, calcium or ammonium salts.
  • the sodium salt of lignin sulfonate is the preferred emulsifier.
  • Any commercially available emulsifier of the type previously described which does not contain added surfactant, may be conveniently employed and many are described in McCutcheon's Detergents and Emulsifier's , North American Edition 1978 (McCutcheon Div., MC Publishing Co., Glen Rock, N.J. ) .
  • LTS LTS
  • LTK LTM
  • potassium, magnesium and sodium salts of lignosulfonate 50%aqueous solutions
  • Scott Paper Co. Forest Chemical Products
  • Marasperse and Marasperse sodium lignosulfonate American Can Co.
  • Polyfon Polyfon Reax Reax sodium salts of lignin sulfonate and Reax calcium salt of lignin sulfonate Westvaco Polychemicals, EL360.
  • Concentration of emulsifier should vary from about 0.1%to about 15%and preferably from about 0.5%to about 6%, based on the weight of the water-immiscible material.
  • Sodium lignosulfonate emulsifier is preferentially employed at a concentration of 0.5%relative to the weight of the water-immiscible material. Higher concentrations of emulsifier may be used without increased ease of dispersability.
  • microcapsules of the present invention require no additional treatment such as separation from the aqueous liquid, but may be directly utilized or combined with, e.g., liquid fertilizers, insecticides or the like to form aqueous solutions which may be conveniently applied in agricultural uses. Most often it is most convenient to bottle or can the aqueous suspension containing the encapsulated water-immiscible material, in which case, it may be desirable to add formulation ingredients to the finished aqueous solution of microcapsules. Formulation ingredients such as thickeners, biocides, surfactants, dispersants, salts, anti-freezing agents and the like can be added to improve stability and ease of application.
  • the process of the present invention is capable of satisfactory performance and production of encapsulated material without adjustment to a specific pH value. That is, no adjustment of the pH of the system need be made during the encapsulation process.
  • conventional cooperating reagents or additions for adjustment of acidity or alkalinity, or like characteristics may be used, e.g., such substances as hydrochloric acid, sodium hydroxide, sodium carbonate, sodium bicarbonate and the like.
  • the agitation employed to establish the dispersion of water-immiscible phase droplets in the aqueous phase may be supplied by any means capable of providing suitably high shear, that is, any variable shear mixing apparatus (e.g., blender) can be usefully employed to provide the desired agitation.
  • any variable shear mixing apparatus e.g., blender
  • the desired condensation reaction at the interface between the water-immiscible phase droplets and the aqueous phase occurs very rapidly and complete within minutes. That is, the formation of the polyurethane-polyurea copolymer capsule wall has been completed, thereby encapsulating the water-immiscible material within a wall of polyurethane-polyurea copolymer and there exists a useable encapsulated product suspended in the aqueous phase.
  • the particle size of the microcapsules can be ranged from about 1 micron to about 100 microns in diameter. In general, the smaller the particle size the better. The particle size of from about 1 to about 10 microns is the optimum range. The particle size of from about 5 to about 50 microns can obtain a satisfactory formulation.
  • the particle size is controlled by the emulsifier used and the degree of agitation employed.
  • One convenient manner of controlling the size of the microcapsules is by adjusting the speed of agitation employed, which is supplied to form the dispersion of the water-immiscible phase droplets in the aqueous phase. The greater the speed of agitation at this stage, the smaller the capsules would be obtained. Control of capsule size by adjustment of the rate of agitation is well known in the art.
  • An isocyanate-terminated polyurethane prepolymers was prepared from polymethylene polyphenylisocyanate (PMPPI) , a polyoxypropylene glycol of OH Number 56 (Union Carbide NIAX Polyol PPG-2025) and a polyoxypropylene triol of OH Number 42 (Union Carbide NIAX Polyol LHT-42) .
  • the molar ratio of diol to triol was 2/1 and enough excess PMPPI was used to give an oligomer with 1.8 wt. %NCO.
  • polyurethane-polyurea copolymer was formed by adding polyfunctional amine.
  • the mixture was heated for four hours at 60°C under continuous agitation. After the initial 4 hour reaction period, 1327g of LHT 240 triol and 0.03 grams of stannous octoate were added. The temperature was maintained at 60°C until the NCO concentration was about 1.8%by weight. This typically took about 16 to 20 hours.
  • the isocyanate content of the polyurethane was determined by the di-n-butyl amine method using bromocresol green indicator.
  • the resulting isocyanate-terminated prepolymer having an NCO content of 1.78%by weight, was cooled to about 25°C and placed in a low humidity chamber.
  • Example 2 The procedure of Example 2 was repeated using various lignin sulfonate emulsifiers in place of EL360 ; the lignin sulfonate emulsifiers were: Reax Reax Marasperse Polyfon Polyfon Polyfon Reax 84A and Marasperse

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un matériau de paroi polymère à microcapsules comprenant un copolymère de polyuréthane-polyurée réticulé et sa préparation, ainsi qu'une composition comprenant un matériau non miscible dans l'eau et/ou hautement volatil encapsulé dans une microcapsule ayant une paroi comprenant le matériau de paroi polymère à microcapsules, et l'utilisation de la composition dans le contrôle de la croissance indésirable de plantes.
EP16913147.1A 2016-08-17 2016-08-17 Composition herbicide comprenant du clomazone et son utilisation Withdrawn EP3500361A4 (fr)

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US20230247986A1 (en) * 2020-06-26 2023-08-10 Bayer Aktiengesellschaft Aqueous capsule suspension concentrates comprising biodegradable ester groups
CN120957806A (zh) * 2023-01-20 2025-11-14 弗门尼舍有限公司 由聚内酯基预聚物得到的微胶囊

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Publication number Priority date Publication date Assignee Title
US3577515A (en) 1963-12-13 1971-05-04 Pennwalt Corp Encapsulation by interfacial polycondensation
US3886085A (en) * 1971-08-31 1975-05-27 Fuji Photo Film Co Ltd Process for producing fine oil-containing microcapsules having strong protective shells and microcapsules produced thereby
DE3020781C2 (de) * 1980-05-31 1982-11-18 Hoechst Ag, 6000 Frankfurt Druckbeständige Mikrokapseln mit einer Polyamid-Außenhülle und einer durch Polyurethan-Polyharnstoff oder Polyharnstoff strukturierten Innenmasse und Verfahren zu ihrer Herstellung
US5126421A (en) * 1990-04-27 1992-06-30 501 Tremco Ltd. Curing system for isocyanate prepolymers
EP1319031A2 (fr) * 2000-09-15 2003-06-18 PPG Industries Ohio, Inc. Procede de preparation de polymere reticule, sous forme de particules
DE10117784A1 (de) * 2001-04-10 2002-10-17 Bayer Ag Mikrokapseln
EP1622713A1 (fr) * 2003-05-11 2006-02-08 Ben Gurion University Of The Negev Research And Development Authority Huiles essentielles encapsulees
JP4986749B2 (ja) * 2007-07-09 2012-07-25 富士フイルム株式会社 圧力測定用材料
CN102548413A (zh) * 2009-08-07 2012-07-04 加特微胶囊股份公司 包含大环内酯阿维菌素、弥拜菌素、齐墩螨素、米尔倍霉素、埃玛菌素、伊维菌素和一般的mectins的微囊
EP2552212B8 (fr) * 2010-03-29 2015-02-25 UPL Limited Formulation améliorée
KR101961505B1 (ko) * 2011-08-10 2019-03-22 유피엘 리미티드 개선된 제초제 제형
CN105076129A (zh) * 2014-04-22 2015-11-25 广东华润涂料有限公司 驱虫微胶囊及其制备方法

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CN109562345A (zh) 2019-04-02
GB2566894B (en) 2021-10-06
EP3500361A4 (fr) 2020-01-15
WO2018032387A1 (fr) 2018-02-22
GB2566894A (en) 2019-03-27

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