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WO2018032388A1 - Composition herbicide comprenant du clomazone et utilisation de celle-ci - Google Patents

Composition herbicide comprenant du clomazone et utilisation de celle-ci Download PDF

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Publication number
WO2018032388A1
WO2018032388A1 PCT/CN2016/095620 CN2016095620W WO2018032388A1 WO 2018032388 A1 WO2018032388 A1 WO 2018032388A1 CN 2016095620 W CN2016095620 W CN 2016095620W WO 2018032388 A1 WO2018032388 A1 WO 2018032388A1
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WIPO (PCT)
Prior art keywords
microcapsules
diisocyanate
skin material
water
terminated
Prior art date
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PCT/CN2016/095620
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English (en)
Inventor
Yifan Wu
James Timothy BRISTOW
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Jiangsu Rotam Chemical Co Ltd
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Jiangsu Rotam Chemical Co Ltd
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Application filed by Jiangsu Rotam Chemical Co Ltd filed Critical Jiangsu Rotam Chemical Co Ltd
Priority to GB1901568.4A priority Critical patent/GB2567098B/en
Priority to CN201680088388.2A priority patent/CN109561695A/zh
Priority to EP16913148.9A priority patent/EP3500103A4/fr
Priority to PCT/CN2016/095620 priority patent/WO2018032388A1/fr
Publication of WO2018032388A1 publication Critical patent/WO2018032388A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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

Definitions

  • This invention concerns an improved microcapsules polymer skin material consisting of crosslinked polyepoxide –polyurea co-polymer and its preparation.
  • Capsules of this character have a variety of uses, as for containing dyes, inks, chemical reagents, pharmaceuticals, flavoring materials, pesticides, herbicides and the like.
  • the liquid or other form is preserved until it is released by some means or instrumentality that breaks, crushes, melts, dissolves, or otherwise removes the capsule skin or until release by diffusion is effected under suitable conditions.
  • the process of the invention is particularly suitable for the production of water-immiscible material containing microcapsules of very small particle size, suspended in an aqueous solution.
  • Aqueous dispersions of water-immiscible material microcapsules are particularly useful in controlled release water-immiscible material formulations because they can be diluted with water or liquid fertilizer and sprayed using conventional equipment, thereby producing uniform field coverage of the water-immiscible material.
  • Additives such as film forming agents can be added directly to the finished formulation to improve the adhesion of microcapsules to foliage. In some cases, reduced toxicity and extended activity of encapsulated water-immiscible material have been noted.
  • the present invention provides a new and improved encapsulation process which is rapid and effective and which avoids the necessity of separation of the encapsulated material from the continuous phase material.
  • the present invention also eliminates the need for using a strong solvent in the organic phase resulting in a savings of energy, and packaging and equipment ware.
  • direct combination of water-based herbicide and pesticide formulations are possible with other water-based pesticides.
  • 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 mixtures.
  • conventional oil/water herbicide emulsifiers fail to produce sufficiently stable emulsions to attain microencapsulation of concentrated amounts of herbicide materials and avoid solidification of the oil/water mass when amine is added.
  • the suspended microcapsules may be stored for extended periods of time and may be exposed for short-terms to elevated temperatures without the occurrence of agglomeration or solidification of the aqueous, capsule mass or herbicide crystal formation.
  • This invention concerns an improved microcapsules polymer skin material consisting of crosslinked polyepoxide –polyurea co-polymer and its preparation.
  • the preferred polyepoxide in this invention is diglycidyl ether of biphenyl-A (DGEBA) and its derivative.
  • DGEBA diglycidyl ether of biphenyl-A
  • Amine terminated or isocyanate terminated diglycidyl ether of biphenyl-A (DGEBA) prepolymers can be prepared first. Amine terminated DGEBA will form polyepoxide -polyurea copolymer with polyfunctional isocyanate. While isocyanate terminated DGEBA will form polyepoxide -polyurea copolymer with polyfunctional amine.
  • a water-immiscible (organic) phase which consists of a water-immiscible material (the material to be encapsulated) and diglycidyl ether of biphenyl-A (DGEBA) prepolymers, is added to an aqueous phase, with agitation, to form a dispersion of small droplets of the water-immiscible phase within the aqueous phase.
  • a polyfunctional amine preferably 1,6-hexamethylene diamine or polyfunctional isocyanate, preferably, polymethylene polyphenyl isocyanates, PMPPI is added, with continued agitation, to the organic/aqueous dispersion.
  • the polyfunctional amine or isocyanate reacts with diglycidyl ether of biphenyl-Aprepolymers to form a capsular polyepoxide –polyurea copolymer shell about the water-immiscible material.
  • the water-immiscible material referred to herein is the material to be encapsulated, such as clomazone, abamectin, pendimethalin, lambda, spinosad, emamectin benzoate, deltamethrin, cypermethrin, acetochlor, alachlor, metolachlor and their mixtures and organic solvents, e.g., xylene and monochlorobenzene are specifically contemplated herein.
  • the material to be encapsulated utilizing the process of the present invention need not consist of only one type, but may be a combination of two or more various types of water-immiscible materials.
  • water-immiscible material can be a combination of different active herbicides; or herbicides and insecticides.
  • a water-immiscible material to be encapsulated which comprises an active ingredient, such as a herbicide, and an inactive ingredient, such as a solvent or adjuvant.
  • Amine terminated diglycidyl ethers of bisphenol A having formula (I) can be prepared by reaction of polyfunctional amines with the epoxy terminated derivatives of glycidyl ethers of bisphenol A as follows:
  • N-R-N is polyamine, such as 1, 6-hexamethylene diamine; R'represents a glycidyl ether having the formula: (II)
  • n' represents 0 or a positive number having a value of 0 to 25.
  • products that are useful in the preparation of epoxy resins are provided, such products constituting epoxy terminated derivatives of polyfunctional amine and diglycidyl ethers of bisphenol A, as hereinafter defined.
  • the present invention is also directed to amine derivatives of the epoxy terminated derivatives of diglycidyl ethers of bisphenol A prepared by reacting polyfunctional amines, as hereinafter specified, with the epoxy terminated derivatives in the manner hereinafter described.
  • An advantage of both the epoxy terminated and the amine terminated derivatives of diglycidyl ethers of bisphenol is that the products are liquid at ambient temperatures and can be used as epoxy curing agents in preparing epoxy resins wherein added flexibility is an important property.
  • the solvent that should be used is either acetone or methyl ethyl ketone (MEK) .
  • the process and products of the present invention provide an improvement in the act of preparing epoxy resins wherein a significant portion of the bisphenol A component is "prereacted" prior to the final epoxy resin formation step to liquid intermediates that are easy to prepare, easy to store and easy to use.
  • an epoxy terminated derivative of bisphenol A as prepared in the manner just described is further reacted with a polyfunctional amine such as 1, 6-hexamethylene diamine.
  • the epoxy terminated diglycidyl derivative is, in effect, an intermediate reaction product and when mixed with the polyfunctional amine provides a second reaction mixture.
  • the second reaction mixture is heated at a temperature of about 100 °C to about 150 °C. for about 0.5 to about 5 hours and thereafter a tetrafunctional amine derivative is recovered.
  • epoxy terminated diglycidyl ethers of bisphenol A is prepared by the following sequence:
  • a diglycidyl ether of bisphenol A having formula IX given above is dissolved in either acetone or methyl ethyl ketone.
  • Acetone is the preferred solvent and gives the best results.
  • the thus prepared solution is added to a reaction vessel and a polyfunctional amine, such as 1, 6-hexamethylene diamine is added, the amount of polyfunctional amine added being such that there is provided about 4 to 5 moles of the diglycidyl ether per mole of polyfunctional amine.
  • the preferred ratio is about 4.5 moles of the diglycidyl ether per mole of polyfunctional amine.
  • the thus formed reaction mixture is heated with agitation at a temperature within the range of about 80°C to about 160°C. for about 1 to about 4 hours sufficient to permit the diglycidyl ether to quantitatively react with the polyfunctional amine and to substantially completely volatilize the ketone solvent initially charged to the reaction vessel. Thereafter, if desired, the epoxy terminated derivative can be recovered from the reaction mixture and will have a formula as given in formula I above.
  • polyfunctional isocyanate is added into amine terminated DGEBA, which form polyepoxide -polyurea copolymer.
  • Isocyanate terminated diglycidyl ethers of bisphenol A which are prepared by reaction polyfunctional isocyanate with the epoxy terminated derivatives of glycidyl ethers of bisphenol A as follows;
  • This invention relates to a process for the preparation of crosslinked polymers by reacting epoxide compounds, containing at least two epoxide groups in the molecule, and polyisocyanates in the presence of catalysts, such as a complex compound of BF 3 with a compound of the group comprising ethers, phosphonium compounds and H 2 O, if desired together with a compound of a metal of the group comprising Sn, Zn and Fe, which compound is soluble in the reaction mixture.
  • catalysts such as a complex compound of BF 3 with a compound of the group comprising ethers, phosphonium compounds and H 2 O, if desired together with a compound of a metal of the group comprising Sn, Zn and Fe, which compound is soluble in the reaction mixture.
  • BF 3 complexes suitable as catalysts for the process according to the invention are, in particular, BF 3 etherates of cyclic ethers, such as tetrahydrofuran and tetrahydropyrane.
  • Suitable complex compounds of BF 3 with phosphonium compounds are, for example, those based on triethyl phosphate and trimethyl phosphonate.
  • Boron trifluoride dihydrate (BF 3 .2H 2 O) is also an effective curing agent for the reactants used according to the invention.
  • the compounds of the metals Sn, Zn and Fe which can be admixed to the reaction mixture if desired, act as accelerators for the curing catalysts.
  • the following compounds are suitable examples: dibutyl-tin dilaurate, Zn naphthenate, Zn octoate, Fe naphthenate and Fe octoate.
  • the ratio is so chosen that there are 0.1 to 2.0 and preferably 0.3 to 1.2 isocyanate groups per epoxide group and BF 3 of the curing catalyst presents in a concentration of 0.2%to 0.5%by weight, based on the amount of both reactants.
  • the reaction mixture additionally also contains a polyhydroxy compound (ternary system) , the ratios in respect of the epoxide compound and the polyisocyanate are the same as in the case of the binary systems according to the invention.
  • the polyhydroxy compound is present in the system in a concentration such that there are 0.1 to 2.0 and preferably 0.2 to 1.0 OH groups per epoxide group.
  • BF 3 of the curing catalyst is contained in a concentration of 0.2%to 0.5%by weight, but in this case the percentages are based on the amount of all three reactants.
  • the concentration of the Sn, Zn or Fe compound which is soluble in the reaction mixture is 0.0001%to 0.5%and preferably 0.0002%to 0.3%by weight in both binary and the ternary systems, the percentages being based on the amount of the 2 or the 3 reactants respectively.
  • the procedure can be for all 3 reactants to be present in the reaction mixture when the reaction is initiated. In principle, however, it is also possible to proceed stepwise; i.e., prepolymers of two reactants are first prepared and the reaction is then brought to completion after adding the third component.
  • polyisocyanate prepolymers obtained from the reaction of di-or polyisocyanates with polyepoxides having no or low levels of hydroxy functionality at temperatures below about 100°C. In the absence of any catalyst contain both isocyanate and epoxide groups and these liquid prepolymers have long shelf stability.
  • a mixture of 80%-90%polyisocyanate liquid methylene bis-phenyl isocyanate having an isocyanate equivalent weight of 144) and 10%-20%of a liquid diglycidyl ether of bisphenol-A (epoxy equivalent weight of 180-190) is heated at about 60°C for about 3 hours, a liquid prepolymer is formed which has a shelf stability at room temperature of more than 2 months.
  • thermoset polymer which contains urethane, isocyanurate and oxazolidone linkages. Isocyanurate and oxazolidone groups in the polymer are believed to impart high heat deformation and thermal stability properties and the urethane linkages are believed to provide the toughness and flexibility to the polymer. In order to improve the impact strength of the thermoset polymer it is advantageous to add to the polymerization mixture soft segments such as a synthetic rubber.
  • the equivalent ratio of isocyanate to epoxy groups in the polyisocyanate-epoxy prepolymer compositions may be in the range of from 1: 0.001 to 1: 1 and preferably from 1: 0.05 to 1: 0.5.
  • the reaction of polyisocyanate and polyepoxide to form a prepolymer can be carried out at temperatures in the range of from about room temperature to about 100°C.
  • the equivalent ratio of isocyanate to combined epoxy and hydroxyl groups may be in the range of from 0.8: 1 to 3: 1.
  • the suitable catalysts for the thermoset polymer formation include cationic catalysts, tetraalkyl ammonium salts, tertiary amines, titanium alkoxides, alkali and alkaline earth metal salts, boron trihalide-tertiary amine adducts, organotin compounds, and others known to those skilled in the art.
  • the prepolymers and the thermoset polymers of this invention can contain fillers, pigments, and the like which are well known to those skilled in the art.
  • the polymerization temperature used in the preparation of the thermoset polymers of this invention can range from about room temperature to about 200°C.
  • polyfunctional amine is added into isocyanate terminated DGEBA, which form polyepoxide -polyurea copolymer.
  • 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:
  • n' 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-Amolar 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 wt. %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 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 , --C 6 H 4
  • 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.
  • Polyisocyantes which can be employed according to the invention are of both aromatic and aliphatic types. 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, isopropylbenzene
  • 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 may have any suitable particle size.
  • the average particle size of the microcapsules generally ranges 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 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.
  • emulsifiers for this purpose are sulfonates such as calcium dodecyl benzenesulfonate.
  • 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
  • POE polyoxyethylated
  • sorbitol esters such as POE (40) sorbitol hexaoleate.
  • Suitable emulsifiers are known in the art and are commercially available.
  • polyvinyl alcohol ( 203) 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.
  • an antifoam agent is a polydimethyl siloxane antifoam agent (Dow 1500) .
  • the mixture may also comprise one or more anti-freezing agent.
  • suitable anti-freezing agents are known in the art.
  • One preferred agent is propylene glycol.
  • Suitable stabilizers include calcium chloride and 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.
  • 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) .
  • 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 was used.
  • 3.000 parts by weight of epichlorohydrin and 585 parts by weight of bisphenol-A (12.6: 1 molar ratio) were fed into the flask.
  • the pressure in the apparatus was regulated to the desired value and the mass was gradually heated to boiling point.
  • 420 parts by weight of a 49%by weight aqueous solution of sodium hydroxide were introduced gradually over a period of about 5 hours.
  • the ratio of the number of moles of sodium hydroxide added to the number of phenolic hydroxyl groups is 1.00: 1.
  • the mass was kept boiling for a further 15 minutes. Then about 500 parts by weight of water were added, the mass was agitated for 20 minutes and the aqueous phase removed by decantation, operating at about 50 °C.
  • the organic phase was distilled, working first at atmospheric pressure and then at sub-atmospheric pressure (about 10 mm Hg) in order to remove the unreacted epichlorohydrin completely.
  • the distillation residue was finally filtered to remove any residual inorganic salts, using diatomaceous earth as a filter aid.
  • 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.
  • Examples 2 to 8 were carried out according to the process of the invention.
  • Example 1 was 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 was obtained with a hydrolysable chlorine content of 0.3%by weight, whilst the other characteristics of the resin remain practically unchanged.
  • Examples 2 to 8 were 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 were obtained with a hydrolysable chlorine content of from 0.02%to 0.09%by weight, whilst the other characteristics remain practically unchanged.
  • Examples 9 to 13 were 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 hydrolysable chlorine content of 0.1%-0.4%by weight whilst the other characteristics remain practically unchanged.
  • the Hazen color of the liquid epoxy resin is of the order of 200; in Examples 15-21 the Hazen color is of the order of 80-120.
  • the pressure in the apparatus is regulated to 160 mm Hg and the mixture was heated to boiling point.
  • the sodium chloride was formed as a by-product of the reaction, was removed by circulating the reaction mass continuously through a centrifuge placed outside the reactor.
  • the reaction yield is equal to 95.3%of the theoretical.
  • the epoxy resin is represented by Formula (I) with "n" equal to 0.014.
  • Example 27 was repeated, 420 parts by weight of an aqueous 49%by weight solution of sodium hydroxide being fed in.
  • the obtained epoxy resin had a hydrolyzable chlorine content of 0.06%by weight whilst the other characteristics are practically unchanged.
  • the first step requires at least a 1: 4 molar ratio of amine to epoxide.
  • Acetone or a low boiling ketone is essential for preparing these products.
  • Example 6 80 g epoxide from Example 6 was mixed well with 20 parts by weight (g) of polymethylene polyphenylisocyanate (PMPPI) , to which 0.25 part by weight (g) of BF 3 had been added beforehand in the form of a 25%tetrahydrofurfuryl alcohol complex.
  • PMPPI polymethylene polyphenylisocyanate
  • a liquid resin forms which had a pot-life of more than 1 hour at room temperature and which can be poured easily.
  • a casting After curing for 15 hours at about 150°C., a casting results which has a flexural strength of 92 N mm -2 , an impact strength of 0.76 N mm -2 , a modulus of elasticity of 3, 000 N mm -2 and a T G max (modulus of shear) of 90 °C.
  • 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. The dispersion was heated and maintained at about 50 °C for 4 hours.
  • Adjuvant such as stabilizers (1.69 g calcium chloride, 0.70 g sodium nitrate) , thickening agent (2%xanthan gum, 0.67g) , antifreeze agent (1.60 g 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. 20g 1, 6-hexamethylene diamine aqueous solution (20g diethylenetriamine in 17.3g 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.
  • 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 3
  • Example 31 and 32 were repeated for the mixture of Clomazone and any one of acetochlor, alachlor and metolachlor.

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)
  • Epoxy Resins (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne une matière de peau en polymère à microcapsules, comprenant un copolymère de polyépoxyde-polyurée réticulé, et sa préparation, ainsi qu'une composition comprenant une matière non miscible à l'eau ou une matière très volatile encapsulée à l'intérieur d'une microcapsule ayant une paroi comprenant la matière de peau en polymère à microcapsules, et l'utilisation de la composition dans la lutte contre la croissance indésirable de plantes.
PCT/CN2016/095620 2016-08-17 2016-08-17 Composition herbicide comprenant du clomazone et utilisation de celle-ci Ceased WO2018032388A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
GB1901568.4A GB2567098B (en) 2016-08-17 2016-08-17 Polymer skin material
CN201680088388.2A CN109561695A (zh) 2016-08-17 2016-08-17 含有异噁草松的除草剂组合物及其用途
EP16913148.9A EP3500103A4 (fr) 2016-08-17 2016-08-17 Composition herbicide comprenant du clomazone et utilisation de celle-ci
PCT/CN2016/095620 WO2018032388A1 (fr) 2016-08-17 2016-08-17 Composition herbicide comprenant du clomazone et utilisation de celle-ci

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3577515A (en) 1963-12-13 1971-05-04 Pennwalt Corp Encapsulation by interfacial polycondensation
GB2135469A (en) * 1983-02-14 1984-08-30 Konishiroku Photo Ind Microcapsule type toner
JPS60222870A (ja) * 1984-04-20 1985-11-07 Konishiroku Photo Ind Co Ltd マイクロカプセル型トナ−
EP0327748A1 (fr) * 1988-02-08 1989-08-16 Moore Business Forms, Inc. Microcapsules en polyurée ou en polyurée-époxy
CN102395277A (zh) * 2009-02-13 2012-03-28 孟山都技术公司 减少作物损伤的胶囊化除草剂

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2552212B8 (fr) * 2010-03-29 2015-02-25 UPL Limited Formulation améliorée
MX2012014132A (es) * 2010-06-07 2013-02-11 Syngenta Participations Ag Composicion quimica estabilizada.
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
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3577515A (en) 1963-12-13 1971-05-04 Pennwalt Corp Encapsulation by interfacial polycondensation
GB2135469A (en) * 1983-02-14 1984-08-30 Konishiroku Photo Ind Microcapsule type toner
JPS60222870A (ja) * 1984-04-20 1985-11-07 Konishiroku Photo Ind Co Ltd マイクロカプセル型トナ−
EP0327748A1 (fr) * 1988-02-08 1989-08-16 Moore Business Forms, Inc. Microcapsules en polyurée ou en polyurée-époxy
CN102395277A (zh) * 2009-02-13 2012-03-28 孟山都技术公司 减少作物损伤的胶囊化除草剂

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3500103A4

Also Published As

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EP3500103A4 (fr) 2020-01-22
CN109561695A (zh) 2019-04-02
GB2567098B (en) 2022-05-18
GB2567098A (en) 2019-04-03
EP3500103A1 (fr) 2019-06-26
GB201901568D0 (en) 2019-03-27

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