Emulsifiable concentrates and emulsion compositions

Abstract

Described herein are emulsifiable concentrate compositions, emulsion compositions, methods of making same, and methods of using same.

Description

EMULSIFIABLE CONCENTRATES AND EMULSION COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority from U.S. Provisional Patent Application No. 63 / 656,771 , filed June 6, 2024, the disclosure of which is incorporated herein by reference.FIELD

[0002] The present disclosure relates to emulsifiable concentrate compositions, emulsion compositions, methods of making same, and methods of using same.BACKGROUND

[0003] Emulsifiers, such as polymer emulsifiers and surfactant emulsifiers, are widely recognized for their ability to emulsify or stabilize emulsion or dispersion systems. They also offer rigidity at interfaces, thereby reducing coalescence and exhibiting less sensitivity to temperature changes.

[0004] Formulators must carefully select emulsifiers that exhibit positive interactions with solvents for emulsion or dispersion systems, such as solvents resulting in improved coalescence at cold temperatures. In agrochemical applications, formulators must also carefully select combinations of emulsifiers and solvents that are suitable for delivering particular agrochemical active ingredients (Als).

[0005] However, conventional emulsifiers prove inadequate in emulsifying solvents or solvent / AI mixtures at acceptable rates. Nonionic, anionic, and extended anionic emulsifiers, for instance, produce emulsions with low interfacial rigidity in highly polar solvents (e.g., anisaldehyde) / water systems. This phenomenon results from solvent molecules opening holes in the interface, thereby allowing the interface to modify its shape and ultimately accelerate the coalescence of solvent / AI mixtures. This effect is particularly pronounced at low temperatures ranging from 4-10°C.

[0006] Accordingly, there is a need for improved emulsifiers that can be used to form stable emulsifiable concentrate compositions and emulsion compositions with polar solvents.BRIEF DESCRIPTION

[0007] In one aspect, an emulsifiable concentrate (EC) composition is provided. The EC composition includes an agrochemical active ingredient including Hansen solubility parameters (HSPs) defined by (bda, 6pa, 6ha), wherein bda is in a range of from about 17.0 to about 21.5, Spa is in a range of from about 2.0 to about 20.0, and <5hais in a range of fromabout 2.0 to about 12.0; a nonpolar solvent including HSPs defined by (bdn, 6Pn, 6hn), wherein bdn is in a range of from about 15.0 to about 20.0, <5pnis in a range of from about 3.0 to about 20.0, and bhn is in a range of from about 2.0 to about 12.0; and a block emulsifier including a polar block and a nonpolar block, wherein the block emulsifier includes average HSPs defined by (bdba, 6Pba, 6hba) , wherein <5dba is in a range of from about 14.5 to about 20.0, <5pba is in a range of from about 3.0 to about 15.0, and <5ba3 is in a range of from about 4.5 to about 27.0. The nonpolar block of the block emulsifier is soluble in the nonpolar solvent and the polar block of the block emulsifier is soluble in a polar solvent.

[0008] In another aspect, a method of making an emulsifiable concentrate (EC) composition is provided. The EC composition includes an agrochemical active ingredient including HSPs defined by (bda, 6pa, 6ha), wherein bda is in a range of from about 17.0 to about 21 .5, bPa is in a range of from about 2.0 to about 20.0, and <5ha is in a range of from about 2.0 to about 12.0; a nonpolar solvent including HSPs defined by (bdn, bpn, bhn), wherein bdn is in a range of from about 15.0 to about 20.0, <5pnis in a range of from about 3.0 to about 20.0, and bhn is in a range of from about 2.0 to about 12.0; and a block emulsifier including a polar block and a nonpolar block, wherein the block emulsifier includes average HSPs defined by (bdba, 5Pba, bhba) , wherein <5dba is in a range of from about 14.5 to about 20.0, <5pba is in a range of from about 3.0 to about 15.0, and <5ba3 is in a range of from about 4.5 to about 27.0. The nonpolar block of the block emulsifier is soluble in the nonpolar solvent and the polar block of the block emulsifier is soluble in a polar solvent. The method includes forming a mixture including the agrochemical active ingredient, the nonpolar solvent, and the block emulsifier.

[0009] In another aspect, a method for controlling a pest is provided. The method includes contacting the pest or its environment with an emulsion composition. The emulsion composition includes a polar phase including: a polar solvent, wherein the polar solvent includes HSPs defined by (bdP, 6PP, 6hP), wherein <5dpis in a range of from about 15.0 to about 20.0, bppis in a range of from about 15.0 to about 18.0, and <5hpis in a range of from about 15.0 to about 45.0; a nonpolar phase including: an agrochemical active ingredient including HSPs defined by (bda, 6Pa, 6ha) , wherein <5dais in a range of from about 17.0 to about 21.5, bPa is in a range of from about 2.0 to about 20.0, and <5ha is in a range of from about 2.0 to about 12.0; and a nonpolar solvent including HSPs defined by (bdn, bpn, bhn), wherein bdn is in a range of from about 15.0 to about 20.0, <5pnis in a range of from about 3.0 to about 20.0, and bhn is in a range of from about 2.0 to about 12.0; and an interfacial phase including: a block emulsifier including a polar block and a nonpolar block, wherein the block emulsifier includes average HSPs defined by (bdba, 5Pba, bhba) , wherein <5dba is in a range offrom about 14.5 to about 20.0, bPba is in a range of from about 3.0 to about 15.0, and bba3 is in a range of from about 4.5 to about 27.0.DETAILED DESCRIPTION

[0010] It was discovered herein that a solvent or solvent / AI mixture with specific Hansen solubility parameters (HSPs) will interact positively with an emulsifier with similar HSPs. This positive interaction can manifest in various ways, depending on the formulation conditions, such as improved emulsion stability, crystal growth inhibition, and suspension stability. This positive interaction can lead to improved emulsifiable concentrate compositions and emulsion compositions.

[0011] The Hansen solubility parameters are generally measured in MPa05. These parameters are defined as follows: bd is the energy from dispersion forces between molecules; bpnis the energy from dipolar intermolecular forces between molecules; and bhn is the energy from hydrogen bonds between molecules.

[0012] The Hansen solubility parameters together make up a three-dimensional space known as the Hansen space. The relatively solubility of two molecules is directly correlated to the relative distance between the two molecules in this three-dimensional Hansen space. This relative distance is calculated as follows:

[0013] In some embodiments, active ingredients and / or solvents may comprise HSPs defined by (bd, bp, bh), wherein bd is in a range of from about 15.0 to about 20.0, bpis in a range of from about 4.0 to about 12.0, and bh is in a range of from about 2.0 to about 10.0.

[0014] Provided herein is an emulsifiable concentrate (EC) composition comprising: an agrochemical active ingredient comprising HSPs defined by (bda, bpa, bha), wherein bda is in a range of from about 17.0 to about 21.5, bpais in a range of from about 2.0 to about 20.0, and bha is in a range of from about 2.0 to about 12.0; a nonpolar solvent comprising HSPs defined by (bdn, bpn, hn), wherein bdn is in a range of from about 15.0 to about 20.0, bpnis in a range of from about 3.0 to about 20.0, and bhn is in a range of from about 2.0 to about 12.0; and a block emulsifier comprising a polar block and a nonpolar block, wherein the block emulsifier comprises average HSPs defined by (bdba, bPba, bhba), wherein bdba is in a range of from about 14.5 to about 20.0, bPba is in a range of from about 3.0 to about 15.0, and bba3 is in a range of from about 4.5 to about 27.0;wherein the nonpolar block of the block emulsifier is soluble in the nonpolar solvent and the polar block of the block emulsifier is soluble in a polar solvent.

[0015] Generally, the polar block of the block emulsifier may include any suitable HSPs known in the art that facilitate the compositions according to the present disclosure. In some embodiments, the polar block of the block emulsifier comprises HSPs defined by (6dbp, 6pbp, 6hbP) , wherein 5dbPis in a range of from about 14.0 to about 20.0, bPbPis in a range of from about 2.0 to about 15.0, and 5hbPis in a range of from about 2.0 to about 30.0.

[0016] Generally, the nonpolar block of the block emulsifier may include any suitable HSPs known in the art that facilitate the compositions according to the present disclosure. In some embodiments, the nonpolar block of the block emulsifier comprises HSPs defined by (6dbn, 6Pbn, 6hbn) , wherein bdbn is in a range of from about 15.0 to about 20.0, 5Pbn is in a range of from about 0.0 to about 12.0, and bhbn is in a range of from about 0.0 to about 25.0.

[0017] Generally, the agrochemical active ingredient may be any suitable agrochemical active ingredient known in the art that facilitates the compositions according to the present disclosure.

[0018] The agrochemical active ingredient may be any substance, whether a chemical or biological agent, used to control pests, such as insecticides, herbicides, fungicides, acaricides, rodenticides, nematicides, and miticides.

[0019] Suitable insecticides may be selected from the group consisting of neonicotinoids, bisamides, benzoylureas and carbamates.

[0020] In some embodiments, the insecticide is selected from the group of fenoxycarb, piperonyl butoxide, imidacloprid, thiacloprid, acetamiprid, aldicarb, aldicarb sulfoxide, aldicarb sulfone, pirimicarb, chlorantraniliprole, terbufos, quinalphos, dyfonate, phosmet, carbaryl, etoxazole, thiamethoxam, flonicamid, etofenprox, phorate, profenofos, parathion, methylparathion, acephate, disulfoton, fenthion, fenvalerate, fipronil, baygon, methomyl, pymetrozine, oxamyl, tau-fluvalinate, cypermethrin, cyfluthrin, bifenthrin, tetramethrin, prallethrin (mix of isomers), permethrin (mix of isomers), resmethrin (mix of isomers), pyrethrin (mix of isomers), spinetoram(J), abamectin (mix of isomers), fenobucarb (BPMC), methiocarb, isoprocarb (MIPC), spirotetramat, Spinosad, trichlorfon, fenamiphos sulfoxide, fenamiphos sulfone, 3-hydroxycarbofuran, aldrin, DDE (p-p'), DDD (o-p), DDD (p-p'), DDE (o-p), DDT (o-p1), dieldrin, endrin, endrin aldehyde, endrin ketone, isodrin, chlordecone, mirex(Dodecachlorooctahydro-1 H-1 ,3,4-(epimethanetriyl)cyclobuta[cd]pentalene), and combinations thereof.

[0021] Suitable herbicides may be selected from the group of triazines and other photosystem 2 inhibitors, 2,6-dinitroanilines, ACCase inhibitors, PPG inhibitors, syntheticauxins, sulfonyl ureas, bipyrillium herbicides, chloroacetanilides, triazolopyrimidines, pyrazoles, herbicidal safeners, and combinations thereof.

[0022] In some embodiments, the herbicide is selected from the group of paclobutrazol, diuron, linuron, isoproturon, alachlor, pendimethalin, chlorpropham, fenoprop, bentazone, metolachlor, propazine, bromacil, 2,4-DB, fenoxaprop, fluometuron, molinate, cyanazine, simazine, atrazine, atrazine desethyl, metribuzin, and combinations thereof.

[0023] Suitable fungicides may be selected from the group of pyrimidines, anilinopyrimidines, triazoles and other sterol demethylation inhibitors, triazolopyrimidines, MAP kinase inhibitors, strobilurins, adenosine deaminase inhibitors, pyrazoles, carboxamides, and combinations thereof.

[0024] In some embodiments, the fungicide is selected from the group of bitertanol, boscalid, bromuconazole, cyproconazole, diclobutrazole, diniconazole, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, myclobutanil, penconazole, propiconazole, prothioconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole,2-aminobutane, 8-hydroxyquinoline sulphate, 2- phenylphenol (OPP), aldi-morph, ampropylfos, anilazine, azoxystrobin, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, blasticidin-S, bupirimate, buthiobate, calcium polysulphide, captafol, captan, carbendazim, carboxin, carpropamid, quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cyazofamid, cymoxanil, cyprodinil, cyprofuram, dichlorophen, diclocymet, diclofluanid, diclomezin, dicloran, diethofencarb, diflumetorim, dimethirimol, dimethomorph, dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos, enestroburin, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenarimol, fenfuram, fenhexamid, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluoromide, fluoxastrobin, flusulfamide, flutolanil, folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox, guazatine, hexachlorobenzene, imazalil, iminoctadine, iprobenfos (IBP), iprodione, iprovalicarb, isoprothiolane, kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copperoxychloride, copper sulphate, copper oxide, oxinecopper and Bordeaux mixture, mancopper, mancozeb, maneb, mepanipyrim, kresoxim- methyl, mepronil, metalaxyl, methasulfocarb, methfuroxam, metiram, metominostrobin, metrafenone, metsulfovax, myclobutanil, nickel dimethyldithiocarbamate, nitrothal- isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxin, pefurazoate, pencycuron, phosdiphen, picoxystrobin, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propineb, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen, quintozene (PCNB), silthiofam, spiroxamine, sulphur and sulphurpreparations, tecloftalam, tecnazene, thiabendazole, thicyofen, thifluzamide, thiophanate- methyl, thiram, tolclophos-methyl, tolylfluanid, triazoxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, validamycin, vinclozolin, zineb, ziram, zoxamide, and combinations thereof.

[0025] Suitable acaricides may be selected from the group of tebufenpyrad, aldicard, azinphosmethyl, carbophenothion, dimethoate, dicrotophos, triazophos, malathion, phosalone, methidathion, hexythiazox, propargite, spirodiclofen, methamidophos, monocrotophos, phenthoate, pirimiphosmethyl, epn, dichlorvos, ethion, fenitrothion, diazinon, chlorpyriphos, oxydemeton methyl, pyridaben, fenpropathrin, bifenazate, spiromesifen, fenpyroximate (mix of isomers), acequinocyl, carbofuran, and combinations thereof.

[0026] One suitable rodenticide is coumaphos.

[0027] One suitable nematicide is ethoprophos.

[0028] One suitable miticide is clofentezine.

[0029] In some embodiments, the agrochemical active ingredient is selected from the group of Imidacloprid, Difenoconazole, Broflanilide, Pyroxsulam, Cloquintocet-mexyl, Pyraclostrobin, Azoxystrobin, Cyflumetofen, Mesotrione, Fenpicoxamid, Metalaxyl, S- Metolachlor, Flonicamid, cypermethrin, Bifenthrin, Pyrethrin II, Azoxystrobin, Fenbuconazole, Cyproconazole, Tebuconazole, Prothioconazole, Trifloxystrobin, and combinations thereof.

[0030] Generally, the nonpolar solvent may be any suitable nonpolar solvent known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the nonpolar solvent is selected from the group of 4-anisaldehyde (Disponil ANA), Cs N,N-dimethyl amide, C N,N-dimethyl amide, Cs / C N,N-dimethyl amide, C12 N,N-dimethyl amide, diisobutyl adipate, benzyl acetate, Agnique AE 829 (1,2-Cyclohexane dicarboxylic acid, di-isononyl ester), Agnique ME 1218 (C12-C18 fatty acid methyl esters), gamma valerolactone, 2-Ethylhexyl lactate ester, soybean oil and rapeseed oil fatty methyl esters, and combinations thereof.

[0031] Generally, the block emulsifier may be any suitable block emulsifier known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the block emulsifier is selected from the group of polyethylene oxide (PEG), polyethylene oxide comprising a number of ethylene oxide (EO) units in a range of from about 28 to about 300, polyethylene oxide comprising 200 ethylene oxide (PO) units, polypropylene oxide, polypropylene oxide comprising a number of propylene oxide units in a range of from about 12 to about 80, polypropylene oxide comprising 40 propylene oxide units, vinyl alcohol, vinyl acetate, vinyl pyrrolidone, N-vinylimidazole, vinyl caprolactam,poly(N-vinyl pyrrolidone), poly(vinyl acetate) (PVAc), poly(vinyl alcohol) (PVA), PEO-g- PVAc, polylactic acid, polylactic acid comprising a number of lactic acid units in a range of from about 1 to about 6, polylactic acid comprising 4 lactic acid units, PEO-g-PVA, monomers thereof, polymers thereof, copolymers thereof, block copolymers thereof, graft copolymers thereof, and combinations thereof.

[0032] In some embodiments, the block emulsifier is selected from the group of dodecyl benzene sulfonates, calcium dodecyl benzene sulfonate, EO-PO-EO block copolymers, castor oil ethoxylates, EO-PO block copolymers, polyvinyl acetates, vinyl pyrrolidones, ethoxylated tridecyl alcohols, copolymers based on vinyl acetate, copolymers of vinylpyrrolidone and vinylacetates, copolymers of maleic acid and acrylic acid, copolymers of vinylpyrrodidones and vinylimidazoles, tridecyl alcohol phosphates, graft copolymers of ethylene glycols and vinyl alcohols, monomers thereof, polymers thereof, copolymers thereof, block copolymers thereof, graft copolymers thereof, and combinations thereof.

[0033] Generally, the agrochemical active ingredient may be present in the EC composition in any suitable amount known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the agrochemical active ingredient is present in an amount in a range of from about 5 wt% to about 40 wt%.

[0034] Generally, the nonpolar solvent may be present in the EC composition in any suitable amount known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the nonpolar solvent is present in an amount in a range of from about 50 wt% to about 90 wt%.

[0035] Generally, the block emulsifier may be present in the EC composition in any suitable amount known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the block emulsifier is present in an amount in a range of from about 2 wt% to about 10 wt%.

[0036] Provided herein is an emulsion composition comprising: the EC composition; and the polar solvent, wherein the polar solvent comprises HSPs defined by (bdP, bPP, 6hP), wherein 6dpis in a range of from about 15.0 to about 20.0, 6PPis in a range of from about 15.0 to about 18.0, and bhPis in a range of from about 15.0 to about 45.0.

[0037] In some embodiments, the emulsion composition comprises a polar phase comprising: the polar solvent; a nonpolar phase comprising: the agrochemical active ingredient; and the nonpolar solvent; and an interfacial phase comprising: the block emulsifier.

[0038] Generally, the polar solvent may be any suitable polar solvent known in the art that facilitates the compositions according to the present disclosure. In some embodiments,the polar solvent is selected from the group of water, N,N-dimethyl lactamide (Agnique AMD 3L), propylene carbonate, and combinations thereof.

[0039] In some embodiments, the polar solvent is water. Water has two reported HSP values when in minority and majority. This is applicable in EC formulations where water may be added in small concentrations for solvency purposes. For water (majority), 6dis about 15.5, bp is about 16.0, and bh is about 42.3. For water (minority), b is about 18.1 , bpis about 17.1 , and bh is about 16.9.

[0040] Generally, the polar phase may include any suitable polar phase component known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the polar phase further comprises salts.

[0041] Generally, the nonpolar phase may include any suitable nonpolar phase component known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the nonpolar phase further comprises salts.

[0042] Generally, the agrochemical active ingredient may be present in the emulsion composition in any suitable amount known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the agrochemical active ingredient is present in an amount in a range of from about 10 wt% to about 20 wt%.

[0043] Generally, the nonpolar solvent may be present in the emulsion composition in any suitable amount known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the nonpolar solvent is present in an amount in a range of from about 70 wt% to about 80 wt%.

[0044] Generally, the block emulsifier may be present in the emulsion composition in any suitable amount known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the block emulsifier is present in an amount in a range of from about 2 wt% to about 10 wt%.

[0045] Generally, the polar solvent may be present in the emulsion composition in any suitable amount known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the polar solvent is present in an amount in a range of from about 50 wt% to about 99 wt%. In some embodiments, the polar solvent is present in an amount in a range of from about 80 wt% to about 99 wt%.

[0046] Generally, the EC concentrate composition may be present in the emulsion composition in any suitable amount known in the art that facilitates the compositions according to the present disclosure. In some embodiments, the EC concentrate composition is present in an amount in a range of from about 1 wt% to about 20 wt%. Insome embodiments, the EC concentrate composition is present in an amount in a range of from about 5 wt% to about 20 wt%.

[0047] Provided herein is a method of making an emulsifiable concentrate (EC) composition, the method comprising: forming a mixture comprising: an agrochemical active ingredient comprising HSPs defined by (bda, bpa, 6ha), wherein bda is in a range of from about 17.0 to about 21.5, 6pais in a range of from about 2.0 to about 20.0, and 6hais in a range of from about 2.0 to about 12.0; a nonpolar solvent comprising HSPs defined by (bdn, bpn, bhn), wherein 6dnis in a range of from about 15.0 to about 20.0, 6pnis in a range of from about 3.0 to about 20.0, and bhn is in a range of from about 2.0 to about 12.0; and a block emulsifier comprising a polar block and a nonpolar block, wherein the block emulsifier comprises average HSPs defined by (bdba, 6Pba, 6hba), wherein bdba is in a range of from about 14.5 to about 20.0, 6pbais in a range of from about 3.0 to about 15.0, and 6ba3 is in a range of from about 4.5 to about 27.0; wherein the nonpolar block of the block emulsifier is soluble in the nonpolar solvent and the polar block of the block emulsifier is soluble in a polar solvent.

[0048] Provided herein is a method of making an emulsion composition, the method comprising: making the EC composition; and adding the polar solvent to the EC composition, wherein the polar solvent comprises HSPs defined by (bdP, 6PP, 6hP), wherein 6dpis in a range of from about 15.0 to about 20.0, bppis in a range of from about 15.0 to about 18.0, and 6hpis in a range of from about 15.0 to about 45.0.

[0049] In many embodiments, the EC composition is diluted in water before adding to the polar solvent to the EC composition, thereby creating a spontaneous emulsion. The EC composition may be diluted in hard water or soft water at a 0.5% to 5% dilution ratio (i.e. , 95 wt% to 99.5 wt% water).

[0050] In some embodiments, the method of making the emulsion composition comprises stirring during addition of the polar solvent to the EC compositions. Stirring may ensure homogeneity of the polymer-solvent / active ingredient system.

[0051] Provided herein is a method for controlling a pest, the method comprising contacting the pest or its environment with an emulsion composition comprising: a polar phase comprising:a polar solvent, wherein the polar solvent comprises HSPs defined by (bdP, bPP, 6hP), wherein 6dpis in a range of from about 15.0 to about 20.0, 6PPis in a range of from about 15.0 to about 18.0, and 6hpis in a range of from about 15.0 to about 45.0; a nonpolar phase comprising: an agrochemical active ingredient comprising HSPs defined by (bda, 6pa, 6ha), wherein bda is in a range of from about 17.0 to about 21.5, 6pais in a range of from about 2.0 to about 20.0, and 6hais in a range of from about 2.0 to about 12.0; and a nonpolar solvent comprising HSPs defined by (bdn, bpn, bhn), wherein 6dnis in a range of from about 15.0 to about 20.0, 6pnis in a range of from about 3.0 to about 20.0, and bhn is in a range of from about 2.0 to about 12.0; and an interfacial phase comprising: a block emulsifier comprising a polar block and a nonpolar block, wherein the block emulsifier comprises average HSPs defined by (5dba, 6Pba, 6hba), wherein bdba is in a range of from about 14.5 to about 20.0, 6pbais in a range of from about 3.0 to about 15.0, and 6ba3 is in a range of from about 4.5 to about 27.0.EXAMPLES

[0052] The present technology will be further described in the following examples, which should be viewed as being illustrative and should not be construed to narrow the scope of the present disclosure or limit the scope to any particular embodiments.

[0053] Example 1 . HSPs.

[0054] HSP values were predicted for individual solvents, block emulsifiers, and agrochemical active ingredients by HSPiP software. The results are shown in the below table.Table 1. HSPs.

[0055] Example 2. No free oil.

[0056] Some compositions may exhibit a benefit of no free oil. Free oil refers to a solvent that has completely separated. Usually when emulsions separate, they cream or settle. If the separation is extreme, i.e. , no compatibility between emulsifier-solvent-water, then the solvent completely separates. In this case, where the density of solvent is high, the free oil separates and sits in the bottom. Therefore, no free oil means that a solvent is beneficially emulsified, while free oil means that a solvent is not emulsified.

[0057] In the below table, each of the components was combined with an anisaldehyde solvent (Disponil ANA) in an amount of 14 wt% polymer / surfactant in 86 wt% Disponil ANA.Table 2. No free oil components.

[0058] Example 3. Emulsifiers.

[0059] Emulsifier compositions were formed according to the below table. CE stands for comparative example and IE stands for inventive example. The units for the shown values are wt% of the EC formulation (before dilution). For each composition, 1 gram of EC (86% solvent + 14% emulsifier) was prepared and subsequently diluted in 99 mL of water.Table 3. Emulsifier compositions.

[0060] Example 4. Emulsion tests.

[0061] The emulsifiable concentrate compositions of Example 3 were combined with ANA solvent (0.86 g solvent and 0.14 g emulsifiers) and added to water (99 mL) and evaluated over time to determine the degree of emulsification. Tests were performed at 5 °C. Results are shown in the below tables.

[0062] In the below tables, X refers to “free oil”, meaning complete separation of solvent in water. For example, X.25 means that 0.25 mL of solvent was separated. 0.35 means that0.35 ml of emulsion was separated but no free oil observed. X0.25+0.1 means that 0.25 mL of solvent and 0.1 mL emulsion was separated / settled.Table 4. Emulsion tests for 342 ppm water hardness.Table 5. Emulsion tests for 1000 ppm water hardness.

[0063] It was discovered herein that compositions and methods in accordance with the present disclosure provide emulsions with remarkably improved stability, thereby enhancing their effectiveness in challenging environmental conditions such as waters with high hardness levels and low temperatures.

[0064] In particular, the addition of small amounts of polymers enhances the emulsification of solvents, such as anisaldehyde and N,N-dimethyl amides. The polymer acts as a coemulsifier by increasing the interaction between the solvent / AI, water, and other components in the system, including surfactants. This effect is particularly significant in challenging conditions, such as cold temperatures or high hardness waters.

[0065] While embodiments of the present disclosure have been described, it should be understood that the present disclosure is not so limited and modifications may be made without departing from the present disclosure. The scope of the present disclosure is defined by the appended claims, and all devices, processes, and methods that come withinthe meaning of the claims, either literally or by equivalence, are intended to be embraced therein.

[0066] Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about”, is not limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Range limitations may be combined and / or interchanged, and such ranges are identified and include all the sub-ranges stated herein unless context or language indicates otherwise. Other than in the operating examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions and the like, used in the specification and the claims, are to be understood as modified in all instances by the term “about”.

[0067] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, or that the subsequently identified material may or may not be present, and that the description includes instances where the event or circumstance occurs or where the material is present, and instances where the event or circumstance does not occur or the material is not present.

[0068] As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having”, or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article or apparatus that comprises a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0069] As used herein, the term “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0070] Where an invention or a portion thereof is defined with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the term “consisting of.”

[0071] Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of thefollowing: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0072] Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

[0073] As used herein, the term “wt%” refers to a percent by weight of the recited component relative to a total weight of the recited composition.

Claims

CLAIMSWHAT IS CLAIMED IS:

1. An emulsifiable concentrate (EC) composition comprising: an agrochemical active ingredient comprising Hansen solubility parameters (HSPs) defined by (bda, bpa, bha), wherein bda is in a range of from about 17.0 to about 21.5, Spa is in a range of from about 2.0 to about 20.0, and bha is in a range of from about 2.0 to about 12.0; a nonpolar solvent comprising HSPs defined by (bdn, bpn, bhn), wherein bdn is in a range of from about 15.0 to about 20.0, bpnis in a range of from about 3.0 to about 20.0, and bhn is in a range of from about 2.0 to about 12.0; and a block emulsifier comprising a polar block and a nonpolar block, wherein the block emulsifier comprises average HSPs defined by (bdba, 5Pba, bhba), wherein bdba is in a range of from about 14.5 to about 20.0, bPba is in a range of from about 3.0 to about 15.0, and bba3 is in a range of from about 4.5 to about 27.0; wherein the nonpolar block of the block emulsifier is soluble in the nonpolar solvent and the polar block of the block emulsifier is soluble in a polar solvent.

2. The EC composition of claim 1 , wherein the polar block of the block emulsifier comprises HSPs defined by (bdbP, 6PbP, 6hbP), wherein bdbPis in a range of from about 14.0 to about 20.0, 5pbPis in a range of from about 2.0 to about 15.0, and hbPis in a range of from about 2.0 to about 30.0.

3. The EC composition of claim 1 , wherein the nonpolar block of the block emulsifier comprises HSPs defined by ( dbn,Pbn, hbn), wherein dbn is in a range of from about 15.0 to about 20.0, pbn is in a range of from about 0.0 to about 12.0, and hbn is in a range of from about 0.0 to about 25.0.

4. The EC composition of claim 1 , wherein the agrochemical active ingredient is selected from the group of Imidacloprid, Difenoconazole, Broflanilide, Pyroxsulam, Cloquintocet-mexyl, Pyraclostrobin, Azoxystrobin, Cyflumetofen, Mesotrione, Fenpicoxamid, Metalaxyl, S-Metolachlor, Flonicamid, cypermethrin, Bifenthrin, Pyrethrin II, Azoxystrobin, Fenbuconazole, Cyproconazole, Tebuconazole, Prothioconazole, Trifloxystrobin, and combinations thereof.

5. The EC composition of claim 1 , wherein the nonpolar solvent is selected from the group of 4-anisaldehyde (Disponil ANA), Cs N,N-dimethyl amide, C N,N-dimethyl amide,Cs / C N,N-dimethyl amide, C12 N,N-dimethyl amide, diisobutyl adipate, benzyl acetate, Agnique AE 829 (1 ,2-Cyclohexane dicarboxylic acid, di-isononyl ester), Agnique ME 1218 (C12-C18 fatty acid methyl esters), gamma valerolactone, 2-Ethylhexyl lactate ester, soybean oil and rapeseed oil fatty methyl esters, and combinations thereof.

6. The EC composition of claim 1 , wherein the block emulsifier is selected from the group of polyethylene oxide (PEO), polyethylene oxide comprising a number of ethylene oxide (EO) units in a range of from about 28 to about 300, polyethylene oxide comprising 200 ethylene oxide (PO) units, polypropylene oxide, polypropylene oxide comprising a number of propylene oxide units in a range of from about 12 to about 80, polypropylene oxide comprising 40 propylene oxide units, vinyl alcohol, vinyl acetate, vinyl pyrrolidone, N- vinylimidazole, vinyl caprolactam, poly(N-vinyl pyrrolidone), poly(vinyl acetate) (PVAc), poly(vinyl alcohol) (PVA), PEO-g-PVAc, polylactic acid, polylactic acid comprising a number of lactic acid units in a range of from about 1 to about 6, polylactic acid comprising 4 lactic acid units, PEO-g-PVA, monomers thereof, polymers thereof, copolymers thereof, block copolymers thereof, graft copolymers thereof, and combinations thereof.

7. The EC composition of claim 1 , wherein the block emulsifier is selected from the group of dodecyl benzene sulfonates, calcium dodecyl benzene sulfonate, EO-PO-EO block copolymers, castor oil ethoxylates, EO-PO block copolymers, polyvinyl acetates, vinyl pyrrolidones, ethoxylated tridecyl alcohols, copolymers based on vinyl acetate, copolymers of vinylpyrrolidone and vinylacetates, copolymers of maleic acid and acrylic acid, copolymers of vinylpyrrodidones and vinylimidazoles, tridecyl alcohol phosphates, graft copolymers of ethylene glycols and vinyl alcohols, monomers thereof, polymers thereof, copolymers thereof, block copolymers thereof, graft copolymers thereof, and combinations thereof.

8. An emulsion composition comprising the EC composition of claim 1 ; and the polar solvent, wherein the polar solvent comprises HSPs defined by (bdP, bPP, 6hP), wherein 6dpis in a range of from about 15.0 to about 20.0, 6PPis in a range of from about 15.0 to about 18.0, and 6hpis in a range of from about 15.0 to about 45.0.

9. The emulsion composition of claim 8, comprising: a polar phase comprising: the polar solvent; a nonpolar phase comprising:the agrochemical active ingredient; and the nonpolar solvent; and an interfacial phase comprising: the block emulsifier.

10. The emulsion composition of claim 9, wherein the polar solvent is selected from the group of water, N,N-dimethyl lactamide (Agnique AMD 3L), propylene carbonate, and combinations thereof.11 . The emulsion composition of claim 9, wherein the polar phase further comprises a salt.

12. The emulsion composition of claim 9, wherein the nonpolar phase further comprises a salt.

13. A method of making an emulsifiable concentrate (EC) composition, the method comprising: forming a mixture comprising: an agrochemical active ingredient comprising HSPs defined by (bda, 6Pa, 6ha) , wherein bda is in a range of from about 17.0 to about 21.5, 6pais in a range of from about 2.0 to about 20.0, and 6hais in a range of from about 2.0 to about 12.0; a nonpolar solvent comprising HSPs defined by (bdn, bpn, bhn), wherein 6dnis in a range of from about 15.0 to about 20.0, 6pnis in a range of from about 3.0 to about 20.0, and bhn is in a range of from about 2.0 to about 12.0; and a block emulsifier comprising a polar block and a nonpolar block, wherein the block emulsifier comprises average HSPs defined by (bdba, 6Pba, 6hba) , wherein bdba is in a range of from about 14.5 to about 20.0, 6pbais in a range of from about 3.0 to about 15.0, and 6ba3 is in a range of from about 4.5 to about 27.0; wherein the nonpolar block of the block emulsifier is soluble in the nonpolar solvent and the polar block of the block emulsifier is soluble in a polar solvent.

14. A method of making an emulsion composition, the method comprising: making the EC composition according to claim 13; and adding the polar solvent to the EC composition, wherein the polar solvent comprises HSPs defined by (bdP, 6PP, 6hP), wherein 6dpis in a range of from about 15.0 to about 20.0, 6PPis in a range of from about 15.0 to about 18.0, and 6hpis in a range of from about 15.0 to about 45.0.

15. A method for controlling a pest, the method comprising contacting the pest or its environment with an emulsion composition comprising: a polar phase comprising: a polar solvent, wherein the polar solvent comprises HSPs defined by (bdP, bPP, 6hP), wherein bdPis in a range of from about 15.0 to about 20.0, <5PPis in a range of from about 15.0 to about 18.0, and bhPis in a range of from about 15.0 to about 45.0; a nonpolar phase comprising: an agrochemical active ingredient comprising HSPs defined by (bda, 6pa, 6ha), wherein bda is in a range of from about 17.0 to about 21 .5, <5pais in a range of from about 2.0 to about 20.0, and <5ha is in a range of from about 2.0 to about 12.0; and a nonpolar solvent comprising HSPs defined by (bdn, bpn, bhn), wherein bdn is in a range of from about 15.0 to about 20.0, <5pnis in a range of from about 3.0 to about 20.0, and bhn is in a range of from about 2.0 to about 12.0; and an interfacial phase comprising: a block emulsifier comprising a polar block and a nonpolar block, wherein the block emulsifier comprises average HSPs defined by (5dba, 5Pba, bhba) , wherein bdba is in a range of from about 14.5 to about 20.0, <5pba is in a range of from about 3.0 to about 15.0, and Sba3 is in a range of from about 4.5 to about 27.0.

Images