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Home , Cyantraniliprole, Cyphenothrin, Empenthrin, Nereistoxin, Organothiophosphate, Pyrethrin II

USOO7655597 B1

(12) United States Patent (10) Patent No.: US 7.655,597 B1 Sanders (45) Date of Patent: Feb. 2, 2010

(54) PESTICIDE COMPOSITIONS INCLUDING 4,867,972 A 9, 1989 Girardeau et al. POLYMERC AIDUVANTS 6,093,679 A 7/2000 AZuma et al. 6,146,652 A 11/2000 Gore et al. 6,515,091 B2 2/2003 Sanders et al. (75) Inventor: John Larry Sanders, Leawood, KS 6,610,282 B1 8, 2003 Ghosh (US) 6,677,399 B2 1/2004 Herbert et al. 6,703,469 B2 3/2004 Sanders et al. (73) Assignee: Specialty Fertilizer Products, LLC, 6,706,666 B2 3/2004 HaSebe et al. Leawood, KS (US) 6,897,184 B2 5/2005 Kurita et al. 7,407,667 B2 8, 2008 Zerrer et al. (*) Notice: Subject to any disclaimer, the term of this 2004/0226331 A1 11/2004 Sanders et al. patent is extended or adjusted under 35 2004/0248741 A1 12/2004 Gotsche et al. U.S.C. 154(b) by 0 days. 2005/00904O2 A1* 4/2005 Dieing et al...... 504,361 2008.0167189 A1 7/2008 Oetter et al. (21) Appl. No.: 12/534,481 2008.0171658 A1 7/2008 Dyllick-Brenzinger et al. (22) Filed: Aug. 3, 2009 * cited by examiner Primary Examiner Johann R Richter (51) Int. Cl. Assistant Examiner—Andriae M Holt AOIN 25/00 (2006.01) (74) Attorney, Agent, or Firm Hovey Williams LLP AOIN 57/26 (2006.01) AOIN 25/28 (2006.01) (57) ABSTRACT (52) U.S. Cl...... 504/116.1; 504/206; 504/360; 504/361 Pesticidal compositions of improved effectiveness are pro (58) Field of Classification Search ...... 424/406, vided, including a pesticide (e.g., an or herbicide) 424/407,408, 409; 504/116.1, 189, 206, together with a copolymer adjuvant or additive selected from 504/207, 326,360, 361 the group consisting of acid or salt copolymers containing See application file for complete search history. individual quantities of maleic and itaconic moieties. The compositions of the invention provide multiple-fold increases (56) References Cited in effectiveness, as compared with an equal amount of the U.S. PATENT DOCUMENTS pesticide in the absence of the copolymer. 4,557,929 A 12/1985 Wysong 18 Claims, No Drawings US 7,655,597 B1 1. 2 PESTICIDE COMPOSITIONS INCLUDING maleic copolymers are the preponderant polymer fraction in POLYMERC AIDUVANTS the compositions. Generally, the compositions include respective pesticide and polymeric fractions, with the poly BACKGROUND OF THE INVENTION meric fraction having at least about 60% by weight (more preferably at least about 80% by weight, and most preferably 1. Field of the Invention at least about 90% by weight) of the preferreditaconic/maleic The present invention is broadly concerned with pesticide copolymers, where the total weight of the polymer fraction is compositions and methods wherein the compositions include taken as 100% by weight. Most preferably, the polymer frac a broad class of pesticides, especially and herbi tion consists essentially of the itaconic/maleic copolymers, cides and mixtures thereof, together with an amount of a 10 i.e., it is essentially free of other types of monomers. copolymer adjuvant or additive serving to significantly The compositions of the invention can be used in essen increase the effectiveness of the pesticide. More particularly, tially any context where pesticidal properties are necessary or the invention is concerned with Such compositions and meth desirable, e.g., in agricultural uses for soil or foliar applica ods wherein a copolymer including respective quantities of tions, or onto hard Surfaces such as in home or building pest maleic and itaconic moieties is mixed or used with a selected 15 control. Likewise, the compositions may be applied by any pesticide. known means as liquids or solids. In agricultural applications, 2. Description of the Prior Art the compositions are preferably aqueous dispersions or solu The chemistries of pesticides, and especially insecticides tions, Suitable for broadcast spray application. Generally, the and herbicides, are diverse and well known. Large numbers of compositions of the invention provide at least about a two Such pesticides have been developed in the past, some of fold, and more preferably about a three-fold, greater pesti which are broad spectrum (e.g., glyphosate) while others cidal effectiveness, as compared with an equal amount of the have more specific utilities (e.g., triazine for corn). In all pesticide in the absence of the copolymer adjuvant or additive instances, however, efforts are made to minimize the use of hereof. pesticide to obtain the same or enhanced effectiveness. This is done for reasons of cost and also to minimize the environ 25 DETAILED DESCRIPTION OF THE PREFERRED mental impact of pesticidal usage. EMBODIMENTS A wide variety of adjuvants and additives have been used in the past with pesticidal formulations. These include pH modi fiers, Surfactants, anti-foam agents, anti-evaporants, buffers, The present invention is predicated upon the discovery that penetrating agents, compatibility agents, defoamers, deposi 30 the effectiveness of a wide spectrum of pesticides can be tion agents, drift-control agents with sprays, extenders, foam significantly improved by a copolymeric adjuvant or additive. ing agents, humectants, spreaders, stickers, wetting agents, Most desirably, the copolymer is blended with the pesticide to and water conditioners. While these expedients are known to form a mixture which then can be applied to soil, in foliar marginally increase pesticide performance, in general they do applications, onto hard Surfaces, as aerosols, as additives to not provide significant, multiple-fold increases in pesticidal 35 liquid or Solid compositions (e.g., manure), or in any other context where pesticidal activity is desired. Alternately, the effectiveness. pesticide and copolymer may be simultaneously or sequen There is accordingly a real and unsatisfied need in the art tially (typically within 24 hours of each other) applied to soil. for a class of adjuvants or additives which can very signifi Where mixed compositions are employed, they are typically cantly increase the effectiveness of pesticides without them in the form of aqueous dispersions or solutions, generally selves posing excessive cost or environmental impact prob 40 having water, pesticide, and copolymer fractions. Other lems. minor ingredients may also be used in the compositions such SUMMARY OF THE INVENTION as Surfactants and pH adjustment agents, or any of the other aforementioned adjuvants or additives known in the art. The present invention overcomes the problems outlined 45 The pesticides used in the compositions of the invention above and provides pesticide compositions comprising are broadly selected from insecticides and herbicides. In the respective quantities of a pesticide and a copolymer contain context of insecticides, synthetic and organo ing individual quantities of maleic and itaconic moieties. The phosphates are particularly preferred. For example, per pesticide component can be any agent with pesticidal activity methrin (C21H20C1203, (3-phenoxyphenyl)methyl 3-(2,2- (e.g., herbicides, insecticides, fungicides, and nematocides) 50 dichloroethenyl)-2,2-dimethyl-cyclopropane-1-carboxylate, and is preferably selected from the group consisting of insec CAS#52645-53-1) and (C23H22ClF302, (2-me ticides, herbicides, and mixtures thereof. The well known thyl-3-phenylphenyl)methyl (1S,3S)-3-(Z)-2-chloro-3,3,3- and pesticides are Suitable for trifluoroprop-1-enyl-2,2-dimethylcyclopropane-1-carboxy use in the invention, as well as glyphosate herbicides. late, CASH82657-04-3) are suitable pyrethroids. A typical The preferred copolymer adjuvants of the invention are the 55 organophosphate pesticide useful in the invention is copolymers containing maleic and itaconic moieties, usually (C10H1906PS2.2-(dimethoxyphosphi derived from the corresponding acids or anhydrides. While nothioylthio) butanedioic acid diethyl ester, CASH 121-75-5). other monomers may also be used in the maleic-itaconic More generally, the following insecticides are useful in the copolymers, it is preferred that these be present only in minor invention: amounts of up to about 7% by weight, more preferably up to 60 antibiotic insecticides: allosamidin, thuringiensin about 4% by weight. Stated otherwise, the copolymers should comprise at least about 93% by weight, more preferably about macrocyclic lactone insecticides 96% by weight, of itaconic and maleic monomers. Most avermectin insecticides: abamectin, doramectin, ema preferably, the copolymer consists essentially of or is entirely mectin, eprinomectin, ivermectin, Selamectin made up of maleic and itaconic moieties. Furthermore, while 65 milbemycin insecticides: lepimectin, ilbemectin, milbe other polymers or copolymers can form a part of the compo mycin Oxime, moxidectin sitions of the invention, in preferred aspects, the itaconic/ spinosyn insecticides: spinetoram, US 7,655,597 B1 3 4 arsenical insecticides: , copper acetoarsen organochlorine insecticides: bromo-DDT, camphechlor, ite, copper arsenate, lead arsenate, potassium arsenite, DDT (pp'-DDT), ethyl-DDD, HCH (gamma-HCH, lin Sodium arsenite dane), , pentachlorophenol, TDE botanical insecticides: , , d-, cyclodiene insecticides: , bromocyclen, chlorbicy nicotine, (cinerins (cinerin I, cinerin II), jasmo 5 clen, , , , dilor, lin I, jasmolin II, I, pyrethrin II), quassia, roten (alpha-endosulfan), , HEOD, , HHDN, one, ryania, Sabadilla , isodrin, kelevan, insecticides: , organophosphorus insecticides benzofuranyl methylcarbamate insecticides: benfuracarb, organophosphate insecticides: bromfenVinfos, chlorfen , , decarbofuran, furathiocarb 10 vinphos, crotoxyphos, , , dimeth dimethylcarbamate insecticides: dimetan, , ylvinphos, fospirate, heptenophos, methocrotophos, hyduincarb, , , , naftalofos, phos Oxime carbamate insecticides: alanycarb, , aldoxy phamidon, propaphos, TEPP, carb, , butoxycarboxim, . nit organothiophosphate insecticides: dioxabenzofos, foSme rilacarb, , tazimcarb, thiocarboxime, thiodicarb, 15 thilan, aliphatic organothiophosphate insecticides: acethion, phenyl methylcarbamate insecticides: allyxycarb, ami amiton, cadusafos, , chlormephos, nocarb, bufencarb, butacarb, carbanolate, cloethocarb, (demephion-O, demephion-S), dicresyl, dioxacarb, EMPC, ethiofencarb, fenethacarb, (demeton-O, demeton-S), demeton-methyl (deme , isoprocarb, , , mexac ton-O-methyl, demeton-S-methyl), demeton-S-me arbate, promacyl, promecarb, , trimethacarb, thylsulphon, , , , IPSP. XMC, xylylcarb isothioate, malathion, methacrifos, oxydemeton-me desiccant insecticides: , diatomaceous earth, silica thyl, oxydeprofos, OXydisulfoton, , Sulfotep, gel , thiometon diamide insecticides: , , 25 aliphatic amide organothiophosphate insecticides: amidithion, cyanthoate, , ethoate-me dinitrophenol insecticides: dinex, dinoprop, dinosam, DNOC thyl, , mecarbam, , pro fluorine insecticides: barium hexafluorosilicate, cryolite, thoate, Sophamide, Vamidothion sodium fluoride, sodium hexafluorosilicate, sulfluramid Oxime organothiophosphate insecticides: chlor formamidine insecticides: , , formet 30 , phoxim, phoxim-methyl anate, heterocyclic organothiophosphate insecticides: azame fumigant insecticides: acrylonitrile, carbon disulfide, carbon thiphos, , coumithoate, , endot tetrachloride, chloroform, chloropicrin, para-dichloroben hion, menazon, morphothion, , pyraclofos, Zene, 1,2-dichloropropane, ethyl formate, ethylene dibro pyridaphenthion, quinothion mide, ethylene dichloride, ethylene oxide, hydrogen cya 35 benzothiopyran organothiophosphate insecticides: nide, iodomethane, methyl bromide, methylchloroform, dithicrofos, thicrofos methylene chloride, naphthalene, phosphine, Sulfuryl fluo benzotriazine organothiophosphate insecticides: ride, tetrachloroethane azinphos-ethyl, azinphos-methyl inorganic insecticides: borax, boric acid, calcium polysulfide, isoindole organothiophosphate insecticides: dialifos, copper oleate, diatomaceous earth, mercurous chloride, 40 potassium thiocyanate, silica gel, Sodium thiocyanate, see isoxazole organothiophosphate insecticides: isox also arsenical insecticides, see also fluorine insecticides athion, ZolaprofoS insect growth regulators pyrazolopyrimidine organothiophosphate insecti chitin synthesis inhibitors: bistrifluoron, , chlo cides: chlorpraZophos, pyrazophos rfluaZuron, , , flucycloXuron, 45 pyridine organothiophosphate insecticides: chlorpy , hexaflumuron, , novaluron, rifos, -methyl noviflumuron, penfluoron, teflubenzuron, triflumuron pyrimidine organothiophosphate insecticides: juvenile hormone mimics: epolfenonane, , butathiofos, , etrimfos, lirimfos, pirimi , kinoprene, , , tri phos-ethyl, pirimiphos-methyl, primidophos, 50 pyrimitate, prene quinoxaline organothiophosphate insecticides: juvenile hormones: juvenile hormone I, juvenile hormone , quinallphos-methyl II, juvenile hormone III thiadiazole organothiophosphate insecticides: athi moulting hormone agonists: chromafenozide, dathion, lythidathion, , prothidathion halofenozide, methoxyfenozide, 55 triazole organothiophosphate insecticides: isazofos, moulting hormones: a-ecdysone, ecdysterone triaZophos moulting inhibitors: diofenolan phenyl organothiophosphate insecticides: azothoate, precocenes: precocene I, precocene II, precocene III bromophos, bromophos-ethyl, , unclassified insect growth regulators: dicyclanil chlorthiophos, , cythioate, dicapthon, analogue insecticides: benSultap, cartap, thiocy 60 dichlofenthion, etaphos, famphur, fenchlorphos, feni clam, thiosultap trothion, fensulfothion, , fenthion-ethyl, het nicotinoid insecticides: flonicamid erophos, jodfenphos, mesulfenfos, , par nitroguanidine insecticides: , , imi athion-methyl, phenkapton, phosnichlor, , dacloprid, prothiofos, Sulprofos, temephos, trichlorimetaphos-3. nitromethylene insecticides: , 65 trifenofos pyridylmethylamine insecticides: , imidaclo phosphonate insecticides: butonate, trichlorfon prid, nitenpyram, phosphonothioate insecticides: mecarphon US 7,655,597 B1 5 6 phenyl ethylphosphonothioate insecticides: , metamifop, monalide, naproanilide, pentanochlor, trichloronat picolinafen, propanil, SulfentraZone phenyl phenylphosphonothioate insecticides: cyanofen arylalanine herbicides: benzoylprop, flamprop (flam phos, EPN, prop-M), phosphoramidate insecticides: crufomate, , chloroacetanilide herbicides: acetochlor, alachlor, fosthietan, mephosfolan, , pirimetaphos butachlor, butenachlor, delachlor, diethatyl, dimeth phosphoramidothioate insecticides: , isocarbo achlor, metaZachlor, metolachlor (S-metolachlor), phos, isofenphos, isofenphos-methyl, , pretilachlor, propachlor, propisochlor, prynachlor, propetamphos terbuchlor, thenylchlor, xylachlor phosphorodiamide insecticides: , mazidox, 10 Sulfonanilide herbicides: benzofluor, cloransulam, , dicloSulam, florasulam, flumetSulam, metoSulam, oxadiazine insecticides: perfluidone, pyrimisulfan, profluaZol oxadiazolone insecticides: metoxadiaZone Sulfonamide herbicides: asulam, carbasulam, fenasulam, phthalimide insecticides: dialifos, phosmet, oryzalin, penoXSulam, pyroxSulam, see also Sulfony insecticides: chlorantraniliprole, cyantraniliprole, 15 lurea herbicides dimetilan, , tolfenpyrad thioamide herbicides: bencarbazone, chlorthiamid phenylpyrazole insecticides: acetoprole, ethiprole, antibiotic herbicides: bilanafos , pyraclofos, pyrafluprole, , Vaniliprole aromatic acid herbicides: pyrethroid insecticides benzoic acid herbicides: chloramben, dicamba, pyrethroid ester insecticides: , allethrin (bioal 2,3,6-TBA, tricamba lethrin), barthrin, bifenthrin, bioethanomethrin, cyclethrin, pyrimidinyloxybenzoic acid herbicides: bispyribac, cycloprothrin, (beta-cyfluthrin), , pyriminobac (gamma-cyhalothrin, lambda-cyhalothrin), pyrimidinylthiobenzoic acid herbicides: pyrithiobac (alpha-cypermethrin, beta-cypermethrin, theta-cyper phthalic acid herbicides: chlorthal methrin, Zeta-cypermethrin), , , 25 picolinic acid herbicides: aminopyralid, clopyralid, piclo dimefluthrin, dimethrin, , fenfluthrin, fen al pirithrin, fempropathrin, (), quinolinecarboxylic acid herbicides: quinclorac, quin flucythrinate, fluvalinate (tau-fluvalinate), furethrin, imi CaC prothrin, , (biopermethrin, arsenical herbicides: cacodylic acid, CMA, DSMA, hexaflu transpermethrin), , , profluthrin, 30 rate, MAA, MAMA, MSMA, potassium arsenite, sodium pyresmethrin, (bioresmethrin, cismethrin), arsenite , terallethrin, tetramethrin, , trans benzoylcyclohexanedione herbicides: mesotrione, Sulcotri fluthrin one, tefuryltrione, tembotrione pyrethroid ether insecticides: etofemprox, flufenprox, halfen benzofuranyl alkylsulfonate herbicides: benfuresate, etho prox, protrifenbute, 35 fumesate pyrimidinamine insecticides: flufenerim, pyrimidifen benzothiazole herbicides: benazolin, benzthiaZuron, fenthi pyrrole insecticides: aprop, mefenacet, methabenzthiazuron tetramic acid insecticides: Spirotetramat carbamate herbicides: asulam, carboxazole, chlorprocarb, tetronic acid insecticides: Spiromesi?en dichlormate, fenasulam, karbutilate, terbucarb thiazole insecticides: clothianidin, thiamethoxam 40 carbanilate herbicides: barban, BCPC, carbasulam, carbeta thiazolidine insecticides: taZimcarb, thiacloprid mide, CEPC, chlorbufam, chlorpropham, CPPC, desme thiourea insecticides: diafenthiuron dipham, phenisopham, phenmedipham, phenmedipham urea insecticides: flucofuron, Sulcofuron, see also chitin Syn ethyl, propham, Swep thesis inhibitors cyclohexene oxime herbicides: alloxydim, butroxydim, unclassified insecticides: closantel, copper naphthenate, 45 clethodim, cloproxydim, cycloxydim, profoxydim, set crotamiton, EXD, fenazaflor, fenoxacrim, hydramethyl hoxydim, tepraloxydim, tralkoxydim non, isoprothiolane, malonoben, , niflurid cyclopropylisoxazole herbicides: isoxachlortole, isoxaflutole ide, plifenate, pyridaben, pyridalyl, pyrifluquinazon, dicarboximide herbicides: cinidon-ethyl, flumezin, flumiclo rafoxanide, , triarathene, triaZamate. rac, flumioxazin, flumipropyn, see also uracil herbicides The foregoing insecticides, and links for a further identifi 50 dinitroaniline herbicides: benfluralin, butralin, dinitramine, cation and description of the insecticides, can be found at ethalfluralin, fluchloralin, isopropalin, methalpropalin, http://www.alanwood.net/pesticides/class insecticides.h- nitralin, ory Zalin, pendimethalin, prodiamine, profluralin, tml, which is incorporated herein in its entirety. trifluralin A particularly preferred herbicide is glyphosate dinitrophenol herbicides: dinofenate, dinoprop, dinosam, (C3H8NO5P (phosphonomethyl)amino acetic acid, 55 dinoseb, dinoterb, DNOC, etinofen, medinoterb CAS#1071-83-6). Other herbicides which can be used in the diphenyl ether herbicides: ethoxyfen invention include: nitrophenyl ether herbicides: acifluorfen, aclonifen, amide herbicides: allidochlor, amicarbazone, beflubutamid, bifenox, chlomethoxyfen, chlornitrofen, etnipromid, benzadox, benzipram, bromobutide, cafenstrole, CDEA, fluorodifen, fluoroglycofen, fluoronitrofen, fomesafen, cyprazole, dimethenamid (dimethenamid-P), diphenamid, 60 furyloxyfen, halosafen, lactofen, nitrofen, nitrofluorfen, epronaz, etnipromid, fentraZamide, flucarbazone, oxyfluorfen flupoxam, fomesafen, halosafen, isocarbamid, isoxaben, dithiocarbamate herbicides: dazomet, metam napropamide, naptalam, pethoxamid, propyZamide, halogenated aliphatic herbicides: allorac, chloropon, dalapon, quinonamid, saflufenacil, tebutam flupropanate, hexachloroacetone, iodomethane, methyl anilide herbicides: chloranocryl, cisanilide, clomeprop, 65 bromide, monochloroacetic acid, SMA, TCA cypromid, diflufenican, etobenzanid, fenasulam, flufen imidazolinone herbicides: imazamethabenZ, imaZamox, acet, flufenican, ipfencarbazone, mefenacet, mefluidide, imaZapic, imazapyr, imaZaquin, imaZethapyr US 7,655,597 B1 7 8 inorganic herbicides: ammonium Sulfamate, borax, calcium triazinone herbicides: ametridione, amibuzin, hexaZinone, chlorate, copper Sulfate, ferrous Sulfate, potassium azide, isomethiozin, metamitron, metribuzin potassium cyanate, sodium azide, Sodium chlorate, Sulfu triazole herbicides: amitrole, cafenstrole, epronaz, flupoxam ric acid triazolone herbicides: amicarbazone, bencarbazone, carfen nitrile herbicides: bromobonil, bromoxynil, chloroxynil, traZone, flucarbazone, ipfencarbazone, propoxycarbazone, dichlobenil, iodobonil, ioxynil, pyraclonil SulfentraZone, thiencarbazone organophosphorus herbicides: amiprofoS-methyl, anilofos, triazolopyrimidine herbicides: cloranSulam, diclosulam, flo , bilanafos, butamifos, 2,4-DEP, DMPA, EBEP, rasulam, flumetSulam, metoSulam, penoXSulam, pyroxSu fosamine, glufosinate (glufosinate-P), glyphosate, pipero lam phos 10 uracil herbicides: benzfendizone, bromacil, butafenacil, flu oxadiazolone herbicides: dimefuron, methazole, oxadiargyl. propacil, isocil, lenacil, saflufenacil, terbacil oxadiaZon urea herbicides: benzthiazuron, cumyluron, cycluron, dichlo oxazole herbicides: carboxazole, fenoxasulfone, isouron, railurea, diflufenZopyr, isonoruron, isouron, methabenz isoxaben, isoxachlortole, isoxaflutole, monisouron, thiaZuron, monisouron, noruron pyroxasulfone, toprameZone 15 phenylurea herbicides: anisuron, buturon, chlorbromuron, phenoxy herbicides: bromofenoxim, clomeprop, 2,4-DEB, chloreturon, chlorotoluron, chloroXuron, daimuron, 2,4-DEP, difenopenten, disul, erbon, etnipromid, fentera difenoXuron, dimefuron, diuron, fenuron, fluometuron, col, trifopsime fluothiuron, isoproturon, linuron, methiuron, meth phenoxyacetic herbicides: 4-CPA, 2,4-D, 3,4-DA, MCPA, yldymron, metobenzuron, metobromuron, metoXuron, MCPA-thioethyl, 2,4,5-T monolinuron, monuron, neburon, parafluoron, phe phenoxybutyric herbicides: 4-CPB, 2,4-DB, 3,4-DB, nobenzuron, Siduron, tetrafluoron, thidiaZuron MCPB, 2,4,5-TEB sulfonylurea herbicides: phenoxypropionic herbicides: cloprop, 4-CPP, dichlorprop pyrimidinylsulfonylurea herbicides: amidosulfuron, (dichlorprop-P), 3,4-DP, fenoprop, mecoprop, (meco azimsulfuron, benSulfuron, chlorimuron, cyclosulfa prop-P) 25 muron, ethoxysulfuron, flaZaSulfuron, flucetosulfu aryloxyphenoxypropionic herbicides: chloraZifop, clo ron, flupyrsulfuron, foramsulfuron, halosulfuron, dinafop, clofop, cyhalofop, diclofop, fenoxaprop, imaZoSulfuron, mesosulfuron, metazosulfuron, nico (fenoxaprop-P), fenthiaprop, fluazifop, (fluazifop-P), Sulfuron, orthosulfamuron, oxasulfuron, primisulfu haloxyfop, (haloxyfop-P), isoxapyrifop, metamifop, ron, propyrisulfuron, pyrazosulfuron, rimsulfuron, propaquizafop, quizalofop, (quizalofop-P), trifop 30 sulfometuron, sulfosulfuron, trifloxysulfuron phenylenediamine herbicides: dinitramine, prodiamine triazinylsulfonylurea herbicides: chlorsulfuron, cinosul pyrazole herbicides: azimsulfuron, difenZoquat, halosulfu furon, ethametsulfuron, iodosulfuron, metSulfuron, ron, metaZachlor, metaZoSulfuron, pyrazosulfuron, prosulfuron, thifensulfuron, triasulfuron, tribenuron, pyroxasulfone triflusulfuron, tritosulfuron benzoylpyrazole herbicides: benzofenap, pyrasulfotole, 35 thiadiazolylurea herbicides: buthiuron, ethidimuron, pyrazolynate, pyrazoxyfen, toprameZone tebuthiuron, thiazafluoron, thidiaZuron phenylpyrazole herbicides: fluazolate, nipyraclofen, unclassified herbicides: acrolein, allyl alcohol, aminocyclo pinoxaden, pyraflufen pyrachlor, azafenidin, bentaZone, benzobicyclon, bicyclo pyridazine herbicides: credazine, pyridafol, pyridate pyrone, buthidazole, calcium cyanamide, cambendichlor, pyridaZinone herbicides: brompyrazon, chloridazon, dimida 40 chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, Zon, flufenpyr, metflurazon, norflurazon, oxapyrazon, cinmethylin, clomazone, CPMF, cresol, cyanamide, ortho pydanon dichlorobenzene, dimepiperate, endothal, fluoromidine, fluridone, fluorochloridone, flurtamone, fluthiacet, indano pyridine herbicides: aminopyralid, cliodinate, clopyralid, fan, methyl isothiocyanate, OCH, oxaziclomefone, pen diflufenican, dithiopyr, flufenican, fluoroxypyr, haloxy 45 tachlorophenol, pentoxaZone, phenylmercury acetate, pro dine, picloram, picolinafen, pyriclor, pyroxSulam, thiaz Sulfalin, pyribenzoxim, pyriftalid, quinoclamine, opyr, triclopyr rhodethanil, Sulglycapin, thidiazimin, tridiphane, trimetu pyrimidinediamine herbicides: iprymidam, tioclorim ron, tripropindan, tritac. quaternary ammonium herbicides: cyperquat, diethamduat, difenZoquat, diguat, morfamquat, paraquat The foregoing herbicides, and links for a further identifi 50 cation and description of the herbicides, can be found at thiocarbamate herbicides: butylate, cycloate, di-allate, http://www.alanwood.net/pesticides/class herbicides.html, EPTC, esprocarb, ethiolate, isopolinate, methiobencarb, which is incorporated herein in its entirety. molinate, orbencarb, pebulate, prosulfocarb, pyributicarb, In many instances, pesticides having an amphoteric or sulfallate, thiobencarb, tiocarbazil, tri-allate, Vernolate positive surface charge are preferred. Such surface charge thiocarbonate herbicides: dimexano, EXD, proxan 55 characteristics may be inherent in the pesticide employed, or thiourea herbicides: methiuron may arise by applying an appropriate cationic or amphoteric triazine herbicides: dipropetryn, indaziflam, triaziflam, trihy Surfactant onto the Surfaces of pesticide particles. Generally, droxytriazine the surfactants are used at a level of from about 0.01-10% by chlorotriazine herbicides: atrazine, chlorazine, cyanazine, weight (more preferably from about 0.1-3% by weight) based cyprazine, eglinazine, ipazine, mesoprazine, pro 60 upon the total weight of the pesticide fraction in the overall cyazine, proglinazine, propazine, Sebuthylazine, composition taken as 100% by weight. simazine, terbuthylazine, trietazine Suitable cationic surfactants include: dieicosyldimethyl methoxytriazine herbicides: atraton, methometon, prome ammonium chloride; didocosyldimethyl ammonium chlo ton, secbumeton, Simeton, terbumeton ride; dioctadecyldimethyl ammonium chloride; dioctade methylthiotriazine herbicides: ametryn, aziprotryne, 65 cyldimethyl ammonium methoSulphate; ditetradecyldim cyanatryn, desmetryn, dimethametryn, methoprotryne, ethyl ammonium chloride and naturally occurring mixtures prometryn, simetryn, terbutryn of above fatty groups, e.g. di(hydrogenated tallow)dimethyl US 7,655,597 B1 9 10 ammonium chloride; di(hydrogenated tallow)dimethyl larly the akali metals and alkaline earth metals, e.g., the ammonium metho-Sulphate; ditallow dimethyl ammonium Sodium, potassium, or calcium salts. chloride; and dioleyidimethyl ammonium chloride. The copolymers of the invention are described in U.S. Pat. These cationic Surfactants also include imidazolinium Nos. 6,515,090 and 6,706,837, both fully and completely compounds, for example, 1-methyl-1-(tallowylamido-)ethyl incorporated by reference herein, with special reference to the 2-tallowy14,5-dihydroimidaz-olinium methosulphate and operative examples of the 837 patent. In general, the copoly 1-methyl-1-(palmitoylamido)ethyl-2-octadecyl 4,5-dihydro mers should desirably contain from about 10-90% by weight imidazolinium methosulphate. Other useful imidazolinium maleic moieties (more preferably from about 25-75% by materials are 2-heptadecyl-1-methyl-1(2-stearoylamido)- weight), and correspondingly from about 90-10% by weight ethyl-imidazoliniu-m methoSulphate and 2-lauryl-lhydroxy 10 itaconic moieties (more preferably from about 75-25% by ethyl-1-oleyl-imidazolinium chloride. weight). One particularly preferred copolymer of this class is Further examples of suitable cationic surfactants include: commercialized by Specialty Fertilizer Products, LLC of dialkyl (C12-C22)dimethylammonium chloride; alkyl (coco Belton, Mo. under the trademark AVAIL(R), which is a 40% by nut)dimethylbenzylammonium chloride; octadecylamine weight solids aqueous copolymer dispersion of Substantially acetate salt, tetradecylamine acetate salt; tallow alkylpropy 15 equimolaramounts ofitaconic and maleic anhydride moieties lenediamine acetate salt; octadecyltrimethylammonium partially neutralized with sodium ion (CASH 556055-76-6) chloride; alkyl(tallow)trimethylammonium chloride; dode and having a pH of 6-8. cyltrimethylammonium chlorid; alkyl (coconut)trimethylam The amount of copolymer in the pesticide compositions of monium chloride; hexadecyltrimethylammonium chloride; the invention can vary over wide limits, and the principal biphenyltrimethylammonium chloride, alkyl (tallow)imida consideration is one of copolymer cost. Generally, the Zoline quaternary salt; tetradecylmethylbenzylammonium copolymer should be present at a level of from about 0.05 chloride; octadecyldimethylbenzylammonium chloride; dio 10% by weight (more preferably from about 0.1-4% by leyidimethylammonium chloride; polyoxyethylene dodecyl weight, and most preferably from about 0.2-2% by weight) monomethylammonium chloride; polyoxyethylene alkyl based upon the total weight of the pesticide composition (C12-C22)benzylammonium chloride; polyoxyethylene 25 taken as 100% by weight. laurylmonomethyl ammonium chloride, 1-hydroxyethyl-2- The copolymer is preferably used in the form of a partial alkyl(tallow)-imidazoline quaternary salt; and a silicone cat salt or a saturated salt. This is formed by the addition of a ionic Surfactant having a siloxane group as a hydrophobic basic material Such as Sodium hydroxide or calcium hydrox group, a fluorine-containing cationic Surfactant having a fluo ide to achieve a pH in the range of from about 5-9, and more roalkyl group as a hydrophobic group. 30 preferably from about 6-8. Lower pH acidic or partial salt Amphoteric (Zwitterionic) surfactants have a positive, copolymers can also be used, particularly with selected negative, or both charges on the hydrophilic part of the mol monomer ratios and pesticides. Generally, the pH should ecule in acidic or alkaline media. Any Suitable amphoteric range from about 2-8. Surfactant may be used. For example, aminoproprionates may The pesticide compositions of the invention, containing be employed where the alkyl chain of the aminoproprionate is 35 only a very minor amount of copolymer adjuvant, can be used preferably between about C.4 and about C.12 and may be at the same levels of use as the standard pesticide products branched or linear. The aminoproprionate may also be a without adjuvant. These levels vary between different pesti Sodium alkylaminoproprionate. One representative commer cides, and the levels of use are well known in theart. However, cially available product is sold under the trade name owing to the synergistic effects of the copolymers, lesser MIRATAINE JC-HA. 40 usage levels may be appropriate. Other suitable amphoteric surfactants include, diproprion The compositions and methods of the invention provide a ates such as Mirataine H2C-HA, Sultaines such as Mirataine greater pesticidal effectiveness as compared with the use of ASC, betaines such as Mirataine BET-O-30, amine oxides equal amount of the selected pesticide alone. Preferably, this such as Barlox 12i and amphoteric imidazoline derivatives in increase should be at least about a three-fold greater effec the acetate form, Miranol JEM Conc, diproprionate form, 45 tiveness, and more preferably a four-fold increase in effec Miranol C2M-SF Conc.), and sulfonates such as Miranol JS tiveness. Conc. The following examples set forth preferred compositions Other examples of amphoteric Surfactants include amino of the invention and pesticidal utilities thereof. It is to be acid, betaine, Sultaine, Sulfobetaines, carboxylates and Sul understood, however, that these examples are provided by fonates of fatty acids, phosphobetaines, imidazolinium 50 way of illustration and nothing therein should be taken as a derivatives, soybean phospholipids, yolk lecithin, the alkali limitation upon the overall scope of the invention. metal, alkaline earth metal, ammonium or Substituted ammo nium salts of alkyl amphocarboxy glycinates and alkyl EXAMPLE 1. amphocarboxypropionates, alkyl amphodipropionates, alkyl amphodiacetates, alkyl amphoglycinates and alkyl amphop 55 In this example a series of commercially available insecti ropionates wherein alkyl represents an alkyl group having 6 cides were tested at various dilution levels and with and to 20 carbon atoms, alkyliminopropionates, alkyl imino without a preferred copolymer, namely the AVAILR) copoly dipropionates and alkyl amphopropylsulfonates having mer previously described (a 40%-60% w/w aqueous compo between 12 and 18 carbon atoms, alkylbetaines and ami sition of a saturated sodium salt of a maleic anhydridefita dopropylbetaines and alkylsultaines and alkylamidopropyl 60 conic acid copolymer in water). In each set of test runs, the hydroxy Sultaines wherein alkyl represents an alkyl group selected insecticide was tested with a population offire ants in having 6 to 20 carbon atoms. order to determine the time required to kill the entire popu As indicated above, the copolymers of the invention con lation. As explained above, the presence of the copolymer tain respective quantities of maleic and itaconic moieties. gave a distinct adjuvant effect and significantly increased the These copolymers may exist in the acid form, as partial salts, 65 potency of the insecticides. or as Saturated salts. When salts are employed, such can be In particular, in each test run 20 ml of the respective liquid formed using virtually any desired cationic species, particu insecticide composition was added to a masonjar and Swirled US 7,655,597 B1 11 12 around the inside bottom thereof. The liquid was then poured The test products were then used in the same fire ant kill off and the remainder was allowed to dry on the inner jar experiment of Example 1, giving the data of Tables 2 and 3. Surface, creating Substantially a monomeric dried layer. The outside neck Surface of the jar was then coated in talc, and the TABLE 2 open end of the jar was placed into a fire ant nest. The talc coating prevented the aggressive fire ants from climbing the TIME TO outer Surface of the jar. A population of fire ants was thus NSECTICIDE COMPOSITION pH DEATH (MIN) established in each jar, and the jar was then topped with an f100X malathion 14 apertured mason jar cap. The time to death of all of the fire Polymaleic Acid + 1/100X malathion 6 9.5 ants was then recorded. 10 Polymaleic Acid + 1/100X malathion 7 9 Polymaleic Acid + 1/100X malathion 8 8 In each case, the recommended concentration of insecti :3 Maleic Anhydride/Itaconic Acid Copolymer + 8 cide was prepared (recorded as “1X), followed by dilutions f100X malathion with water to create the diluted compositions. Where copoly :3 Maleic Anhydride/Itaconic Acid Copolymer + 6 7 f100X malathion mer was used, the copolymer was added to the insecticide :3 Maleic Anhydride/Itaconic Acid Copolymer + 7 5 with gentle mixing, at a level of 30 ml per gallon. If desired, 15 f100X malathion lesser amounts of copolymer could be used, e.g., 20 ml per :3 Maleic Anhydride/Itaconic Acid Copolymer + 8 8 gallon. f100X malathion Maleic Anhydride/Itaconic Acid Copolymer + 12 The following table sets forth the results of these tests. f100X malathion Maleic Anhydride/Itaconic Acid Copolymer + 6 8 TABLE 1. f100X malathion Maleic Anhydride/Itaconic Acid Copolymer + 7 8.5 TIME TO DEATH f100X malathion INSECTICIDE COMPOSITION (MIN) Maleic Anhydride/Itaconic Acid Copolymer + 8 8.5 f100X malathion malathion 1X 1 3:1 Maleic Anhydride/Itaconic Acid Copolymer + 7.5 malathion 1,1OX 2 25 f100X malathion malathion 1,2OX 5 3:1 Maleic Anhydride/Itaconic Acid Copolymer + 6 6 malathion 1,1OOX 30 f100X malathion malathion + AVAIL (R) 1,1OOX 7 3:1 Maleic Anhydride/Itaconic Acid Copolymer + 7 7 permethrin 1X 5 f100X malathion permethrin 1,3X 5 3:1 Maleic Anhydride/Itaconic Acid Copolymer + 8 5 permethrin 1,1OX 5 f100X malathion permethrin 1,2OX 2O 7:1. Maleic Anhydride/Itaconic Acid Copolymer + 9 permethrin + AVAIL (R) 1,2OX 2 f100X malathion bifenthrin 1,2OX 15 7:1. Maleic Anhydride/Itaconic Acid Copolymer + 6 4 bifenthrin + AVAIL (R) 1,2OX 5 f100X malathion 7:1. Maleic Anhydride/Itaconic Acid Copolymer + 7 6.5 f100X malathion The data of Table 1 clearly establishes the adjuvant effect 35 7:1. Maleic Anhydride/Itaconic Acid Copolymer + 8 6 of the copolymer with the tested insecticides. In all cases, the f100X malathion kill time for the lowest effective level of insecticide was materially lowered by the presence of the copolymer. Although the mechanism of this effect is not fully understood, it is believed that the tested insecticides, having an amphot 40 TABLE 3 eric or positive charge, are modified by the copolymer to TIME TO change the membrane potential thereof, e.g., the copolymer NSECTICIDE COMPOSITION pH DEATH (MIN) aggregates the charge, rendering the insecticide/copolymer Polymaleic Acid + 1/20X permethrin — Still Alive, 33 mixture more effective. This is confirmed by a series of tests Polymaleic Acid + 1/20X permethrin 6 10 with a negatively charged insecticide (Diazinon R) where the 45 Polymaleic Acid + 1/20X permethrin 7 1O.S copolymer gave no decrease in kill times as compared with Polymaleic Acid + 1/20X permethrin 8 12 :3 Maleic Anhydride/Itaconic Acid Copolymer + - Still Alive, 27 the insecticide itself. f2OX permethrin :3 Maleic Anhydride/Itaconic Acid Copolymer + 6 16 EXAMPLE 2 f2OX permethrin 50 :3 Maleic Anhydride/Itaconic Acid Copolymer + 7 15 f2OX permethrin In another series of tests, insecticides were tested with :3 Maleic Anhydride/Itaconic Acid Copolymer + 8 13 various copolymers having different ratios of maleic anhy f2OX permethrin dride and itaconic acid moieties, and at different pH levels. In :1 Maleic Anhydride/Itaconic Acid Copolymer + - Still Alive, 37 particular, respective copolymeric compositions were pre f2OX permethrin 55 :1 Maleic Anhydride/Itaconic Acid Copolymer + 6 35 pared made up of polymaleic acid, a 1:3 weight ratio of maleic f2OX permethrin anhydride to itaconic acid, a 1:1 weight ratio of maleic anhy :1 Maleic Anhydride/Itaconic Acid Copolymer + 7 19.5 dride to itaconic acid, a 3:1 weight ratio of maleic anhydride f2OX permethrin to itaconic acid, and a 7:1 weight ratio of maleic anhydride to :1 Maleic Anhydride/Itaconic Acid Copolymer + 8 19 f2OX permethrin itaconic acid. Individual portions of each of these copolymers 3:1 Maleic Anhydride/Itaconic Acid Copolymer + — Still Alive, 32 were then pH-modified using sodium hydroxide to provide, 60 f2OX permethrin for each copolymer, portions with no pHadjustment, and with 3:1 Maleic Anhydride/Itaconic Acid Copolymer + 6 29 adjustment to pHs of 6, 7, and 8. These pH-modified test f2OX permethrin 3:1 Maleic Anhydride/Itaconic Acid Copolymer + 7 27 copolymers were then mixed with a 1/100x dilution of f2OX permethrin malathion at a level of 30 ml of copolymer per gallon of 3:1 Maleic Anhydride/Itaconic Acid Copolymer + 8 17 insecticide. Similarly, the same pH-adjusted copolymers 65 f2OX permethrin were mixed with 1/20x water dilutions of permethrin, again at 7:1. Maleic Anhydride/Itaconic Acid Copolymer + — Still Alive, 20 a level of 30 ml of copolymer per gallon of insecticide. US 7,655,597 B1 14 2. The pesticide composition of claim 1, said pesticide TABLE 3-continued selected from the group consisting of insecticides and herbi cides and mixtures thereof. TIME TO 3. The pesticide composition of claim 1, said composition INSECTICIDE COMPOSITION pH DEATH (MIN) having at least about a two-fold greater pesticidal effective 1/20X permethrin ness, as compared with an equal amount of the pesticide 7:1. Maleic Anhydride/Itaconic Acid Copolymer + 6 15 without the copolymer. 1/20X permethrin 7:1. Maleic Anhydride/Itaconic Acid Copolymer + 7 13 4. The pesticide composition of claim 1, said copolymer 1/20X permethrin + NaOH permethrin being a copolymer containing from about 10-90% by weight 7:1. Maleic Anhydride/Itaconic Acid Copolymer + 8 13 10 maleic moieties, and from about 90-10% by weight itaconic 1/20X permethrin moieties. 5. The pesticide composition of claim 1, said copolymer The data of Tables 2 and 3 demonstrate that the preferred being present of from about 0.05-10% by weight, based upon copolymers are useful over a wide range of different maleic the total weight of the composition taken as 100% by weight. anhydridefitaconic acid ratios, and that the copolymers are 15 6. The pesticide composition of claim 5, said level being likewise effective over wide pH ranges. from about 0.2-2% by weight. 7. The pesticide composition of claim 1, said composition EXAMPLE 3 being an aqueous composition and having a pH of from about 5-9. In this example the effectiveness of the copolymers of the 8. The pesticide composition of claim 1, said pesticide invention was tested with a glyphosate herbicide. An Iowa being glyphosate. field having approximately 18-inch tall mixed bromegrass 9. A method of pesticidal treatment comprising the step of and orchard grass being prepared for corn planting was used applying a pesticide composition to a surface, said composi as a test field. In order to plant, it was necessary to kill the tion comprising respective quantities of a pesticide and a weed grasses. It is known that an effective kill is very difficult 25 copolymer consisting of individual quantities of maleic and using only one glyphosate application. itaconic moieties, wherein said quantities total at least 93% In the test, two quarts of standard commercial glyphosate by weight of itaconic and maleic moieties. was mixed with 40 gallons of 28% nitrogen liquid fertilizer 10. The method of claim 9, said pesticide selected from the made up of /3 urea by weight, /3 ammonium nitrate by group consisting of insecticides and herbicides and mixtures weight, and /3 water by weight. As a comparison, two quarts 30 thereof. of a 40% by weight solids maleic anhydride/itaconic acid 11. The method of claim 9, said composition having at least copolymer (Nutrisphere(R) for liquids commercialized by about a two-fold greater pesticidal effectiveness, as compared Specialty Fertilizer Products, LLC, a calcium salt of maleic with an equal amount of the pesticide without the copolymer. itaconic copolymer, as a 30%-60% w/w solution in water, pH 12. The method of claim 9, said copolymer being a copoly 1.5) was added to a separate quantity of the glyphosate 35 mer containing from about 10-90% by weight maleic moi supplemented fertilizer. eties, and from about 90-10% by weight itaconic moieties. Both test compositions were sprayed onto adjacent test 13. The method of claim 9, said copolymer being present of plots of the field at a rate of 10 gallons per acre. After ten days, from about 0.05-10% by weight, based upon the total weight the plot sprayed with the glyphosate and copolymer-Supple of the composition taken as 100% by weight. mented fertilizer exhibited essentially complete kill of the 40 14. The method of claim 13, said level being from about grasses. With the glyphosate-supplemented fertilizer without 0.2-2% by weight. the copolymer, a second glyphosate spray application was 15. The method of claim 9, said composition being an required for a complete kill. aqueous composition and having a pH of from about 5-9. Thus, the copolymer of the inventionallowed plantingatan 16. The method of claim 9, said pesticide being glyphosate. earlier time with reduced glyphosate consumption. 45 17. The pesticide composition of claim 1, said copolymer I claim: being essentially free of any moieties other than said maleic 1. A pesticide composition comprising respective quanti and itaconic moieties. ties of a pesticide and a copolymer consisting of individual 18. The method of claim 9, said copolymer being essen quantities of maleic and itaconic moieties, wherein said quan tially free of any moieties other than said maleic and itaconic tities total at least 93% by weight of itaconic and maleic 50 moieties. moieties. UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION

PATENT NO. : 7.655,597 B1 Page 1 of 1 APPLICATIONNO. : 12/534481 DATED : February 2, 2010 INVENTOR(S) : John Larry Sanders It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

Column 13, line 47, cancel the text beginning with “1. A pesticide composition comprising to and ending “maleic moieties. in column 13, line 51, and insert the following claim: --1. A pesticide composition comprising respective quantities of a pesticide and a copolymer, wherein the copolymer consists of at least 93% by weight quantities of maleic and itaconic moieties.-- Column 14, line 22, cancel the text beginning with “9. A method of pesticidal treatment comprising to and ending “maleic moieties. in column 14, line 27, and insert the following claim: --9. A method of pesticidal treatment comprising the step of applying a pesticide composition to a Surface, Said composition comprising respective quantities of a pesticide and a copolymer, wherein the copolymer consists of at least 93% by weight quantities of maleic and itaconic moieties.--

Signed and Sealed this Sixteenth Day of November, 2010

David J. Kappos Director of the United States Patent and Trademark Office