MXPA98002591A - Pesticial compositions - Google Patents

Abstract

The present invention relates to insecticidal compositions, in which at least one of the components of the composition is a polymeric material, which reduces the rate of crystallization of the insecticidal active ingredient in the composition. This invention also provides a method for reducing the rate of crystallization of insecticidal active ingredients and a method for controlling pests, which comprises applying the composition containing the polymer to the pest.

Description

INSECTICIDE COMPOSITIONS The present invention relates to insecticidal compositions, in which at least one of the components of the composition is a polymeric material, which reduces the rate of crystallization of the insecticidal active ingredient in the composition. This invention also provides a method for reducing the rate of crystallization of insecticidal active ingredients. In the formulation of insecticidal active ingredients, one of the greatest difficulties is to keep this active ingredient in a non-crystalline form. For example, the presence of crystalline active ingredients may make the preparation of some types of formulations more difficult, because the crystalline structure must be reduced in order to formulate the active ingredient appropriately. Processes to reduce the crystal structure of crystalline active ingredients, such as grinding, grinding or dissolving in a solvent, are often costly and time consuming. Likewise, certain insecticidal formulations can not be prepared using some active ingredients, because these active ingredients crystallize from the formulation. It has also been observed that the effectiveness of certain active ingredients is reduced when they are present in a crystalline state. Thus, there is a continuing need for insecticidal compositions in which the crystallization rate of the active ingredient is reduced. U.S. Patent No. 3,131,119 discloses a class of polymers soluble in organic solvents, which possess a balance of hydrophilic and lipophilic groups, which are useful for dispersing water-insoluble metal salts of dithiocarbamic acids in oil systems. . The polymers have both lipophilic and hydrophilic portions in a non-polar / polar equilibrium and have a solubility parameter of 7.7 to 8.3. We have discovered that such polymers, like polymers related to a wider range of solubility parameters, are, surprisingly, effective in reducing the crystallization rate of many insecticidal active ingredients. The addition of 0.01% to 40% by weight of the polymer to an active ingredient or active ingredient formulation has shown such reductions. This invention provides an insecticidal composition comprising: a) one or more insecticides and b) from 0.01 to 40% by weight of one or more oil-soluble polymers, where the polymer has a solubility parameter of 6.9 to 9.0 and has a character or lipophilic or both lipophilic and hydrophilic, and in that the insecticide is soluble in at least one of 1) the monomers that make up the polymer; 2) oligomers of approximately the same proportional composition of the monomer unit as the polymer; 3) the polymer and 4) a solution of the polymer and an organic solvent. In a second embodiment, this invention provides a method for reducing the rate of crystallization of an insecticide, which comprises effectively mixing one or more insecticides with 0.01 to 40% by weight of one or more oil-soluble polymers, in which the polymer has a solubility parameter of 6.9 to 9.0 and has lipophilic or both lipophilic and hydrophilic portions. In another embodiment, this invention provides a method for controlling a pest, this method comprises applying to the pest, the food source of the pest, or the habitat of the pest, a composition comprising: a) one or more insecticides and ) from 0.01 to 40% by weight, based on the total weight of the composition, of one or more oil-soluble polymers, derived from at least one polymerizable, monoethylenically unsaturated monomer, in which the polymer has a solubility parameter of 6.9 to 9.0, and has a character or lipophilic or both lipophilic and hydrophilic and where the insecticide is soluble in at least one of: 1) the monomers that make up the polymer; 2) oligomers of approximately the same monomer unit composition as the polymer; 3) the polymer and 4) a solution of the polymer and an organic solvent. The polymers of this invention are effective in concentrations of about 0.01 to 40% of the composition, depending on the particular active ingredient present. Typically they reduce the crystallization rate of the active ingredient to levels of 0.01 to 5% of the composition. Under optimal conditions, they are very effective at levels of 0.01 to 2% of the composition. The terms "insecticides" and "active ingredients", mean a chemical which is intended to mitigate a pest, which includes insects, weeds, fungi and related organisms. The insecticide of the compositions of this invention may be in the form of a pure active ingredient, a technical grade of the active ingredient, ie, the active ingredient in a concentration produced during typical manufacturing processes, or an active ingredient formulated with one or more agronomically acceptable carriers. The term "agronomically acceptable carrier" means any substance which can be used. to assist in the dispersion of the active ingredient of the composition in water, oil or in a formulation used to control pests, such as a powder, without impairing the effectiveness of the active ingredient and which itself does not have a significant detrimental effect on the soil , equipment, desired plants, or agronomic environment. If desired, adjuvants, such as surfactants, stabilizers, anti-foaming agents and anti-impulse agents can also be combined in the formulation. The insecticide may comprise 0.01 to 99.9% by weight of the composition. When the insecticide is in the form of the pure active ingredient or a technical grade of the active ingredient, it is convenient to maintain the percentage of the active ingredient at a level as high as possible. When formulated, the insecticide preferably comprises from 5 to 90% by weight of the insecticidal composition. Preferably, the insecticide has a solubility greater than one percent by weight in the organic solvents, at room temperature, or at a temperature at which the insecticide and the polymer combine, when the composition includes such a solvent. Preferably, the insecticide has a melting point less than about 150 ° C or, if the melting point is greater than 150 ° C, it is stable at the melting point. Insecticides that are water soluble salts do not form stable compositions with the polymers of this invention. For some applications, two or more insecticides can be combined in a formulation comprising the compositions of the present invention, whereby additional advantages and effectiveness are provided, including smaller total applications of the insecticide, than if the insecticides are applied in separate compositions. . When mixtures of insecticides are employed, the relative proportions of each of the compositions will depend on the relative efficacy and the desired application rate of each insecticide with respect to the pests to be treated, as well as the effectiveness of the chosen polymer. Those skilled in the art will recognize that mixtures of insecticides can provide advantages, such as a broader spectrum of activity than an insecticide used alone. Examples of insecticides that can be used in the compositions of the present invention include: (1) fungicides, such as, for example, (a) nitrophenol derivatives, such as dinocap, binapacryl and 2-sec carbonate. -butyl-4,6-dinitrophenyl-isopropyl; (b) heterocyclic structures, such as captan folpet, glyodine, dithianon, thioquinox, benomyl, thiabendazole, vinolozolin, iprodione, procymidone, triadimenol, triadimefon, bitertanol fluoroimide, triarimol, cycloheximide, ethirimol, dodemorph, dimethomorph, thiofluzamide and quinomethionate; (c) various halogenated fungicides, such as chloranil, dichlone, chloroneb, dichloran and polychloronitribenzenes; (d) fungicidal antibiotics, such as: griseofulvin, kasugamycin and streptomycin; (e) various fungicides, such as diphenylsulphone, dodine, methoxyl, l-thiocyano-2,4-dinitrobenzene, 1-phenylthio-semicarbazide, thiophanate-methyl and cymoxanil, as well as acrylalanines, such as furalaxyl, cyprofuram, ofurace , benalaxyl and oxadixyl; fluazinam, flumetover, phenylbenzamide derivatives, such as those disclosed in patent EP 578586 Al, amino acid derivatives, such as valine derivatives, disclosed in patent EP 550788 Al, methoxyacrylates, such as (E) -2- ( 2- (6- (2-Cyanophenoxy) pyrimidin-4-yloxy) phenyl) -3-methoxy-methacrylate methyl; S-methyl ester of benzo (1, 2, 3) thiadiazole-7-carbothioic acid; propamocarb; imazalil; carbendazim; myclobutanil; phenobucanazole; tridemorph; pyrazophos; fenarimol; fenpiclonil; and pyrimethanil; (2) herbicides, such as, (a) carboxylic acid derivatives, including benzoic acids and their salts; carboxylic acids substituted with phenoxy and phenyl and their salts; and trichloroacetic acid and its salts; (b) carbamic acid derivatives, including ethyl N, N-di (n-propyl) thiolcarbamate and pronamide; (c) substituted ureas, (d) substituted triazines, (e) diphenyl ether derivatives, such as oxyfluorfen and fluoroglycofen, (f) anuides, such as propanil, (g) oxyphenoxy herbicides, (h) uracils, (e) i) nitriles and (j) other organic herbicides, such as dithiopyr and thiazopyr; and (3) insecticides, which include acephate, aldicarb, alpha-cypermethrin, azinphos-methyl, binapacryl, buprofezin, carbaryl, carbofuran, chlorpyrifos, clofentezine, cyhexatin, cypermethrin, deltamethrin, dicofol, diflubenzuron, dimethoate, dinocap, endosulfan, endothion , esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprop, fenbutatin-oxide, fenoxycarb, fenoxicarb, fensulfothion flucycloxuron, flufenoxuron, fosmethilan, hexythiazox, ethamidophos, methidathion, methiocarb, methomyl, methyl-parathion, mexacarbate, oxamyl, permethrin, phosalone, phosmet, promecarb, pyridaben, resmethrin, rotenone, tebufenozide, thiodicarb, triaza ate and vamidothion. The polymers used in the compositions of this invention may be homopolymers or copolymers, including graft, block, star, random and variable composition polymers, which are soluble in organic solvents or vegetable, mineral or synthetic oils and which contain lipophilic or both lipophilic and hydrophilic. The lipophilic character is supplied by hydrocarbon groups containing an average of eight carbon atoms, preferably an average of 12 or more carbon atoms, up to 24 carbon atoms. The polymer can contain a mixture of such groups and also groups with smaller carbon atoms. In an oil-based system, the polymer will preferably contain groups that average eight carbon atoms. The hydrophilic character is supplied by ether groups, carbonyl groups, carboxylic acid groups, carboxylic ester groups, alcohol groups, amide groups, and their thio analogues, as well as amino groups. The amino and amide nitrogen may be primary, secondary or tertiary. Nitrogen substituents may include open chain or cyclic groups, including, for example, alkyl, cycloalkyl, phenyl, benzyl, aminoalkyl, phenoxyalkyl, hydroxyalkyl, alkoxyalkyl, alkoxyethoxyethyl, alkoxy-propoxypropyl, alkoxypolyethoxyethyl, benzoxyethoxyethyl, phenoxy polyethoxyethyl or groups. similar ones that contain polyether. The polymer may include more than one such hydrophilic substituent. The lipophilic character must be sufficient to ensure the solubility of the polymer in an organic solvent or oil. The hydrophilicity required will depend primarily on the nature of the insecticide. The lipophilic character of the polymer of this invention is provided by one or more ethylenically unsaturated monomers, such as, for example, methyl groups, butyl, hexyl, octyl, decyl, lauryl, myristyl, cetyl, stearyl, icosyl or tetracosyl in esters of acrylic, methacrylic, fumaric, maleic or itaconic acids, or by vinyl carboxylates with alkyl groups of at least eight carbon atoms. Depending on the particular active ingredient, copolymer polymers of these long chain esters by themselves may not possess, however, the necessary lipophilic / hydrophilic or polar balance. In such cases, they should also have present either in the polymerization molecule or in the copolymer, at least one source of polar or hydrophilic substituents, such substituents being of sufficient polarity or present in a sufficient proportion to create the necessary polar balance. Another class of suitable ethylenically unsaturated monomers are vinylaromatic monomers, including, for example, styrene, α-methylstyrene, vinyltoluene, ortho-, meta- and para-methylstyrene, ethylvinylbenzene, vinylnaphthalene and vinylxylenes. The vinylaromatic monomers can also include their corresponding substituted counterparts, for example the halogenated derivatives, that is to say they contain one or more halogen groups, such as fluorine, chlorine or bromine, and nitro, cyano, alkoxy, haloalkyl, carbalkoxy derivatives, carboxy, amino and alkylamino. Other suitable monomers, ethylenically unsaturated, include the ethylene and substituted ethylene monomers, for example the α-olefins, (such as C 2 or C 2 alkyl α-olefins); vinyl alcohol esters, such as vinyl acetate and vinyl stearate; vinyl halides such as vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, vinylidene fluoride and vinylidene bromide; and vinyl nitriles, such as acrylonitrile and methacrylonitrile.

A preferred class of acrylic and methacrylic acid derivatives (hereinafter referred to as "(meth) acrylic" or "(meth) acrylate" or "(meth) acrylamide") is represented by alkyl (meth) acrylate monomers, ( meth) substituted acrylates and substituted acrylamide and substituted methacrylamide. Each of the monomers may be a single monomer or a mixture having different numbers of carbon atoms in the alkyl moiety. Preferably, the monomers are selected from the group consisting of (C 1 -C 24) alkyl (meth) acrylates, hydroxy (C 2 -C g) (meth) acrylates, dialkyl (C) _ (Cg) (meth) acrylates) amino (C2-C5) aminoalkyl (meth) acrylamides of dialkyl (C? -Cg) amino-alkyl (C2 ~ Cg). The alkyl portion of each monomer can be linear or branched. Particularly preferred polymers useful in the present invention are poly (meth) acrylates derived from the polymerization of the alkyl (meth) acrylate monomers. Examples of alkyl (meth) acrylate monomers, where the alkyl group contains from 1 to 6 carbon atoms, are methyl methacrylate (MMA), methyl and ethyl acrylate, propyl methacrylate, butyl methacrylate (BMA) and butyl acrylate (BA), isobutyl methacrylate (IBMA), hexyl methacrylate and cyclohexyl, cyclohexyl acrylate and combinations thereof. Examples of the alkyl (meth) acrylate monomer, where the alkyl group contains from 7 to 15 carbon atoms are 2-ethylhexyl acrylate (EHA), 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, methacrylate isodecyl (IDMA, based on a mixture of branched alkyl (C? o) isomers), undecyl methacrylate, dodecyl methacrylate (also known as lauryl methacrylate), tridecyl methacrylate, tetradecyl methacrylate (also known as myristyl methacrylate) ), pentadecyl methacrylate and their combinations. Also useful are dodecyl-pentadecyl methacrylate (DPMA), a mixture of linear and branched isomers of dodecyl, tridecyl, tetradecyl and pentadecyl methacrylates, and lauryl-myristyl methacrylate (LMA), a mixture of dodecyl methacrylates and tetradecyl. Preferred alkyl methacrylates are lauryl-myristyl methacrylate, dodecyl-pentadecyl methacrylate and isodecyl methacrylate. Examples of monomers of (meth) alkyl acrylate where the alkyl group contains 16 to 24 carbon atoms are hexadecyl methacrylate (also known as cetyl methacrylate), heptadecyl methacrylate, octadecyl methacrylate (also known as stearyl methacrylate), nonadecyl methacrylate, icosyl methacrylate, behenyl methacrylate and combinations thereof. Also useful are cetyl-icosyl methacrylate (CEMA), a mixture of methacrylates of hexadecyl, octadecyl and icosyl, and cetyl-stearyl methacrylate (SMA), a mixture of hexadecyl and octadecyl methacrylates. Preferred alkyl methacrylates (C? G-C24) are cetyl-icosyl methacrylate and cetyl-stearyl methacrylate. The above-described (C7-C24) alkyl (meth) acrylate monomers are generally prepared by standard esterification methods, with the use of technical grades of long-chain aliphatic alcohols. These alcohols, commercially available, are mixtures of alcohols which vary in chain lengths and contain between 10 and 15 or 16 and 20 carbon atoms in the alkyl group. Consequently, for the purposes of this invention, the alkyl (meth) acrylate tries to include not only the individual product of (meth) alkyl acrylate mentioned, but also includes mixtures of alkyl (meth) acrylates with a predominant amount of the particular named alkyl (meth) acrylate. The use of these commercially available alcohol blends to prepare the (meth) acrylate esters results in the types of LMA, DPMA, SMA and CEMA monomers described above. Preferred acid derivatives (meth) acrylic, useful in the process of the present invention, are methyl methacrylate, butyl methacrylate, isodecyl methacrylate, lauryl-myristyl methacrylate, dodecyl-pentadecyl methacrylate, cetyl-icosyl methacrylate and cetyl methacrylate. stearyl.

For the purposes of the present invention, it will be understood that copolymer compositions representing combinations of the monomers of the aforementioned classes of monomers can be prepared using the processes described herein. For example, copolymers of alkyl (meth) acrylate monomers and vinylaromatic monomers, such as styrene; copolymers of alkyl (meth) acrylate monomers and substituted (meth) acrylamide monomers, such as N, N-dimethylaminopropyl methacrylamide; copolymers of alkyl (meth) acrylate monomers and monomers based on nitrogen-containing ring compounds, such as N-vinylpyrrolidone; copolymers of vinyl acetate with fumaric acid and their derivatives; and (meth) acrylic acid copolymers and their derivatives with maleic acid and its derivatives. Examples of monomers that deliver homopolymers with an effective polar equilibrium include N-tert.-methacrylate. -dodecylaminoethyl, and N-tert-alkylaminoethyl methacrylate, with the tertiary alkyl group being a group (C9-C21) • These same types of monomers are also used in forming copolymers with other comonomers, both lipophilic and hydrophilic in nature. Typical comonomers, useful for providing the hydrophilic balance, include acrylates, methacrylates, itaconates, fumarates or lower alkyl maleates and polymerizable, ethylenically unsaturated monomers, in which the alkyl portion does not exceed Cg and is preferably Cj_ to C4 . Alkyloxy-polyethoxyethyl acrylates and methacrylates also provide polar groups. The alkyloxy group in such esters and ethers can be replaced with alkylamino, alkylthio or acyloxy groups. Vinyl acetate, propionate and butyrate are similar sources of polar ester groups to form copolymers. Groups containing nitrogen, such as amines, amides, imides and heterocycles, can also be used to supply the polarity. Typical comonomers for this purpose include the acrylates or methacrylates of dimethylaminoethyl or dimethylaminopropyl, acrylamide, methacrylamide, vinyl pyridines, such as 2-methyl-5-vinylpyridine or 4- or 2-vinylpyridine, N-methylolacrylamide, N-methylolmethacrylamide or N -methylacrylamide. Comparable polar groups can be supplied by the lactams, which carry a vinylidene group, such as,. for example, N-vinyl-2-pyrrolidinone, N-vinylpiperidinone, N-vinyl caprolactam and 2-pyrrolidinonylethyl methacrylate. Oxazolidine derivatives, such as N-vinyloxazolidinone or N- (methacryloxyoxyethyl) oxazolininone can also be used.

Examples of methacrylate and alkyl acrylate monomers with one or more hydroxyl groups in the allyl radical, especially those where the hydroxyl group is in the b position (2-position) in the alkyl radical. The methacrylate and hydroxyalkyl acrylate monomers wherein the substituted alkyl group is a branched or unbranched (C2-Cg) alkyl, are preferred. Among the methacrylate and hydroxy alkyl acrylate monomers suitable for use in the present invention are 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, l-methyl methacrylate, 2-hydroxyethyl, 2-hydroxypropyl acrylate, l-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate, The preferred monomers of methacrylate and hydroxyalkyl acrylate are HEMA, l-methyl methacrylate -2-hydroxyethyl and 2-hydroxypropyl methacrylate. A mixture of the last two monomers is commonly referred to as "hydroxypropyl methacrylate" or HPMA, which is the most preferred hydroxyalkyl methacrylate, as each component of HPMA. The polymers and copolymers of this invention are prepared by mixing the appropriate monomers in the presence of a polymerization initiator, with or without a solvent and optionally a chain transfer agent. the reaction can be carried out under agitation, in an inert atmosphere, at a temperature of about 60 to 140 ° C and more preferably of 115 to 125 ° C. Typically, the batch will be exothermic at the polymerization temperature of 115 to 120 ° C. The reaction is generally carried out for about 4 to 10 hours, or until the desired degree of polymerization has been achieved. As will be recognized by those skilled in the art, the time and temperature of the reaction are dependent on the selection of the initiator and may vary conveniently. Useful initiators for this polymerization are any of the well-known compounds, which produce free radicals, such as the peroxy, hydroperoxy and azo initiators, which include acetyl peroxide, benzoyl peroxide, lauroyl peroxide, t-butyl peroxyisobutyrate, caproyl peroxide, eumenohydroperoxide, 1,1-di (t-butylperoxy) -3,3,5-tri-methylcyclohexane, azobis-isobutyronitrile and t-butylperoctoate. The initiator concentration is usually between 0.025 and 1% by weight, based on the total weight of the monomers and more preferably 0.05 to 0.25%. The chain transfer agents can also be added to the polymerization reaction to control the molecular weight of the polymer. When used, the preferred chain transfer agents are alkyl mercaptans, such as lauryl mercaptan (dodecyl), used in a concentration of about 0.1 to 3% by weight. The polymer can be prepared in the presence or absence of a solvent. Among the solvents suitable for use during the polymerization and for the preparation of the concentrates are hydrocarbons, aromatic hydrocarbons, such as benzene, toluene, xylene and aromatic naphthas, chlorinated hydrocarbons, such as ethylene dichloride, esters, such as ethyl propionate or butyl acetate, ketones, such as N-methyl-pyrrolidinone and also petroleum oils, vegetable oils and synthetic oils. After polymerization, the resulting solution of the polymer has a content of this polymer between about 20 to 100% by weight. The polymer can be isolated and used directly or diluted with a solvent, as described for use in the polymerization, or the solution of the polymer or diluent can be used in a concentrated form. When used in the concentrated form, the concentration of the polymer can be adjusted to any desired level with an additional diluent, for example, an organic solvent or a light mineral oil. The preferred concentration of the polymer in the concentrate is 30 to 70% by weight.

The homopolymers and copolymers of this invention can be defined as those which are soluble in organic solvents or oils and which contain a lipophilic or both lipophilic and hydrophilic character. This lipophilic / hydrophilic character can be expressed in terms of the solubility parameter d, as described by Hildebrand in Solubility of Nonelectrolytes, 3rd Edition, Reinhold Publishing Corp., NY (1949). This value, which is equal to the square root of the cohesive energy density, has been determined for a wide variety of solvents and also for several polymers. See, for example, H. Burrell, Inter- chemical Review, vol. 14, No. 1, 3-16 (1955). The solubility parameters can be approximated by calculations according to the method of Small, J. Appl. Chem. , 3, 71 (1953). They can be determined experimentally from solubilities of polymers in a series of solvents of known d values. The solubility parameters for the copolymers can be calculated based on the d values for the units of each type of comonomer, on a weight average basis. Typical values are given in Table 1 for polymers and copolymers.

Table 1 Solubility Parameters of Polymers and Copolymers Polymer of: 5 MMA 9.5 Vinyl acetate 9.4 Styrene 9.1 BMA 9.0 Hexagon MA 8.7 OC Oct 8.5 MA de tere. -dodecylaminoethyl 8.2 ViEH 8.1 AML (72% / 28%) 8.0 ViSt 7.6 Stearyl methacrylate 7.0 Dilauryl Fumarate 6.8 Dicetyl Itaconato 6.5 NVP 12 diMAEMA 10 2-methyl-5-vinyl-pyridine 10 Composition of Copolymer (% by weight) AML / SMA (65/35) 7.7 diLMF / NVP (80/20) 7.8 BMA / SMA (50/50) 8.0 MMA / LMA / SMA / NVP (14/51/30/5) 8.0 BMA / HMA / AML / SMA (25/15/30/30) 8.1 BMA / AML / SMA / diMAEMA (33.5 / 35/30 / 1.5) 8.1 ViSt / ViEH / NVP (31.6 / 63.2 / 5.2) 8.1 BMA / AML / SMA / NVP (17 / 45.2 / 30 / 7.8) 8.2 BMA / AML / SMA / NVP (32 / 25/35/8) 8.3 MA = methacrylate F = fumarate NVP = N-vinyl-2-pyrrolidinin M = methyl B = butyl L = lauryl-myristyl S = cetyl-stearyl EH = 2-ethylhexoate Vi = vinyl St = stearate diMAEMA = dimethylaminoethyl methacrylate.

The optimum molecular weight range, to obtain the greatest effectiveness of the polymer, will vary depending on the properties of the active ingredient. However, the weight average molecular weights (Mw) of 10,000 to 2,000,000 AMU, approximately (as determined by gel permeation chromatography (GPC)), which use the poly (alkyl methacrylate) standard, are useful. between 15,000 and 500,000 AMU are preferred.More preferred are polymers with molecular weights between 25,000 and 100,000 AMU In order for the polymer to modify the crystallization rate of the active ingredient, it is important that there is a high interaction between the active ingredient and the active ingredient. polymer, that is, the molecules of the active ingredient and the polymer molecules must be mixed homogeneously together, so that they interact at the molecular level.This will occur under a variety of conditions.The preferred conditions will occur when: 1) the active ingredient is soluble in the monomers that make up the polymer; or 2) the active ingredient is soluble in the oligomers, which include the dimers, trimers and other short chain polymers, of about the same proportional composition of the monomer unit as the polymer, or 3) the active ingredient is soluble in the own polymer, particularly when this active ingredient is a liquid or 4) both the active ingredient and the polymer are soluble in a cosolvent. In addition, there are several factors that can affect the mixing of the active ingredient with the polymer, which include the temperature of the mixture, the presence of other components and the degree of agitation. Typically, the higher the temperature of the mixture, the greater the mobility of the polymer and the active ingredient. This greater mobility improves the mixture. For example, a solid, technical grade active ingredient will not mix well with most polymers. However, if the system is heated above the melting temperature of the technical grade ingredient, the two components will often mix easily. The presence of the third component, such as a solvent or mixture of solvents, wherein both the active ingredient and the polymer are soluble, will help to interrupt the phase separations between the active ingredient and the polymer and improve the mixing. Both the quantity and the composition of the third component can vary to achieve optimal results. The third component can be a mixture of a number of substances. The addition of the third component is particularly important if the heating of the active ingredient and the polymer is not a good option, due to the problems of thermal instability, with either the active ingredient or the polymer. Finally, the mechanical force (stirring and cutting rate) used in the mixing process, can affect the homogeneity of the mixture, generally, increasing the degree of agitation used in the mixing process will produce an improved mixture. When more than one active ingredient is present in the composition, the selection of the polymer becomes more difficult, because the optimal polymer for an active ingredient may be poor selection for the other active ingredient. However, a satisfactory compromise of the polymer or a mixture of different polymers can be chosen using the above selection criteria, but also considering the total concentration of the active ingredient and the ratio between the various active ingredients present in the final composition. Although the compositions of this invention may comprise only the active ingredient and the polymer, it is preferable to dissolve the polymer, the active ingredient or both in a solvent, before or during mixing. When used, the solvent may be any or a combination of aromatic solvents, such as xylenes or mixtures of xylenes, toluene, benzene or alkylbenzenes; ketones such as cyclohexanone, ethylethyl ketone, methylbutyl ketone, or methyl isobutyl ketone; alcohols, such as methanol, propylene glycol or ethylene glycol; esters, such as ethyl acetate, propyl acetate or butyl acetate; and other organic solvents, such as dimethyl formamide, dimethyl sulfoxide, tetrahydrofuran or N-methylpyrrolidinone. The selection of the solvent will depend on the particular active ingredient and the particular polymer chosen. For example, if the active ingredient is soluble in a ketone, the appropriate polymer will be polar and also soluble in the ketone, such as vinyl acetate or a (meth) acrylate with a short side chain. In addition, many of the compositions of this invention will benefit from the addition of one or more surfactants. Useful surfactants may be nonionic, anionic, cationic or amphoteric. Not all combinations of active ingredients and polymers will provide a composition in which the crystallization rate of the active ingredient is reduced. However, those skilled in the art of the fomulations will be able to select a limited group of combinations of active ingredients / polymer, with the use of the above selection criteria. For agrochemical uses, the formulations of the compositions of the present invention can be applied as powders, granules, wettable powders, oil-based sprays or aqueous sprays, by commonly employed methods, such as conventional high-volume hydraulic sprays, sprays of low volume, air choros and aerial sprays. The dilution and the application regime will depend on the type of equipment used, the method and frequency of the desired application, the regime of the insecticide application, and the pests that will be controlled. The formulations or diluted formulations of the compositions of this invention may also contain agronomically acceptable adjuvants. These adjuvants include surfactants, dispersants, spreading agents, adhesion agents, defoamers, emulsifiers and other similar materials, described in McCutcheon's Emulsifiers and Detergent, McCutcheon's Emulsifiers and Detergents / Ma terials Functional, and McCutcheon's Functional Materials, all published annually by McCutcheon Division of MC Publishing Company (New Jersey). An advantage of reducing the crystallization rate of the insecticide is that formulations having higher concentrations of the insecticide than can be obtained in the absence of the polymer can often be prepared. The compositions of the present invention can also be mixed with fertilizers or fertilizer materials, before their application. The compositions and the fertilizer material can also be mixed in the mixing or combination equipment or can be incorporated with fertilizers into granular formulations. Any relative proportion of the fertilizer can be used, which is suitable for the crops and weeds to be treated. The compositions of the invention will commonly comprise from 5 to 50% of the fertilizer composition. These compositions provide fertilizer materials that promote the rapid growth of the desired plants, and at the same time control the pests.

EXAMPLES The following examples are provided in order to illustrate some aspects of the present invention. Unless otherwise specified, all percentages are by weight, relative to the total weight of the composition. The following general processes were used to prepare the compositions of this invention: I. Preparation of a mixture of active ingredient / polymer, in the absence of a solvent: For active ingredients, which are stable at or above their melting point, this active ingredient can be melted in the presence of the polymer. The active ingredient and the polymer are then mixed for one to five minutes, using a homogenizer, or any other kind of mixing apparatus, which can supply a medium to the high cut mixing regime. If necessary, the mixture can be reheated. Formulations of the active ingredient / polymer mixture were prepared using standard formulation processes, as follows: For an emulsifiable concentrate: The active ingredient / polymer mixture is dissolved in appropriate organic solvents and surfactants, with stirring. For a wettable powder: Impregnate the mixture of the active ingredient / polymer on an inert solid carrier, then mix it with other ingredients, such as dispersants, surfactants, and anti-foaming agents, to obtain a pre-mix of a huctable powder, Grind the Pre-mixing to obtain the final formulation of the wettable powder. For an aqueous flowable product: Impregnate the mixture of the active ingredient / polymer on an inert solid carrier, then mix with the other ingredients, such as dispersants, surfactants, biocides, antifoaming agents, thickening agents, and water. Grind the mixture to produce the final formulation that can flow. For Water Dispersible Granules: Prepare the dispersible granules from either a wettable powder or an aqueous formulation that can flow, using standard granular preparation procedures, such as spray drying, container granulation or extrusion.

II. Preparation of a mixture of active ingredient / polymer in the presence of a solvent: For active ingredients having a solubility greater than one percent in common organic solvents, the active ingredient and the polymer were dissolved in the solvent or solvent mixtures chosen and They combined. The heating of the mixture or mixtures is often useful to accelerate the dissolution process and obtain a highly saturated solution of the active ingredient and the polymer. One option for the low melting point active ingredients is to first melt the active ingredient and then mix it with the polymer in the solvent or mixture of chosen solvents. Formulations of the active ingredient / polymer / solvent mixture were prepared using standard formulation processes as follows: For emulsifiable concentrates: Mix the active ingredient / polymer / solvent mixture with the surfactants, antifoaming agents and any other selected components, using the agitation or homogenization. For wettable powders, flowable aqueous formulations or water dispersible granules: Separate the mixture of the active ingredient / polymer from the solvent by evaporation or precipitation and then follow the processes described above. The following examples illustrate the effect of polymers on the crystallization rate of the active ingredients: The following parameters are key factors in the evaluation: a) Visual inspection of the crystallization: When a net technical grade is used, the crystallization rate is estimated quantitatively by the color and physical state change of the test material. The non-crystallized samples remained clear and flowable, while the crystallized material typically changed to a solid mass of opaque color. The crystallization regime was recorded as the time it takes for this kind of change to take place. b) Measurement of crystals in emulsifiable concentrates or solutions of organic solvents: The emulsifiable concentrate or organic solution was examined visually in the growth of crystals or the crystals were separated from the solution and weighed. c) Measurement of the weight of crystals in emulsions: This procedure was used in the evaluations of the emulsifiable concentrate formulations, only. A 1% (volume) dilution of the emulsifiable concentrate formulation, with 342 ppm hot water, was obtained and allowed to stand on the top of a bench, for a given period of time. Then the emulsion mixture was emptied through a 325 mesh screen. Any solid crystal collected on the screen was washed with deionized water and dried. The weight of the crystals was measured as a dry weight. d) Degree of crystallinity measured by Differential Scanning Calorimetry ("DSC"). This method was used to determine the degree of crystallinity of a solid sample: the solid precipitated from the organic solution, the solid obtained by evaporating the organic solvents and / or the solid powder prepared by impregnating the technical melt product on a porous carrier.

Example I: Reduction of the crystallization rate of technical oxyfluorfen A 20 gram sample of technical oxyfluorfen (2-chloro-1- (3-ethoxy-4-nitrophenoxy) -4-trifluoromethyl-benzene) (72% active ingredient) in A glass jar was melted at 100 ° C and then cooled to 25 ° C. The technical material crystallized completely within 2 hours. An identical sample was melted at 100 ° C. The poly-SMA, 0.5% by weight, was then added, the mixture was manually shaken to uniformity, and then heated at 100 ° C for an additional 30 minutes. The technical material remained free of crystals for 24 hours and then gradually crystallized completely over the next 26 hours.

Example 2: Reduction of crystallization of oxyfluorfen from an emulsifiable concentrate formulation Using the polymer can significantly reduce the amount of crystal formation in the water dilution of an emulsifiable concentrate formulation (EC), which contains 33% oxyfluorfen ( 95% pure) technical, alkylbenzenes (Aromatic 200®, Exxon Chemical Co.) and N-methyl-pyrrolidinone solvents and 8-12% ethoxylated castor oil, with calcium dodecylbenzenesulfonate emulsifiers. When the formulation alone was diluted with 342 ppm of hard water to provide a 2% dilution, 0.0170 grams of oxyfluorfen crystallized after 17 hours. The addition of 0.5% of the polyisodecylmethacrylate (poly-IDMA) in an identical formulation, before making the dilution, reduced the amount of oxyfluorfen crystal formation to 0.0001 grams after 17 hours.

Example 3: Reduction of oxyforfen crystallization from organic solvents The use of polymers increased the solubility of oxyfluorfen in common organic solvents or organic material. At 25 ° C and without the polymer present, a solution containing oxyfluorfen, 50% alkylbenzenes and 30% ethoxylated trisiloxane (Silwet® L-77, Witco Chemical Co.) can contain a maximum of 20% oxyfluorfen. With the addition of 1.0% polymers of 28% CEMA, 62% IDMA, 10% MMA, it was possible to obtain a stable solution containing 50% oxyfluorfen, 29% Aromatic 200® and 20% Silwet® L -77.

Example 4: Reduction of the crystallization of tebufenozide from an emulsion In an EC formulation, containing 5% tebufenozide, 60% alkylbenzenes and 35% ethoxylated trisiloxane, the use of the polymer can significantly reduce the amount of crystal formation in water dilution. When such a formulation was diluted in 342 ppm of hard water, to provide a 1% dilution, 0.0532 grams of the tebufenozide crystallized after 17 hours. The addition of 0.5% polymers of 28% CEMA, 62% IDMA, 10% MMA, in a 5% EC formulation, before making the dilution, reduced the amount of crystal formation of tebufenozide to 0.0017 grams , after 17 hours.

Example 5: Reduction of the crystallization of fenbuconazole from an emulsion In an EC formulation of 15% fenbuconazole, containing alkylbenzenes as the solvent and 8-12% calcium dodecylbenzene sulfonate, with alkylphenol ethoxylate (Sponto® 232- 234, Witco Chemical Co.) as an emulsifier, the use of the polymer could significantly reduce the amount of crystal formation in water dilution. When such a 15% EC sample was diluted in 342 ppm of hard water, to provide a 1% dilution, 0.0120 grams of fenbuconazole crystallized after 17 hours. The addition of 0.5% poly-SMA in an identical formulation of 15% EC, before making the dilution, could reduce the amount of crystal formation of fenbuconazole to 0.0001 gram after 17 hours.

Example 6: Reduction of the crystallization of fluoroglycofen-y ilo The use of the polymer could stop the crystallization of technical fluoroglycofen-ethyl. This technical-grade fluoroglycofen-ethyl was melted at 80 ° C and then cooled to 25 ° C. The technical material crystallized completely within 50 hours. However, when an identical material of technical grade was melted with the addition of 0.5% of a 28% CEMA polymer, 62% IDMA, 10% MMA, the technical material did not crystallize even after 600 days. In a similar manner, a variety of polymers were evaluated in their ability to reduce the crystallization time of fluoroglycofen-ethyl (technical material, 93% pure). The results of these evaluations are as follows: * = Less Molecular Weight. These data indicate that the presence of the polymer, with appropriate concentrations, will significantly reduce the rate of crystallization.

Claims (11)

1. CLAIMS 1. A composition comprising: a) one or more insecticides; and b) one or more oil-soluble polymers, having a solubility parameter of 6.9 to 9.0, selected from: 1) polymers with lipophilic character and 2) polymers with both lipophilic and hydrophilic character; wherein each insecticide is soluble in at least one of the group consisting of: i) the monomers that make up the polymer; ii) oligomers of approximately the same proportional composition of monomer bound as the polymer; iii) the polymer and iv) a solution of the polymer and an organic solvent.
2. 2. The composition of claim 1, wherein each polymer is soluble in one or more of the group consisting of: a) organic solvents; b) vegetable oils; c) mineral oils; and d) synthetic oils.
3. 3. The composition of claim 1, wherein the molecular weight of the polymer is 10,000 to 2,000,000 AMU.
4. 4. A method for reducing the rate of crystallization of an insecticide, this method comprises mixing the insecticide with one or more oil-soluble polymers, which have a solubility parameter of 6.9 to 9.0 selected from: 1) polymers with lipophilic character and 2) polymers with both lipophilic and hydrophilic character; wherein each insecticide is soluble in at least one of the group consisting of: i) the monomers that make up the polymer; ii) oligomers of approximately the same proportional composition of monomer bound as the polymer; iii) the polymer and iv) a solution of the polymer and an organic solvent.
5. 5. The composition of claim 1, wherein the lipophilic character of the polymer is derived from monomer units selected from: a) (C 1 -C 24) alkyl esters, substituted or unsubstituted, of one or more monoethylenically unsaturated monomers, selected from the acids acrylic, methacrylic, fumaric, maleic and itaconic; b) alkyl (1-C24) amides, substituted or unsubstituted, of one or more monoethylenically unsaturated monomers selected from acrylic, methacrylic, fumaric, maleic and itaconic acids; c) α-olefins; and d) esters of vinyl alcohol, vinyl halides, vinyl nitriles and vinyl carboxylates.
6. 6. The composition of claim 5, wherein the monomer units are selected from the group consisting of one or more alkyl, alkyl methacrylates, acrylamides and methacrylamides, substituted and unsubstituted.
7. 7. The composition of claim 6, wherein the monomer units are selected from the group consisting of one or more (C1-C24) alkyl acrylates, (C1-C24) alkyl methacrylates, hydroxyalkyl acrylates (C2 ~ Cg), hydroxyalkyl methacrylates (C2 ~ Cg), dialkyl- (C? -Cg) amino-alkyl acrylates (C2 ~ Cg), dialkyl- (C-Cg) amino-alkyl methacrylates (C2 ~ Cg), dialkyl acrylamide (C -Cg) amino-alkyl (C2 ~ Cg), and dialkyl (C? -Cg) aminoalkyl (C2 ~ Cg) methacrylamide.
8. 8. The composition of claim 1, wherein the hydrophilic character of the polymer is derived from monomer units, selected from the group consisting of one or more (C? -Cg) alkyl esters, substituted or unsubstituted; thioesters of alkyl (C? -Cg), and mono- or di-alkyl (C? -Cg) -amides of one or more monoethylenically unsaturated monomers, selected from acrylic, methacrylic, fumaric, maleic and itaconic acids; vinyl esters, substituted and unsubstituted of carboxylates (C -C4); cyclic esters, amides and heterocycles; and amines substituted with vinyl.
9. 9. The composition of claim 8, wherein the monomer units are selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, dimethylaminoethyl and dimethylaminopropyl acrylates, dimethylaminoethyl methacrylates and dimethylaminopropyl, acrylamide, methacrylamide, substituted and unsubstituted vinylpyridines, N -methyl methacrylamide, N-methylolmethacrylamide, N-methylacrylamide, N-vinyl-2-pyrrolidinone, N-vinylpiperidinone, N-vinyl caprolactam, 2-pyrrolidinonylethyl methacrylate, N-vinyloxazolidinone and N- (methacryloxyloxyethyl) oxazolidinone.
10. 10. The composition of claim 1, wherein the insecticide is selected from one or more of the group consisting of: (a) fungicides selected from (1) nitrophenol derivatives; (2) heterocyclic structures; (3) various halogenated fungicides; (4) fungicidal antibiotics; (5) phenylbenzamide derivatives; (6) amino acid derivatives and (7) methoxyacrylates; (b) herbicides selected from: (1) carboxylic acid derivatives; (2) carbamic acid derivatives; (3) substituted ureas; (4) substituted triazines; (5) diphenyl ether derivatives; (6) aborted; (7) oxyphenoxy herbicides; (8) uracils and (9) nitriles; and (c) insecticides and miticides.
11. 11. A method for controlling a pest, this method comprises applying the composition of claim 1 to one or more of the group consisting of: (a) the pest, (b) the food source of the pest and (c) the habitat of the pest. the plague.