COMPOSITIONS OF INSOLUBLE FILM-FORMING POLYMERS AND USES THEREFOR

Abstract: A composition comprising a long-chain alkylpyrrolidone, a surfactant, and film-forming water-soluble polymer wherein the amounts of the components are such that on dilution with water, a clear liquid is formed. The composition may be used as a medium for agriculturally active ingredients as well as other active ingredients which are suitable for film formation, e.g., wood protectants, and the like. Also, emulsion concentrates of water-insoluble film-forming polymers are disclosed which can be utilized to form water-resistant films of active ingredients, such as, agriculturally active chemicals. Methods for preparation and use of the emulsion concentrates are disclosed.

Description: COMPOSITIONS OF INSOLUBLE FILM-FORMING POLYMERS AND USES THEREFOR BACKGROUND OF THE INVENTION A significant problem in the use of agriculturally active chemicals is that since they are applied to soil and plant surfaces, they are susceptible to being washed off by rain and/or water spray used for irrigation. This adversely affects the efficience of the chemicals, since the longer the chemical remains in contact with the plant or soil surface, the more effective it is. Certain types of polymers exhibit film-forming properties and when dissolved in an organic solvent, can be applied for the purpose of providing a water- resistant coating on a substrate. Usually, the film-forming polymer in the solvent is applied to the particular substrate to be coated, and the solvent is allowed to evaporate or removed leaving a film of the polymer. Generally, however, such water-resistant, film-forming polymers are soluble only in organic solvents, i. e., they are substantially insoluble in water. The use of such organic solvents generally is undesirable since they exhibit environ- mentally adverse properties, are often hazardous or flammable, and are generally expensive. In order to avoid the environmentally adverse effects of such organic sol¬ vents as well as to reduce the cost involved with using such solvents, rather complicated solvent recovery procedures must be used. Typical of such polymers are copolymers of N-vinylpyrrolidone with α-olefins, vinyl acetate, styrene, acrylates, acrylic acids, amides, maleic acid, mono and diesters of maleic acids, and the like. SUMMARY OF THE INVENTION I have discovered a method for providing a stable microemulsion of a particular class of water-insoluble film-forming polymers in water. The microemulsi- ons thus formed can be utilized to produce films of the particular film-forming polymer on a given substrate. For example, the microemulsion can be used as a coating for substrates, such as, wood, metal, glass, and the like. In addition, various active ingredient, e.g., fungicides, preservatives, insecticides, insect repellents, pheromones, radiation absorbents, dyes, and the like, can be included in the composition. A first class of the inventive compositions are composed of the water- insoluble polymer, a surfactant, and a long-chain alkylpyrrolidone. The amounts of the polymer surfactant and long-chain alkylpyrrolidone can vary within a broad range. However, the relative compositional ranges of each must be such that a clear, stable microemulsion or solution of the insoluble polymer is obtained on the addition of water. I have further discovered a second class of emulsion concentrates of such water-insoluble film-forming polymers which comprise a water-insoluble polymer, an agriculturally active chemical, and an organic solvent for the agricultur¬ ally active chemical. The water-insoluble polymers used in the present invention are graft polymers of vinylpyrrolidone and α-olefin wherein the N-vinylpyrrolidone is present in more than about 5 percent on a weight basis. Preferably, the weight percent of N- vinyl pyrrolidone is about 10 percent. The α-olefin should contain from 8 to 30, and preferably, from 16 to 20 carbon atoms. The emulsion concentrate of the present invention provides a stable emulsion upon dilution with water. Thus, the emulsion concentrate of the invention is particularly suitable for use with an agriculturally active chemical or ingredient (hereinafter, sometimes referred to as a.i.). The diluted inventive concentrate of the film-forming polymer may include an agriculturally active chemical or ingredient, such as, pesticides, herbi¬ cides, and the like. This composition may then be applied to plants, or soil, in the usual manner. I have found that the inventive composition, thus used, forms a fihn incorporating the a.i. on the leaf, soil or seeds and can prevent wash-out of the agri¬ culturally active ingredient due to rain. Thus, for example, the composition with an agriculturally active ingredient forms a film on the particular substrate, e.g., the plant or soil, which results in improved retention and enhanced bioactivity of the agricul- turally active ingredient and also provides superior rainfastness for such ingredients on leaf and substrate surfaces. The second class of inventive compositions are particularly convenient for use with oil-based concentrates, e.g., commercial Prowl, Fusilade, and Thiadiazuron. However, they can also be used in aqueous-based hydrophobic active ingredients, e.g, aqueous emulsions or dispersions "of carbaryl (Sevin). DETAILED DESCRIPTION OF THE INVENTION As used herein, the following terms have the meaning indicated: "macroemulsion" means an emulsion of water-in-oil or oil-in-water wherein the interior phase is in the form of visually discernable droplets and the overall emulsion is cloudy, and wherein the droplet diameter is greater than about 10 millimicrons (1 micron), and usually greater than 1000 millimicrons (about 10 microns), "microemulsion" means an oil-in-water or water-in-oil, transparent thermodynamical- ly stable dispersion of two or more immiscible liquids or a solid in a liquid wherein the dispersed phase consists of small droplets with diameters in the range of about 10 to 100 millimicrons. Such microemulsions are clear and appear as a single phase to the naked eye. "single phase" as applied to a liquid means that to the naked eye, the liquid is homogeneous and does not appear to contain any other separatable liquid phase. "clear" or "transparent" as applied to a liquid means that the liquid appears as a single phase without any particulate or colloidal material or a second phase being present when viewed by the naked eye. "substantially insoluble" or "insoluble" means that for all practical purposes, the solubility of the compound in water is insufficient to make the compound practicably usable in an agricultural end use without some modification either to increase its solubility or dispersability in water, so as to increase the compound's bioavailability or avoid the use of excessively large volumes of solvent. "High degree of loading in the concentrate" means an agriculturally active ingredient content of at least about 5 percent by weight, "agriculturally active chemical or ingredient" (AAC or a.i.) means compounds and mixtures thereof which can be used as agricultural fertilizers, nutrients, plant growth accelerants, herbicides, plant growth controlling chemicals, and chemicals which are effective in killing plants, insects, microorganisms, fungi, bacteria and the like which are commonly referred to as insecticides, bacteri- cides, fungicides, nematocides, fumigants, synergists, i.e., compounds which when used in conjunction with other AAC's enhance their activity and the like, as well as any other chemicals having properties which are suitable for agricultural uses in terms of application to plants or domestic uses for controlling insects and pests. Long-chain N-alkylpyrrolidones suitable for use as a solvent in the present invention have the formula wherein R 2 is hydrogen or alkyl having from 6 to 14 carbon atoms and R 3 is alkyl having from 6 to 14 carbon atoms with the proviso that at least one of R 2 or R 3 must contain at least 6 carbon atoms and the sum of the carbon atoms in R 2 and R 3 cannot exceed 14. Preferably, R 2 is hydrogen and R 3 is C g or C 12 . Mixtures of two long- chain alkylpyrrolidones may also be used. N-methyl pyrrolidone may also be includ¬ ed along with long chain N-alkylpyrrolidones in an amount effective to help maintain the solubility of the long chain alkylpyrrolidones. The solvent may be an organic diluent which is a synthetic or naturally occurring oil having a high hydrophobic character or having a fractional dispersive solubility parameter of greater than 70% and preferably greater than 85% and a molar volume of greater than 90 cm 3 /mole. These properties are defined in the C.R.C. Handbook referred to hereinabove. Typical diluents include soybean oil, rapeseed oil, long chain alcohols, long chain ketones, long chain esters, and ethers. As used herein, "long chain" means with 6 or more carbon atoms. Also suitable as the organic diluent are aromatic petroleum oils including those which are commercial¬ ly available distillates from crude oils having an average boiling point greater than 120°C. Typical of such materials are those sold under the trademarks Exxon 200 or Texaco 400. Of course, such aromatics should be approved for use as a carrier for agriculturally active chemicals. The composition of the aromatic petroleum oil is generally: Heavy aromatic solvent naphtha - about 60%; Middle distillate solvent extractant - about 40%; Normally, these oils contain predominantly the C9-C15 aromatic hydrocarbons and primarily the C10-C12 hydrocarbons having a flash point of about 203 °F. When a surfactant is used, e.g., because of the nature of the active ingredient, the concentration of the active ingredient desired, and the like, suitable surfactants include both water and oil-soluble surfactants, e.g., ethoxylated alkyl phenols, linear aliphatic polyesters, linear aromatic polyesters, polyalkenyloxy- alcohol, linear aliphatic ethoxylates, polyethoxylated castor oil, poly ethoxylated carboxylates, and polyethoxylated alkylamines. Oil and water-soluble anionic surfactants may be used as the emulsifier and include phosphate esters and their salts, alkyl sulfates, sulfonates, and their salts, salts of sulfate nonylphenoxypoly(ethylene- oxy) ethanol, salts of alkylbenzene sulfonates, e.g., the sodium, calcium and alkylammonium salts, salts of alkylnaphthalene sulfonate, and sulfonated aliphatic polyesters and their salts. Also suitable are complex phosphate esters of nonionic surfactants of the ethylene oxide type which are mixtures of diesters of phosphoric acid. (See, for example, McCutcheon's, Emulsifiers and detergents (1989), published by McCutcheon's Division of M.C. Publishing Co., Glen Rock, New Jersey.) Polymers particularly suitable for use in the present invention include polymers, such as, Ganex 516, which is copolymer of an α-olefin and N-vinylpyrro- lidone (50/50 percent mixture), copolymers of vinyl pyrrolidone and α-olefins. Typically, such α-olefins contain up to 20 carbon atoms, and preferably contain 16, carbon atoms. The weight average molecular weight of such polymers is generally greater than about 10,000. Particularly suitable are water-insoluble polymers, such as, Agrimer AL25 (International Specialty Products (ISP) Corporation), which is a copolymer of an α-olefin having the formula C 14 H 29 CH=CH 2 (50%) and N-vinyl- pyrrolidone (50%), and Agrimer AL30 (ISP Corporation), which is a copolymer of an α-olefin having 20 carbon atoms (80%), and N-vinylpyrrolidone (20%). Co- polymers of N-vinylpyrrolidone and vinyl acetate should contain at least about 10% N-vinylpyrrolidone and have a weight based on the total average molecular weight of at least about 10,000. Typically, the inventive concentrate comprises from about 2 to 90 percent, preferably from 5 to 85 percent, and most preferably, from about 30 to 80 percent by weight N-alkyl pyrrolidone organic solvent or both from about 2 to 30 and preferably, from about 8 to 15 percent by weight surfactant, and from about 1 to 60, and preferably from about 5 to 30 percent, and most preferably, 10 to 25 weight percent of the water insoluble polymer. If a surfactant is present, water may be present in an amount from 1 to 85 % and, preferably, from 3 to 70 percent, and most preferably, from about 5 to 60 percent by weight. All percents herein are percent by weight based on the total weight of the composition. The inventive compositions are particularly suitable for end use applications wherein films of water-insoluble polymers are formed on substrates. The films may be formed for adhesive, protective, decorative, lubricating, to impart hydrophobicity or hydrophilicity, and the like, purposes. Since it is desirable to avoid organic solvents due to their cost and adverse toxicological and environmental properties, the use of water as a solvent for the film-making procedure is preferred. With the inventive composition, it becomes possible to place such ordinarily water- insoluble film-forming polymers in an aqueous based vehicle, i.e., solution, emulsion or dispersion-solubilizing liquid, which can be handled and utilized in the same manner as a true solution of the polymer to form a film therewith. Thus, the inventive composition in microemulsion form may be coated as is, or after further dilution with water, if desired, onto a substrate. The water is then removed as by evaporation to leave the polymer film remaining. I have further discovered that the rainfastness of agriculturally active ingredients, and in particular, pesticides, can be substantially improved by formulat¬ ing the pesticides in the inventive composition including the water insoluble film- forming polymer. Thus, many pesticides, and particularly water soluble agricultural- ly active chemicals, are washed off by rain after they have been applied to the plants or soil. For effective pest and weed control, it takes from a few hours to three weeks for the pesticide to penetrate into the biological system. The present invention assures that the agriculturally active ingredient will be retained for a sufficiently long time to allow it to be effective and avoid or reduce rain wash-off. In use, the inventive composition is diluted with water and applied to the crop, plants, or soil. Normally, this dilution is carried out at the field site. As used herei: . rainfast resistant, rainfast or rainfastness in connection with the inventive compositions means that a film formed from the composition exhibits increased resis¬ tance to removal by water washing as compared to the same composition which does not contain the film-forming polymer under the test procedures as described hereinafter. Pesticides which can be used with the present invention, may be characterized by their physical properties, depending on their physical state at normal or ambient conditions, i.e., between 40°F and 90°F and their solubility or miscibility with water or other common organic solvents, e.g., aromatics, such as, toluene, xylene, methylated and polyalkylated naphthalenes, and aliphatic solvents. Based on the physical properties, the pesticides may be classified into three groups: The first group includes those which are oily liquids at ambient temperatures and are immiscible with water. Specific pesticides include: Common esters of 2,4-dichlorophenoxyacetic acid, Common esters of 2,4,5-trichlorophenoxyacetic acid, Common esters of 2-(2,4-dichlorophenoxy) propionic acid, Common esters of 2-(2,4,5-trichlorophenoxy) propionic acid, Common esters of 2,4-dichlorobutyric acid, Common esters of 2,methoxy-3,6-dichlorobenzoic acid, Common esters of 2-methyl-4-chlorophenoxyacetic acid, Piperonyl butoxide 3,4-methylenedioxy-6-propyl benzyl n-butyl diethylene glycol ether, Bromophos ethyl: 0,0-diethyl-0-2,5-dichloro-4-bromophenyl thionophosphate, N-(2-mercaptoethyl) benzene-sulfonamide (BETAS AN ® ), Isobornyl Thiocyanoacetate (THANITE ® ), Ioxynil ester of octanoic acid, Molinate S-ethyl hexahydro - 1 H - azepine-1-carbothioate, PP 511 0,0-dimethyl-(2-diethylamine 4-methyl-6-pyrimidinyl) carbamate, PP 211 0,0-diethyl O-(2-diethylamine-4-methyl-6- pyrimidinyl) phosphorocarbamate, 5-Ethoxy-3-(trichlorometyl)-l ,2,4-thiadiazole (TERRAZALE ® ), Ethyl-s-s-dipropyl-phosphodithioate (MOC AP ® ) , S-Ethyl dipropylthiocarbamate (EPTAM ® ), S-Ethyl diisobutylthiocarbamate (SUTAN ® ), S-n. propyl-di-n-propylthiocarbamate (VERNAM ® ), S-propyl butylethylthiocarbamatae (TILLAM ® ), S-ethyl ethylcyclohexylthiocarbamate (RO-NEET ® ), Malathion (S-(l,2-dicarboxyethyl)-0,0-dimethyl phosphorodithioate), Diazinon (0,0-diethyl,0-(2-isopropyl-4-methyl-6- pyrimidinyl) phosphorothioate, O-Ethyl-S-phenyl-ethylphosphonodithioate (D YFONATE ® ) , Toxaphene (Octachlorocamphene), Bromoxynil (3,5-dibromo-4-hydroxy benzonitrile ester of n.octanoic acid, 2-chloro-N-2,6-diethylphenyl-N-methoxymethylacetamide (LASSO ® ), Diallate S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate, Triallate S-2,33-trichloroallyl N,N-diisopropylthiolcarbamate. The second group comprises those pesticides which are solids at ambient temperatures and for all practical purposes, insoluble in water. 2,4,5-T (2,4,5-trichlorophenoxy acetic acid) Monuron (3-(p-chlorophenyl)- 1,1 -dimethyl urea) Diuron (3-(3,4-dichlorophenyl)-l,l-dimethyl urea) Bromacil (5 bromo-3-sec. butyl-6-methyl uracil) Isocil (5 bromo-3-isopropyl-6-methyl uracil) Linuron (3-(3,4 dichlorophenyl)-l-methoxy-l methyl urea Atrazine (2-chloro-4-ethylamino-6 isopropylamino-s- triazine) Simazine (2-chloro- 4, 6, -bis (ethylamino)-s-triazine Dodine (ώ-dodecylguanidine acetate) Thiram (tetramethylthiuram disulfide) N-(mercaptomethyl)phthalimide -(ό,ό dunethylphosphorodithioate) (IMIDAN®) Lindane (gamma 1,2,3,4,5,6 hexachlorocyclohexane) Folpet (N-trichloromethylphthalimide) Manazon (s-(4,6-diamino-l,3,5-triazin-2-yl methyl)dimethyl phosphorothiolthionate) Barban (4-chloro-2 butynyl m-chlorocarbanilate) Tricumba 2-methoxy-3 , 5 , 6-trichlorobenzoic acid Trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) (2,3 dihydro-5- carboxanilido-6-methyl-l ,4-oxathiin) (VITAVAX ® ) 2,4-dichlorophenoxyacetic acid 4-(4-chloro-2 methylphenoxy) butyric acid 2-(2,4-dichlorophenoxy) propionic acid Ioxynil: 3,5 diiodo-4-hydroxybenzonitrile Bromoxynil: 3,5 dibromo-4-hydroxy benzonitrile Methoxychlor: 2,2,-Bisφ-methoxyphenyl)-l , 1-trichloroethane PP 781: 4(2-chloro phenylhydrazono)-3-methyl-5-isoxazolone* PP 675: 5-butyl-2-dimethylamino-4-hydroxy-6-methyl pyrimidine* PP 062: 5, 6-dimethyl-2-dimethylamino-4 pyrimidinyl dimethylcarbamate* PP 149: 5-n-butyl-2 ethylamino-4-hydroxy-6 methylpyrimidine* * Manufactured by Imperial Chemical Industries Limited C 6313 N'-(4-bromo-3-chlorophenyl)-N-methoxy-N-methylurea C 6989 2,4'dinitro-4-trifluoromethyl-diphenylether Chloroxuron N'-4-(chlorophenoxy) phenyl-NN-dimethylurea Dichlobenil 2,6-dichlorobenzonitrile Diphenamid NN-dimethyl-2,2-diphenylacetamide Fenac 2,3,6-trichlorophenylacetic acid Fluometuron N'-(3-trifluoromethylphenyl)-NN-dimethylurea GS 14260 4-ethylamino-2-methylthio-6-t-butyl-amino-l,3,5-triazine PCP Pentachlorophenol Lenacil 3-cyclohexyl-6,7-dihydro-lH-cyclo-pentapyrimidine-2,4-(3H,5H)-dione Pyrazon 5-amino-4-chloro-2-phenyl-3-pyridazone Metrobromuron N'-(4-bromophenyl)-N-methoxy-N-methylurea Metoxymarc N-(4-methoxybenzoyl)-N-(3 ,4-dichlorophenyl)-N ' , N ' -dimethylurea Neburon N-butyl-N'-(3 ,4-dichlorophenyl-N-methylurea NI A 11092 1 , 1 -dimethyl-3-[3-(n-t-butyl carbamyloxy)phenyl] urea Mecoprop 2-(4-chloro-2 methylphenoxy)propionic acid Monolinuron N'-(4-chlorophenyl)-N-methoxy-N-methylurea Nitrofen 2,4-dichlorophenyl 4-nitrophenylether Propanil N-(3 ,4-dichlororphenyl)propionamide Pyriclor 2,3,5-trichloro-4-pyridinol Solan 3 '-chloro-2-methyl-p-valerotoluidide Terbacil 5-chloro-3-t-butyl-6-methyluracil UC 22463 (SIRMATE)-3,4-dichlorobenzyl N-methylcarbamate WL 9385 2-Azido-4-ethylamino-6-t-butylamino-s-triazine Propachlor 2-chloro-N-isopropylacetanilide CP 50144 2-chloro-N-2,6-diethylphenyl-N- methoxymethylacetamide CP 31675 2-chloro-N-(2 methyl-6-t-butylρhenyl)acetamide Cypromid 3',4'-dichlorocyclopropane carboxanilide Fenuron NN-dimethyl-N-phenylurea Chlorbromuron N'-(4-bromo-3-chlorophenyl)-N-methoxy-N-methylurea Ametryne 2-methylmercapto-4-ethylamino-6-isopropyl-amino-s-triazine Prometryne 2-methylmercapto-4,6-bisisopropyl amino-s-triazine DCPA dimethyl 2,3,5,6, tetrachloroterephthalate Benefin N-butyl-N-ethyl-2,2,2-trifluoro-2,6-dinitro-p-toluidine Nitralin 2,6-dinitro-4-methylsulfonyl-N, N-dipropyl-aniline PP 493 2, 6-difluoro-3,5-dichloro-4-hydroxy pyridine CNP 2,4,6-trichlorophenyl-4'-nitrophenyl ether Pentachloro nitrobenzene 1 -(butyl carbamoyl)-2-benzimidazole carbamic acid, methyl ester (BENLATE ® ). Carbaryl (methylnaphthyl carbamate) (active ingredient in Sevin). The third group constitutes those compounds which are water-soluble, such as, salts, e.g., the isopropylamine salt of phosphonomethyl glycine, the sodium salt of 2,4-dichlorophenoxy acetic acid, the sodium salt of methoxy dichloro benzoic acid (dichloro anisic acid), and dicamba (dimethylamine salt of methoxy dichloro- benzoic acid), Assert bisulfate (American Cyanamid), the ammonium salt of imazaquin (American Cyanamid), and the like. The following Examples illustrate the invention: The materials used in the Examples and designated by trademark or tradename are as follows: Agrimer AL25 copolymer of vinyl pyrrolidone and C 16 α- olefin in 50:50 weight ratio with a number average molecular weight of about 9500; Agrimer AL30 graft copolymer containing 80% by weight of C 20 α-olefin and 20% by weight of polymerized vinylpyrrolidone with a number average molecular weight of about 8600 available as a solid; Agrimer AL22 graft copolymer containing 80% by weight of C 16 α-olefin and 20% by weight of polymerized vinylpyrrolidone with a number average molecular weight of about 7300 available as a liquid; Agrimer VA3 copolymer containing 30 mole % vinylpyrrolidone units and 70 mole % vinylacetate unit with a number average molecular weight of 5700 and weight average molecular weight of 28,800 determined by the GPC method; Acrylidone ACP-1004 copolymer containing 50:50 weight ratio of the monomer with number average molecular weight = 30,000 - 60,000, 100,000 - 300,000. Rodeo a commercially available pesticide of an aqueous solution con¬ taining 53.8% of the isopropylamine salt of phosphonomethyl- glycine (a.i.-l) (Monsanto). Latron B1956 77% modified phthalic glycol alkyl resin, and 23% inert ingredients including organic solvent (Rohm & Haas); Prowl an emulsion concentrate containing 42.0% by wt. pendimethalin (a.i.-2). The balance constitutes surfactants and solvents, Roundup a commercially available concentrate of glyphosate with suitable wetting agents. Glyphosate is the isopropylamine salt of phosphonomethy lglycine . Gramoxone a commercially available concentrate of Paraquat in suitable wetting agents. Paraquat is l,l-dimethyl-4,4'-bipyridinium dichloride (American Cyanamid). Alcasurf CA a commercial form of calcium dodecyl benzene sulfonate produced by Rhone Poulenc containing an oil-soluble anionic surfactant (0.32 parts propylene glycol, 0.65 parts n-butanol, 3.90 parts calcium dodecyl benzene sulfonate and 1.62 parts of aromatic hydrocarbons). Pendimethalin N-(l-ethylpropyl)-3,4-dimethyl-2,6-dinitrobenzenamine. Fusilade EC a commercial formulation of the active ingredient butyl 2-[4-(5- trifluoromethyl-2-pyridyloxy)phenoxy] propionate (FUSILADE 2000) which is a selective systemic herbicide for control of grass weeds in broadleaved crops. Thiadiazuron N-phenyl-N'-l ,2,4-thiadiazol-5-yl urea. The following examples (Examples 1 through 23) relate to the first class of the inventive composition as described above. Example 1 Compositions containing water insoluble polymers in a water-based medium were prepared as follows: Preparation of Matrix In a 4 oz. stoppered glass bottle, 48.33 g of N-octylpyrrolidone, and 41.67 g of a 29% by weight aqueous solution of sodium dodecyl sulfate (commercial¬ ly available) were added and stirred to form a homogeneous solution containing 48.33 g of N-octylpyrrolidone, 12.06 g of sodium dodecyl sulfate and 29.61 g water. This solution is referred to herein as the stock matrix solution. To 90 g of the stock matrix solution were added 10 g of the dry water-insoluble Agrimer AL25. The solution was stirred in an automatic orbital shaker at 400 RPM for a period of 3 hours, which produced a homogeneous single phase system. On 10X, 500X and 1000X dilution with deionized water, the diluted composition remained homogeneous for more than 72 hours. The dry Agrimer AL25 was prepared by evaporation of the commercially available 50 percent solution of AL25 in isopropyl alcohol under reduced pressure, drying the residue in vacuum oven at about 60 - 70 °C at 1 mm Hg., and then grinding under a blanket of liquid nitrogen to produce a particulate solid. Example 2 • Example 1 was repeated using 85 parts of stock matrix solution and 15 parts of the polymer. The resulting composition is shown in Table 1 and is referred to herein as Composition I. This composition was also in a homogeneous single phase system. On 10X, 500X, and 1,000X dilution with deionized water, the diluted composition remained homogeneous for more than 72 hours. Example 3 Example 1 was repeated using 80 parts of stock matrix solution and 20 parts of the polymer. The resulting composition is shown in Table 1. At 10X and 500X dilution with deionized water, the compositions produced exhibited no separation for more than 72 hours. When 1 part of the composition was diluted to 1000 parts with deionized water, a single minute crystal was observed. TABLE 1 Compositions of a Single Phase System Containing Agrimer AL25 in an Aqueous Medium *) single phase with minute crystal separations Example 4 This example illustrates the inability of an isopropyl alcohol (IPA) solution of Agrimer AL25 to remain homogeneous in the absence of the inventive stock matrix. A composition was prepared by mixing 40 g of a 50 % solution of Agrimer AL25 in IPA, 35.72 g of a 29% aqueous SDS solution and 24.20 g of deionized water. The resulting composition contained by weight: 25% Agrimer AL25, 20% IPA, 10.36% SDS, and 49.64% water. The resulting product was a milky, cloudy emulsion. Microscopic observation at 250x showed particles/oil droplets of about 5-10 μ in size. Examples 5 through 9 illustrate the importance of the presence of more than 20% on a weight basis of vinyl pyrrolidone in the copolymer. Example 5 90 parts stock matrix solution, and 10 parts of Agrimer AL30 were mixed in an automatic orbital shaker for 4 hours. No dissolution occurred. Example 6 Example 5 was repeated replacing Agrimer AL30 with 10 g of Agrimer AL22. After stirring for 4 hours in an automatic orbital shaker, oil separation was observed. Example 7 Example 4 was repeated using 98 parts of stock matrix solution and 2 parts of Agrimer VA3. The composition did not produce a single phase system on stirring in an automatic orbital shaker for 4 hours. Example 8 Example 4 was repeated with 95 parts of stock matrix solution and 5 parts of Acrylidone ACP-1004. A homogeneous phase was not obtained after 4 hours of stirring. Example 9 Example 4 was repeated using 95 parts of stock matrix solution and 5 parts of cross-linked polyvmylpyrrolidone with a molecular weight of about 1 MM. A single phase system was not obtained. However, the polymer was wetted by the matrix. Part A A series of polymer films formed from the inventive composition were evaluated for rain-fastness. The formulations were prepared as follows: 1. A commercial formulation of a given agriculturally active ingredient was admixed with the inventive composition. 2. The liquid mixture was then diluted to end use concentrations. 3. An appropriate dose (0.1 g to 0.5 g) was applied to a 6" x 6" glass plate uniformly as a 1-3" square patch. The patch was dried in a hood under ambient conditions for 48 -72 hours. 4. After a dry film was formed, a fine spray of water was applied to simulate 0.5 - 2 inches of rain wash-off. The washings were collected in a waste jar. 5. The remaining washed patch was extracted with a solvent (ethanol is preferred) quantitatively into a 100 ml volumetric flask. If desired, appropriate dilutions of the ethanol extract were made. 6. The ethanol extract was subjected to ultraviolet spectra examination and the absorbance at a λ max. was determined (value Xj). 7. Blank samples of diluted formulations were prepared and measured using UV absorption. These values were utilized to prepare a calibra¬ tion chart. This value is X 2 . 8. The percent retained was then determined by dividing X_ by X 2 and multiplying by 100. 9. Blanks were run without polymer using the commercial formulations under identical conditions. The percent retained is identified as R,,. 10. For samples wherein the pesticide used is Pendimethalin, λ max. is 239 nm. 0.3 g of diluted samples were used for patches (1 - 2 square inches). The amount of wash-off water used was 1.5 to 2.5 g. Using this technique, a series of compositions were formulated and tested for retention of the active ingredient. Part B Rainfast evaluations The following solutions were prepared: Solution 9A 4.0036 g of Rodeo was diluted to 100 g with deionized water. This solution contained 2.15% a.i.-l. on a weight basis. Solution 9B 4.0101 g Rodeo was mixed with 0.13 g of Composition I and diluted to 100 g with deionized water producing a clear solution. Solution 9C 4.0033 g Rodeo was mixed with 0.34 g of Composition I and diluted to 100 g with deionized water producing a clear solution. Solution 9C 4.0095 g Rodeo was mixed with 0.66 g of Composition I and diluted to 100 g with deionized water producing a clear solution. Samples of solutions 9A, 9B, 9C, and 9D were analyzed for the a.i.-l. content via potentiometric titration using standard NaOH (0.0217 N). The NaOH was standardized using a standard solution of sodium hydrogen phthalate. For 0.6911 g of 9A, 0.7044 g of 9B, and 0.7189 g of 9D, 3.00 ml of NaOH was required. For 0.7045 g of 9C, 2.95 ml of the NaOH solution was required for neutralization. The % a.i.-l. for the samples 9A, 9B, 9C, and 9D were 2.17, 2.13, 2.13, and 2.08%, respectively, against the theoretical value of 2.15%, thus validating the experimental procedure. Rainwash Treatment Samples of solutions 9A, 9B, 9C, and 9D were spotted on glass plates using the above-described procedure and dried at room temperature for 72 hours. The dried films were subjected to a fine spray of water using a spray bottle deliver¬ ing a fine spray of water from an aspirator. The amount of water delivered was 1.49 g to 1.54 g. The remaining film was recovered into a beaker by washing the slide with a 10% EtOH aqueous solution and the washings were titrated with 0.0219 N NaOH. The endpoint of the titration was evaluated either potentiometrically or by using phenolphthalein as the indicator. The % a.i.-l. retained was calculated by dividing the experimental concentration of a.i.-l by the theoretical or actual concentration of the a.i.-l found in the samples. Table 2 summarizes the results. TABLE 2 Results of Rainfast Evaluation TABLE 2 Results of Rainfast Evaluation Example 10 The procedure of Example 9 was repeated using the following solutions: 10A: 4.0069 g Rodeo diluted to 100 g with deionized water; 10B: 4.0018 g Rodeo and 0.1559 g of Composition I diluted to 100 g with deionized water; 10C: 4.0076 g Rodeo and 0.1133 g of the stock matrix solution of Example 1. The results are shown in Table 3. TABLE 3 Results of Rain Wash Evaluation TABLE 3 Results of Rain Wash Evaluation The difference between Examples 10B and IOC is the presence of polymer Agrimer AL25 which increases the retention of the water soluble a.i.-l. from 14.9% to 36.6%. The matrix when used alone without the polymer accelerates the washing of the a.i. The polymer forms a water resistant film when used in combination with the matrix and retains the a.i.-l. Example 11 Evaluation of Rainfastness of Rodeo with and without Composition I The procedure of Example 9 was repeated using compositions 9A and 9B (herein designated 11A and 11B, respectively). However, the glass plate was covered by parafilm sheets to provide a hydrophobic surface similar to that of a plant leaf surface. Composition 11A was prepared by diluting 4.000 g of Rodeo to 100 g with deionized water to form a homogeneous solution. Composition 11B was pre- pared by mixing 4.0101 g of Rodeo and 0.3327 g of Composition I and diluting the mixture to 100 g with deionized water. The results are shown in Table 4. TABLE 4 Rainfast Evaluation of Rodeo with Composition I on Parafilm Surface Example 12 A rainfast evaluation of Rodeo with commercially available Latron B1956 as a tank mix additive was carried out. For comparison, samples of Latron B1956 stripped of its solvent and Composition I with Rodeo were prepared. The mixture was diluted before use after storing the concentrate with the adjuvant for 72 hours. The following compositions were prepared: 12A-R3: 4.00 g Rodeo diluted to 102 g with deionized water to produce a clear homogeneous solution. 12A-R4: 4.00 g Rodeo diluted to 100 g with deionized water. 12A: 4.00 g Rodeo was mixed with 0.2 g Latron B1956 diluted to 100 g to produce an emulsion. 12B: 100 g of commercial Latron was stripped of the volatile solvents by evaporation at 82° C. under 65 mm Hg vacuum for a period of 2 hours. The weight loss was 19 g. The resulting product (81 g) is designated solvent stripped Latron B1956. 1.57 g of the solvent stripped Latron was mixed with 29.26 g Rodeo and stored as a concentrate containing 95% Rodeo and 5% a solvent stripped Latron B1956. The concentrate described above was stored for 72 hours. 4.00 g was diluted to 100 g with deionized water to produce an emulsion. 12C: 22.924 g Rodeo was mixed with 2.075 g of Composition I to produce a composition containing 91.69% Rodeo and 8.30% of Composition I. The mixture was an emulsion due to the concentration of the salt (Rodeo). After 24 hours standing, it separated into two layers. However the two layers mixed completely upon two to four inversions and produced a stable emulsion that could be used within a few hours. A 4.0 g sample of the above emulsion (obtained after storage for 72 hours and inverting 2-4 times just before withdrawing the samples) was diluted to 101.9 g with deionized water which produced a clear solution. The compositions were evaluated for rainfastness as described in Example 9. The results are set forth in Table 5. As shown, Latron B1956 exhibited an enhanced wash-off effect for a.i.-l rather than improving its retention. The inventive composition exhibited an 80% higher retention of the a.i.-l under the conditions of the experiments. TABLE 5 Rainfastness Evaluation of Rodeo with Latron B1956 and Composition I (added to concentrate) TABLE 5 Rainfastness Evaluation of Rodeo with Latron B1956 and Composition I (added to concentrate) TABLE 5 Rainfastness Evaluation of Rodeo with Latron B1956 and Composition I (added to concentrate) Example 13 Rainfast evaluations for the inventive composition with pendimethalin (a.i.-2) were carried out. The a.i.-2 was in the commercial formulation Prowl. The procedure of Example 9 was followed. The a.i. -2 retention was determined by measuring the differential absorbance of the wash solution and EtOH at λ = 238.5 nm. The following compositions were prepared for comparative evaluation. 13A: 1 g of Prowl was diluted to 100 ml with deionized water which produced a stable emulsion having an a.i. -2 concentration of 0.42% . An emulsion rather than a single phase was formed because pendi- methalin is water insoluble. However, this does not affect the im¬ provements obtained with the inventive composition. 13B: 1 g of Prowl was mixed with 0.13 g of Composition I, Example 2, and diluted to 100 g to form an emulsion containing 0.42% pendimethalin and 0.02% Agrimer AL25 which was well dispersed in the medium. 13C: Example 13B was repeated using 0.33 g of Composition I, to produce an emulsion containing 0.42% pendimethalin and 0.05% Agrimer AL25. 13D: Example 13B was repeated using 0.66 g of Composition I, producing an emulsion containing 0.42% a.i.-2 and 0.1% Agrimer AL25. Details of the Procedure: Emulsions were prepared as above from 13A, 13B, 13C, and 13D. While stirring, aliquots were taken. 1 g of each aliquot was diluted with EtOH to 100 g, and further diluted 10X to 50X with EtOH. UV spectra of the diluted samples were obtained. The absorbance readings at λ = 238.5 nm for the samples fell in the range from 0.77 to 0.80, and the corresponding concentrations of the a.i.-2 were calculated to be 0.476 %-0.492%. These values were used as the 100% reten- tion values. The concentrations were calculated using a least squares line constructed using standard solutions of pendimethalin in EtOH. The least squares formula used was: absorbance = 0.080579 x concentration (ppm) + 0.0008785. Glass plates were spotted in triplicate with about 0.3 g of the above emulsions. Films were formed by drying under ambient conditions for 72 hours. The films were rainwashed using water from an aspirated spray bottle. The remaining films were washed with 50-100 ml EtOH and the washings were collected. The absorbance of the ethanol solutions at λ = 238.5 nm were measured, and the % retention was calculated. The results are summarized in Table 6. The data shows that when Agrimer AL25 is used in the form of Composition I, much higher retention of the a.i.-2 is obtained. (64% Ex. 13C as compared to 21.3% for control Ex. 13A.) TABLE 6 Spreader-sticker Evaluation of Pendimethalin with Composition I TABLE 6 Spreader-sticker Evaluation of Pendimethalin with Composition I Example 14 An evaluation of the rainfastness of compositions of Latron B1956 and pendimethalin were carried out. Example 13 was repeated using Prowl and commercial Latron B1956. The following compositions were prepared: 14A: 1 g of Prowl was diluted to 100 g with deionized water to produce a uniform emulsion. 14B: 1 g of Prowl was mixed with 0.1 g Latron B1956 and diluted to 100 g with deionized water to produce a uniform emulsion. 14C: Example 14B was repeated using 0.2 g Latron B1956 in the place of 0.1 g Latron B1956. In Example 13, all spots were dried outside the hood and the spray bottle was held about 1-2" away from the spot where 1 g of rain wash water was used. In Example 14, all spots were dried inside the hood and the spray bottle was held about 4" away from the spot where 2 g of rainwater was used. The results of the evaluation of Latron are summarized in Table 7. TABLE 7 Spreader-sticker Evaluation of Pendimethalin with Latron B1956 TABLE 7 Spreader-sticker Evaluation of Pendimethalin with Latron B1956 Example 15 Preparation of Modified Matrix The following weighed ingredients were introduced into a 4 oz. stoppered glass bottle: The following composition was similarly prepared except that N- methylpyrrolidone was not included. The following compositions were obtained: TOTAL 100.0% 100.0 Composition 15 A was a single-phase clear solution, while composition 15B separated into two layers on standing. Composition 15A was diluted 1/10, 1/50, 1/100 with deionized water. All of these diluted three samples were clear when observed up to 24 hours. Composition 15A was used as an alternate matrix to solubilize Agrimer AL25. Example 16 To 47.51 g of composition 15A. 2.5 g of solid Agrimer AL25 were added and stirred in an orbital shaker for 4 hours at 350 RPM. 50.03 g of a clear homogeneous solution were obtained. This solution was diluted with deionized water in ratios of 1/10, 1/500, and 1/1000. No separation was observed in the diluted solution after for 24 hours. Example 17 Example 16 was repeated but using 45 g of composition 15A and 5.00 g of Agrimer AL25. The resulting composition remained a homogeneous single phase solution. On dilution with deionized water at ratios of 1/10, 1/500, and 1/1000, no separation was observed. Example 18 Example 16 was repeated using 42.5 g of composition 15 A and 7.51 g of Agrimer AL25. The resulting polymer solution was clear and homogeneous and did not show any separation on dilution with deionized water at ratios of 1/10, 1/500, and 1/1000. Example 19 " A series of examples were carried out using various alkyl pyrrόlidones, including N-methyl pyrrolidone, N-octyl pyrrolidone, and N-dodecyl pyrrolidone. The N-dodecyl pyrrolidone exhibits stronger surfactant properties whereas the N-octyl exhibits stronger wetting properties, i.e., it wets hydrophobic surfaces as evidenced by the Draves Wetting test. The N-methyl pynolidone, on the other hand, is a better solvent and also provides enhanced plant and leaf penetration properties. I have found that a particularly desirable composition contains about 0.1 to 10, and preferably, about 0.5 to 2 parts of N-dodecyl pynolidone, and 0.1 to 10, and preferably, about 0.5 to 2 parts of N-methylpynolidone to 1 parts of N-octyl pyrrolidone, respectively. This composition provides not only enhanced leaf penetration, but also, better spreading due to the N-dodecyl component. Additional¬ ly, this composition allows increased amounts of the polymer component to be included in a single phase system. For this purpose, Example 16 was repeated using 40.03 g of composi¬ tion 15A and 10.01 g of Agrimer AL25. A homogeneous polymer solution was obtained after stining for 4 hours in an automatic orbital shaker. No separation on dilution with deionized water at ratios of 1/10, 1/500, and 1/1000 was observed. Compositions of Examples 16, 17, 18, and 19 and results of dilution are shown in Table 8. TABLE 8 Additional Compositions of Single Phase Systems Containing Agrimer AL25 in an Aqueous Medium Example 20 A series of microemulsions were prepared using the compositions of Examples 9B, 9D, 11B, 12C and 13B, with the exception that in place of Composi¬ tion I, the composition of Example 19 was utilized. The compositions thus obtained were tested for rainfastness and produced results essentially similar to those depicted for the compositions 9B, 9D, 11B, 12C and 13B. Example 21 Compositions I of Example 19 were prepared as follows: The commercially available 50% solution of Agrimer AL25 in isopropylalcohol was mixed with the appropriate quantity of N-octyl pynolidone or N-dodecyl pynolidone. The mixture was then subjected to distillation conditions to distill off the isopropylalcohol either at atmospheric or under reduced pressure (17 mm Hg). When all of the isopropylalcohol was removed, the remaining ingredients constituting the compositions as shown were added. These compositions were evaluated for rainfastness in the manner described above by repeating Examples 9 A, 9D, 13 A and 13B. The results obtained were essentially similar to those of these examples. Accordingly, it is possible to add the polymer in an in situ manner as well as the dried polymer as described in connection with the preparation of the matrix. Example 22 A freeze dried formulation in accordance with the invention was prepared as follows: Phosphonomethylglycine, 169 g (1 mole), was blended with NaHCO 3 , 168 g (2 moles), both of these being solids, to produce a mixture which forms the sodium salt of the phosphonomethylglycine on contact with water. The mixture was ground to a fine powder. 80 g of this mixture was then blended with 20 g of the inventive composition (Composition I), followed by the addition of 50 g of water. This composition was subjected to freeze-drying and produced 70 g of a free-flowing powder product. Upon mixing with water on the basis of 1 % by weight of the free- flowing powder product, a clear liquid (single phase) was obtained. This procedure thus allows for preparation of an inventive composition which is in dry form and thus easily transportable and which can, at the use or field site, be converted to a clear liquid upon the addition of water. It is particularly convenient as the dry inventive composition can be packaged in predetermined weights in a water-soluble container, e.g. , a bag, which can simply be added to a dilution tank in the field. If the active ingredient is water-soluble, then the use of bicarbonate or other soluble salt-forming reactant is not necessary. If effervescence is desired to enhance the rate of dissolution of the solid on the addition of water, an effervescing component, e.g., citric acid, or additional of bicarbonate may be added. Example 23 A series of tests were canied out to evaluate the effect of the inventive compositions on the efficacy of two commercially available herbicides, namely, Roundup and Gramoxone for Bahia grass and broad-leaf weed control. The tests were conducted in Lake Alfred, Florida in citrus groves having trees of two years of age. The chemicals applied, conditions and application parameters at the time of application were as follows: The concentrates were diluted so as to provide 1 lb Glyphosate at 20 gallons per acre and 0.625 lbs. Paraquat at 20 gallons per acre. Weather clear Humidity 50% Wind velocity calm Water source well pH 7.1 Volume of spray 20 GPA (Gallons per acre) Spray pressure 35 psi Source of pressure compressed air Nozzle type/size Teejet tips 8001 Nozzle spacing 10 inches Type of sprayer Tractor mounted boom sprayer Tractor speed 2.73 mph Plot size 45 x 10 ft. Number of treatments 31 Number of replications 3 Total number of plots 93 Stage of weed growth 4 - 6" high Major weeds Broadleaf weeds: camphor weeks Florida pusley Jerusalem oak lambsquarters pigweed Spanish needles tea weed The application was carried out in one day from 8:00 A.M. to 5:00 P.M. Tables 9 and 10 show the effects of the treatment with controls and the inventive compositions on the growth of the respective weeds over a period of 63 days. The herbicide was mixed with either inventive Composition I or Complex so as to give the active ingredient concentrations (a.i.-l) as indicated on Table 8. Complex had the following composition: Alkyl polyoxyethylene esters Polymerized resins and fatty acid 16.6% Reactive amines 5.2% Aromatic petroleum solvent 4.9% Inert solvents 72.3% TABLE 9 Evaluation for Bahia grass control (%) Kill TABLE 9 Evaluation for Bahia grass control (%) Kill TABLE 10 Evaluation for Broadleaf Weed Control (%) Kill TABLE 10 Evaluation for Broadleaf Weed Control (%) Kill NOTES FOR TABLES 9 AND 10 A Composition I was diluted at the rate of 0.025 gallon in 10 gallons of water to produce 0.25% solution. B "Complex" was diluted as in Example 23 A. C Commercial Roundup containing 4 lbs. a.i. per gallon was diluted to 80 gal. to be sprayed in 4 acres. D Composition C was prepared except 0.05 gal. of Composition I was added to 1 gal. of Roundup and diluted to 80 gal. to be sprayed in 4 acres. E Composition D was altered by using 0.1 gal. of Composition I instead of 0.05 gal. F Composition D was altered by using 0.2 gal. of Composition I instead of 0.05 gal. G Composition D was altered by using 0.05 gal. Complex in the place of Composition I. H In 20 gal., 0.1 gal. Complex was used in the place of 0.05 gal. I In 20 gal., 0.2 gal. Complex was used in the place of 0.05 gal. J Commercial Gramoxone containing 2 bis. a.i. per gal was diluted at the following rate: 1.25 gal. was diluted to 80 gal. to be sprayed in 4 acres. K J was modified by adding 0.05 gal. of Composition I before final dilution. L K was modified by using 0.1 gal. of Composition I in the place of 0.05 gal. M K was modified by using 0.2 gal. of Composition I in the place of 0.05 gal. N K was modified by using 0.05 gal. of Complex in the place of Compo¬ sition I. O N was modified by using 0.1 gal. of Complex in the place of 0.05 gal. P N was modified by using 0.2 gal. of Complex in the place of 0.05 gal. These results show that an enhanced biological efficacy is obtained when the a.i. is used as an adjuvant in the inventive composition. In particular the effect of the a.i. is accelerated and/or increased. Thus, with the present invention, it becomes possible to decrease the amount of active ingredient and still achieve a high efficacy. The following examples (Examples 24 through ...) relate to the second class of the inventive composition as described above. In accordance with this embodiment of the invention, emulsion concentrates (EC) may be prepared by mixing an active ingredient with a water- insoluble polymer in accordance with the invention and a solvent for the water- insoluble polymer. Such solvents can include aromatic diluents as well as long-chain alkyl pynolidones. These concentrates may then be diluted with water to provide stable emulsions. I have discovered that a stable emulsion can be prepared from such a concentrate without the presence of a water-soluble surfactant. Thus, in Example 24, comparison of a composition with an aromatic diluent and with and without a water-soluble surfactant is shown. In Example 25, the use of N-octyl pynolidone as a solvent is shown with and without the presence of a water-soluble surfactant. In each case, a stable macroemulsion could be obtained by dilution of the compositions without the water-soluble surfactant. In addition, as is shown in Example 26, the inventive emulsion concentrates provide excellent rainfastness with respect to retention of the active ingredient. Examples 24 and 25 illustrate the preparation of inventive compositions wherein a solvent, e.g., an aromatic diluent or long-chain alkyl pynolidone, are used. Example 24 The compositions shown in Table 11 below were prepared by mixing the ingredients and shaking in an orbital shaker for 30 minutes to form homogeneous concentrates. TABLE 11 AL 25 is commercially available as a 50 percent solution in isopropyl alcohol (IPA). It is used in these examples as a solid obtained by stripping the IPA by evaporation under vacuum below 65 °C. The emulsifiable concentrates I A and I B were evaluated for cold stability and the quality of the emulsion obtained on dilution to two percent with water. It is noted that this is the conventional dilution rate for use in the field. The results are shown in Table 11 A. TABLE 11A FREEZE STABILITY OF Pendimethalin EC* * measured at 2 ± The emulsions were evaluated to determine the amount of active ingredient which could be recovered. For this purpose, 50 g of the emulsions obtained on dilution of the compositions I A and I B were introduced to a long Nessler tube. 1 g aliquots of samples were withdrawn from the middle of the tube periodical- ly, diluted with ethanol 1/500 times and UV spectra were taken. The absorbance at 238.5 nm (λ max. i.e., the wavelength conesponding to maximum absorbance) was measured and calibration data for absorbance versus concentrations was obtained using standard solutions. Using a least squares line (absorbance = 0.08058 x concentration (ppm) + 0.0008785), the amount of active ingredient present in the sample taken from the Nessler tube was evaluated over a period of 24 hours. A constant recovery rate of 100% was obtained for each of compositions I A and I B . The above diluted emulsion concentrate (Ec) I A and I B were evaluated for emulsion stability on standing. Formation of foam, solid, cream, oil and crystal formation upon microscopic examination were observed. The emulsion was passed through various mesh screens to separate any crystals formed which were observed under 250 x magnification. The results are shown in Table 1 IB hereinafter. TABLE 11B EMULSION EVALUATION OF PENDIMETHALIN EC ON STANDING As used herein, the oil means a clear layer and cream means a cloudy layer of solid and oil. Table 11C shows the formation of crystals for compositions I A and I B over a period of time. TABLE 11C CRYSTAL FORMATION OBSERVATIONS FOR PENDIMETHALIN EC MICROSCOPE 250X Example 25 Compositions were prepared using the procedure of Example 24 and the following ingredients: TABLE 12 The emulsifiable concentrates were evaluated for quality of emulsion on dilution. These results obtained using the same procedure as for compositions I A and I B are shown in Table 12A and 12B. TABLE 12A EMULSION EVALUATION OF Thiadiazuron EC ON STANDING T = Top; = ottom TABLE 12B CRYSTAL FORMATION OBSERVATIONS FOR THIADIAZURON EC MICROSCOPE 250X As shown, a stable emulsion on dilution with water can be obtained with the inventive emulsion concentrate without the use of a water-soluble surfactant. Example 26 Rainfastness evaluations were carried out for polymer films formed in accordance with the invention. These evaluations were canied out using composi¬ tions prepared from commercially available formulations. Such formulations conventionally are composed of an agriculturally active chemical (the active ingredient), surfactants and organic diluents as solvents. Consequently, with such commercial formulations, simply by adding the water insoluble polymer in accor¬ dance with the present invention, one can obtain the emulsion concentrate of the invention, the solvent and surfactant being present. It is noted that while the surfactant is already present in the commercial formulation as obtained and, consequently, cannot be removed, it is actually not necessary when used with the water-insoluble polymer according to the invention. However, its presence does not adversely affect the ability to produce a significant improvement in the rainfastness of the commercial formulation. The general procedure used was as follows: 1. A commercial formulation of a given agriculturally active ingredient was admixed with a film-forming water-insoluble polymer. 2. The liquid mixture was then diluted to end use concentrations. 3. An appropriate dose (0.1 g to 0.5 g) was uniformly applied to a 6" x 6" glass plate uniformly as a 1-3" square patch. The patch was dried in a hood under ambient conditions for 48 -72 hours. (3 samples were tested for each formulation.) 4. After a dry film was formed, a fine spray of water was applied to simulate 0.5 - 2 inches of rain wash-off. The washings were collected in a waste jar. 5. The remaining washed patch was extracted with a solvent (ethanol is prefened) quantitatively into a 100 ml volumetric flask. If desired, appropriate dilutions of the ethanol extract were made. 6. The ethanol extract was subjected to ultraviolet spectra examination and the absorbance at a λ max. was determined (this value is designat¬ ed X,). 7. Blank samples of compositions III A , III B , III C , III D , III E , III F , and III G were obtained by diluting each in ethanol to yield a solution containing 8 ppm of the active ingredient. The UV absorption of each was measured. These values were utilized to prepare a calibration chart. This value is designated X 2 . 8. The percent retained was then determined by dividing Xj by X 2 and multiplying by 100. 9. Blanks of the commercial formulations without polymer were run under identical conditions. The percentage was calculated. 10. For samples wherein the pesticide used is Pendimethalin, λ max. is 239 nm. 0.3 g of diluted samples were used for patches (1 - 2 square inches). The amount of wash-off water used was 1.5 to 2.5 g. In all examples using an aromatic oil in the formulations, samples of the alcohol extract from the dried spot after the rain wash were completely evaporat- ed in a vacuum oven to remove any residual aromatic solvent so as to avoid interference therefrom in the absorbance analysis. Using the above general procedure, rainfastness evaluations for commercial pendimethalin formulations using Prowl as a commercially available emulsifiable concentrate of this active ingredient. This commercial formulation contains 42.0% of the active ingredient with the balance being surfactants and organic solvents. The compositions used were as follows: Composition III A - 1 g of Prowl was diluted with 100 ml of D.I. water to provide an end use composition containing 0.42% active ingredient. Composition III B - 90 parts of Prowl were mixed with solid Agrimer AL 25 (10 parts). 1 g of this mixture was diluted to 100 parts with D.I. water. Composition III C The formulation of I A (1 g diluted to 50 g with D.I. water). Composition IH D The formulation of I B (1 g diluted to 50 g with D.I. water). Composition III E This composition was the same as III B except that Agrimer VA3 was used in place of Agrimer AL 25. Agrimer VA 3 is com¬ mercially available as a 50% solution in ethanol. In these examples, it was used in solid form obtained by stripping the ethanol from the solution under vacuum at low temperature - under 65 °C). The resulting composition was obtained by diluting 1 g to 100 ml with D.I. water. Composition III F 90 parts of Prowl were mixed with 10 parts of solvent-stripped Latron B1956. 1 g of this composition was diluted to 100 g with D.I. water. Composition III G - The composition was the same as composition III B except that Agrimer AL 25 was replaced with Agrimer AL 30. The results of the rainfastoess formulations are shown in Table 13. TABLE 3 cr> o For comparison with III F and IIIQ. To test the validity of the procedure, compositions III A , IH B , III C , III D , III E , III F , and III G were diluted in ethanol to yield a solution containing 8 ppm of the active ingredient. The UV absorbance was measured at λ max. and all values (concentration of active ingredient) were within ± 2 % of the theoretical values. Example 27 The following compositions were prepared: Composition IV A - identical to composition πi A Composition IV B - same as composition HI B except that 2 parts of Agrimer AL 25 were mixed with 98 parts of Prowl and 1 g of this mixture was diluted to 100 g with D.I. water. Composition IV C - This was the same as composition HI B except 5 parts of Agrimer AL 25 were mixed with 95 parts of Prowl. The rainfastness was evaluated using the experimental procedure of Example 26. The percent of active ingredient recovered from the formulations is shown in Table 14. TABLE 14 Compositions % Agrimer AL 25 % a.i. recovered in the final dilution IV A 0 54.7 ± 6 IV B 0.02 77.2 ± 2 IV C 0.05 80.1 ± 7 EXAMPLE 28 The following formulations were prepared: Composition V A - 14.61 g of dried Agrimer AL 25 were dissolved in 64.29 g of Exxon Aromatic 150, 14.61 g N-octyl pynolidone were added, followed by the addition of 6.49 g of a surfactant, Alcasurf CA. The mixture was stined for 40 minutes in an orbital shaker to produce a clear solution. The composition can also be prepared by using 29.2 g of a 50% isopropyl alcohol solution of the polymer (Agrimer AL 25) and 14.61 g of N-octylpynolidone with 64.3 g of Exxon Aromatic 150 (or other higher boiling diluents). The isopropyl alcohol may be separated by evapora¬ tion under atmospheric or reduced pressure. 6.49 g Alcasurf CA, is then added to produce 100 g of the inventive compo¬ sition. Composition V B - 14.6 g of Agrimer AL 30 were dissolved in 14.6 g of N-octyl pynolidone, 64.3 g of Exxon aromatic 150 and 6.5 g of Alcasurf CA. The mixture was stined for 30 minutes to produce a clear solution. Composition V c - 15 g of Agrimer AL 25 (solvent-stripped) were dissolved in 85 g of Exxon aromatic 150. Composition V D - This composition was the same as composition V c except that the Agrimer AL 25 was replaced by an equivalent amount of Agrimer AL 30 (solvent-stripped). (The above-noted compositions are depicted in Table 15) TABLE 15 % WEIGHT COMPOSITIONS OF SOLVENT BASED POLYMER COMPOSITIONS: Compositions V A and V B were diluted with D.I. water or 342 ppm hard water to produce stable emulsions at dilution rates of 1/10, 1/20, 1/50, 1/100 and 1/1000. The emulsions produced from composition V A were more stable than those from composition V B . Hard water produced more stable emulsions than D.I. water. Formulation of stable emulsions in water makes it possible to use the above compositions in both oil based and water based active ingredient formulations. It is noted that compositions V A and V B are particularly advantageous for use in oil base active ingredient concentrates in aqueous medium. EXAMPLE 29 Rainfast evaluations using the procedure of Example 26 hereinabove were carried out for compositions V A , V B , V c , and V D as well as at Latron B 1956 for comparison purposes. The compositions used were as follows: Composition VI blank This was essentially the same as composition I_Q A . Composition VI A 1 g of Prowl was mixed with 0.67 g of composition V A and then diluted to 100 g with D-.I. water. Composition VI B 1 g of Prowl was mixed with 0.67 g of composition V B and then diluted to 100 g with D.I. water. Composition VI C 1 g of Prowl was mixed with 0.67 g of composition V c and then diluted to 100 g with D.I. water. Composition VI D 1 g of Prowl was mixed with 0.67 g of composition V D and then diluted to 100 g with D.I. water. Formulations VI blank, VI A , VI B , Vlς and VI D were evaluated for rainfastness of the pendimethalin using 0.32 - 0.34 g for spotting and 2.2 to 2.4 g of wash water to simulate rain. The evaluation showed that formulations VI A , VI B , VI C and VI D exhibited increased retention of the active ingredient as compared to the blank. The effectiveness was in the following decreasing order: VI A (38.7 ± 6) > VI B (30 ± 1) > VI D (23 ± 4) > V^ (19.4 ± 3) > VI (12 ± 1) The foregoing represent the averages of three runs for each composi¬ tion. In the above experiment, the pump spray equipment used, i.e., force of spray, to simulate rain was different from the procedure outlined in Example 26. This could explain the lower retention. The evaluation of Latron B1956 as a tank mix additive showed that the inventive formulations produced 60 to 80% higher retention at the same level of application as the Latron B1956 containing composition. EXAMPLE 30 A series of formulations was prepared containing commercial carbaryl (Sevin) and evaluated for rainfastoess. Sevin is a formulation containing 27% of carbaryl as an active ingredient. The compositions were as follows: Composition VII blank 1 g of commercial Sevin was diluted to 200 g with D.I. water to produce an emulsion of about 0.14% active ingre¬ dient. Composition VII A - Same composition as VII blank except that 0.27 g of composi¬ tion V A was added prior to dilution. Composition VII B - Same composition as VII A except that 0.67 g of composition V A were added. Composition VII C - Same composition as VII A except that composition V A was replaced with composition V B . Composition VII D - Same as composition VII B except that composition V A was replaced by composition V B . Composition VII E - Same as composition VII B except that composition V A was replaced by composition V c . Composition VII F - Same as composition VII B except that composition V A was replaced by composition V D . These formulations were evaluated using the same procedure as set for in Example 26. Specifically, 0.45 - 0.54 g of the sample were spotted onto glass plates and 1.5 - 1.7 g of water was used to simulate rain wash. The λ max. used for the evaluation was 279 nm and the least square line was used according to the following formula: absorbance = 0.03276 X concentration (ppm) - 0.016416. The results of the evaluations are shown in Table 16. TABLE 16 SUMMARY RESULTS OF RAINFASTNESS FOR CARBAMYL ("SEVIN") FORMULATIONS EXAMPLE 31 It is noted that formulation V A is particularly useful as an adjuvant for oil based concentrates. Such oil based concentrates (concentrates based on a non- aqueous hydrophobic solvent) normally are composed of: active ingredients - 10 to 60 percent; surfactants (wetting agents and emulsifiers) - 1 to 30 percent; hydrophobic non-aqueous solvents - 10 to 80 percent; and optionally, defoamers, rheology modifiers and the like as needed 0 to 5 percent. It exhibits enhanced efficacy with the active ingredient Fusilade EC when used at a 0.2 % concentration in the final dilution. Also, increased biological activity with chloropyrifos, an insecticide, was observed when composition V A was used with an oil based concentrate for this active ingredient at a 0.2 % concentration in the final dilution. EXAMPLE 32 The compositions of the present invention, for example, Compositions V A and V B can be used as granulating fluids to incorporate the water-insoluble polymers in solid water-dispersible granular formulations. A typical formulation is as follows: Active ingredient (Atrazine) 82.3 % by weight Binder (poly vinyl pynolidone - optional) 3.0 Dispersant 3.0 Wetting agent 1.5 Defoamer 0.2 Composition V A or V B 10.0 Typical examples of the dispersants, wetting agents, and defoamers are: Morwet D-425, alkylated naphthalene sulfonate sodium salt, Morwet EFW which is a proprietary mixture of sulfated alkylcarboxylate and a sulfonated alkylnaphthalene sodium salt, and FOAMASTER soap L which is a proprietary soda soap. In such a composition, the aromatic oil diluent can be dispensed with. The water-dispersible granules are prepared by charging the weight ingredients (200 g) in a V-blender and mixing for 10 to 30 minutes. The charge is then loaded to a 24 inch pan granulator set at an angle of 50 to 55°. The pan is rotated at a speed of 15 rpm and granulation is accomplished by spraying the charge with water at an appropriate speed, typically, 20 to 30 ml of water is used over a period of 10 to 30 minutes. After granulation, the wet granules are dried at 40 to 50°C to reduce the moisture level to about 1 to 2%. The dry granules can be sieved to segregate them into different size fractions as desired. Undersized granules can be reformulated by recycling to the process. The granules can also be prepared by using a conventional extrusion process with a suitable extruder.

Claims: WHAT IS CLAIMED IS: 1. A composition comprising: a. a long chain alkylpynolidone; b. a surfactant; and c. a film-forming water insoluble polymer; and the amounts of the components being such that the composition on dilution with water forms a clear liquid. 2. The composition of claim 1 which further comprises water. 3. The composition of claim 2 which comprises from about 2 to 90 percent alkylpynolidone, from about 2 to 30 percent surfactant, from about 1 to 560 percent water-insoluble polymer and from about 1 to 50 percent water, all percents being by weight based on the total weight of the composition. 4. The composition of claim 1 wherein the long chain N- alkyl pynolidone has the formula: wherein R 2 is hydrogen or alkyl having from 6 to 14 carbon atoms and R 3 is alkyl having from 6 to 14 carbon atoms with the proviso that at least one of R 2 or R 3 must contain at least 6 carbon atoms and the sum of the carbon atoms in R 2 and R 3 cannot exceed 14. 5. The composition of claim 1 wherein the water insoluble polymer is a graft copolymer of N-vinyl pynolidone and an α-olefm containing up to 20 carbon atoms and having a number average molecular weight in the range from about 3000 to 50,000. 6. The composition of claim 5 wherein the alpha olefin contains from 6 to 20 carbon atoms. 7. The composition of claim 5 wherein the N-vinyl pynolidone is present in an amount of more than 20 percent on a weight basis in the graft copolymer. 8. The composition of claim 5 wherein the N-vinyl pynolidone is present in an amount of more than 50 percent on a weight basis in the graft copolymer. 9. The composition of claim 4 wherein R 2 is hydrogen and R 3 is and alkyl containing from 8 to 12 carbon atoms. 10. The composition of claim 4 wherein the water-insoluble polymer is a graft copolymer of N-vinylpynolidone and an alpha olefin containing 16 carbon atoms in a weight ratio of 50:50 and having a number average molecular weight of about 9500. 11. The composition of claim 1 which further comprises N-methyl pynolidone in an amount effective to solubilize the long-chain alkyl pynolidone. 12. The composition of claim 1 wherein the long-chain alkyl pynolidone is selected from the group consisting of N-alkylpynolidone, N-dodecyl- pynolidone, and mixtures thereof. 13. The composition of claim 12 which further comprises N-methyl pynolidone in an amount effective to solubilize the long-chain alkyl pynolidone. 14. The composition of claim 13 which contains N-dodecyl- pynolidone and N-methyl pynolidone, each in a weight ratio of from about 0.1 to 10 parts to 1 part N-octyl pynolidone. 15. The composition of claim 14 wherein the ratio is from about 0.5 to 2 parts each of N-dodecyl pynolidone and N-methyl pynolidone to 1 part of N-octyl pynolidone. 16. A composition comprising: a. a long chain alkylpynolidone; b. a surfactant; c. a film-forming water insoluble polymer; and d. an agriculturally active chemical; the amounts of the components being such that the composition forms a rainfast microemulsion or emulsion. 17. The composition of claim 16 which further comprises water. 18. The composition of claim 17 which comprises from about 2 to 90 percent alkylpyrrolidone, from about 2 to 30 percent surfactant, from about 1 to 50 percent water-insoluble polymer and from about 1 to 50 percent water, all percents being by weight based on the total weight of the composition. 19. The composition of claim 16 wherein the long chain N- alkyl pynolidone has the formula: wherein R 2 is hydrogen or alkyl having from 6 to 14 carbon atoms and R 3 is alkyl having from 6 to 14 carbon atoms with the proviso that at least one of R 2 or R 3 must contain at least 6 carbon atoms and the sum of the carbon atoms in R 2 and R 3 cannot exceed 14. 20. The composition of claim 19 wherein the water insoluble polymer is a graft copolymer of N-vinyl pynolidone and a alpha-olefin containing up to 20 carbon atoms and having a number average molecular weight up to about 50,000. 21. The composition of claim 20 wherein the alpha olefin contains from 6 to 20 carbon atoms. 22. The composition of claim 20 wherein the N-vinyl pynolidone is present in an amount of more than 20 percent on a weight basis in the graft copolymer. 23. The composition of claim 20 wherein the N-vinyl pynolidone is present in an amount of more than 50 percent on a weight basis in the graft copolymer. 24. The composition of claim 20 wherein R 2 is hydrogen and R 3 is and alkyl containing from 8 to 12 carbon atoms. 25. The composition of claim 20 wherein the water-insoluble polymer is a graft copolymer of N-vinylpynolidone and an alpha olefin containing 16 carbon atoms in a weight ratio of 50:50 and having a number average molecular weight of about 9500. 26. The composition of claim 25 wherein the agriculturally active chemical is selected from the group consisting of pesticides and herbicides. 27. The composition of claim 26 which further comprises N-methyl pynolidone in an amount effective to solubilize the long-chain alkyl pynolidone. 28. The composition of claim 26 wherein the long-chain alkyl pynolidone is selected from the group consisting of N-alkylpynolidone, N-dodecyl- pynolidone, and mixtures thereof. 29. The composition of claim 26 which further comprises N-methyl pynolidone in an amount effective to solubilize the long-chain alkyl pynolidone. 30. The composition of claim 26 which contains N-dodecyl- pynolidone and N-methyl pynolidone, each in a weight ratio of from about 0.1 to 10 parts to 1 part N-octyl pynolidone. 31. The composition of claim 26 wherein the ratio is from about 0.5 to 2 parts each of N-dodecyl pynolidone and N-methyl pynolidone to 1 part of N-octyl pynolidone. 32. The composition of claim 26 wherein the agriculturally active chemical is the isopropylamine salt of phosphonomethylglycine, pendimethalin, and 1 , l-dimethyl-4,4'-bipyridinium dichloride. 33. The composition of claim 1 wherein the water-insoluble polymer forms a film having adhesive properties. 34. The composition of claim 1 wherein the water-insoluble polymer forms a film having protective properties. 35. The composition of claim 1 wherein the water-insoluble polymer forms a film having decorative properties. 36. The composition of claim 1 wherein the water-insoluble polymer forms a film having lubricating properties. 37. The composition of claim 1 wherein the water-insoluble polymer forms a film having hydrophobic properties. 38. The composition of claim 1 wherein the water-insoluble polymer forms a film having hydrophilic properties. 39. A method for forming a polymeric film on a substrate comprising applying the composition of claim 1 onto the substrate and removing the water. 40. A method for treating plants or soil with an agriculturally active chemical comprising applying the composition of claim 16 to the plant or soil. 41. A solid composition comprising a. a long chain alkylpynolidone; b. a surfactant; c. a film-forming water insoluble polymer; and d. sodium bicarbonate; which composition, on the addition of water thereto, produces a clear liquid. 42. A solid composition comprising a. a long chain alkylpynolidone; b. a surfactant; c. a film-forming water insoluble polymer; d. an agriculturally active chemical; and e. sodium bicarbonate; the amounts of the components being such that the composition forms a rainfast clear liquid on the addition of water. 43. A method for forming the solid composition of claim 42 comprising the steps of A) mixing a solid agriculturally active chemical in particulate form with NaHCOx 3 in particulate form; B) mixing the product from step a) with a composition comprising a. a long chain alkylpynolidone; b. a surfactant; and c. a film-forming water insoluble polymer; and D) freeze-drying the product from step B). 44. An emulsion concentrate comprising: a) an effective amount of an agriculturally active chemical; b) a solvent for the agriculturally active chemical; and c) a water-insoluble film-forming polymer. 45. The emulsion concentrate of claim 44 wherein the solvent is a long-chain alkylpynolidone having the formula wherein R 2 is hydrogen or alkyl having from 6 to 14 carbon atoms and R 3 is alkyl having from 6 to 14 carbon atoms with the proviso that at least one of R 2 or R 3 must contain at least 6 carbon atoms and the sum of the- carbon atoms in R 2 and R 3 cannot exceed 14, preferably, R 2 is hydrogen and R 3 is C g or C 12 , or a synthetic or naturally occuning oil having a high hydrophobic character or having a fractional dispersive solubility parameter of greater than 70%. 46. The emulsion concentrate of claim 45 which further contains N- methy lpy nolidone . 47. The emulsion concentrate of claim 45 wherein the solvent is selected from the group consisting of soybean oil, rapeseed oil, long chain alcohols, long chain ketones, long chain esters, ethers, aromatic petroleum oils composed of heavy aromatic solvent naphtha - about 60%; middle distillate solvent extractant - about 40%, and combinations thereof. 48. The emulsion concentrate of claim 44 wherein the water- insoluble polymer is a graft polymer of N-vinylpynolidone and an α-olefin wherein the N-vinylpynolidone is present in at least 20 percent on a weight basis. 49. The emulsion concentrate of claim 44 wherein the α-olefin contains up to 20 carbon atoms. 50. The emulsion concentrate of claim 44 comprising from about 2 to 90 weight percent of a solvent selected from the group consisting of N-octyl¬ pyrrolidone, a crude oil distillate having an average boiling point of at least 120°C and mixtures thereof, from about 1 to 60 weight percent of a copolymer of N-vinyl¬ pynolidone and a Cj 6 α-olefin in a 50:50 weight ratio and a number average weight of about 9500. 51. The emulsion concentrate of claim 44 wherein the solvent is selected from the group consisting of N-octylpynolidone, N-methylpynolidone, a crude oil distillate having an average boiling point of at least 120°C, and mixtures thereof. 52. An emulsion concentrate comprising: a) 2 to 90 % by weight of a solvent selected from the group consisting of long-chain alkyl pynolidones, synthetic or naturally occurring hydro¬ phobic oils, and mixtures thereof; b) 1 to 60 % by weight of a water-insoluble graft polymer of N-vinyl¬ pynolidone and an α-olefin wherein the N-vinylpynolidone is present in at least 20% on a weight basis; and c) 1 to 85 % by weight of an oil-soluble surfactant. 53. The concentrate of claim 52 wherein the solvent is selected from the group consisting of 10 - 20% by weight N-octylpynolidone, 50 - 70% by weight of the hydrophibic oil, or mixtures thereof, the water-soluble polymer is present in an amount from 10 to 20 % by weight and the oil-soluble surfactant is present in the amount from 5 to 10% by weight. 54. The concentrate of claim 52 wherein the polymer is a copoly¬ mer of N-vinylpynolidone and a C l6 α-olefm in a 50:50 weight ratio and having a number average weight of about 9500. 55. The concentrate of claim 52 wherein the polymer is a copoly¬ mer of N-vinylpynolidone and a C 20 α-olefin in a 20:80 weight ratio. 56. The concentrate of claim 52 wherein the solvent is a long-chain alkylpynolidone. 57. A composition for application to agricultural crops comprising an emulsion of the emulsion concentrate of claim 44 diluted at least 2-fold with water. 58. A method for treating crops comprising applying the composi¬ tion of claim 57 to the crops. 59. A method for producing a water-dispersible granule of an agriculturally active ingredient comprising charging an agriculturally active ingredient and the emulsion concentrate of claim 44 to a granulator to form granules, and drying the granules. 60. Granules obtained by the method claim 59. 61. A method for treating crops comprising mixing the granules of claim 60 with water to form an emulsion and applying the emulsion to the crops.

Inventors: NARAYANAN KOLAZI S, NARAYANAN, KOLAZI, S.
Applicants: ISP INVESTMENTS INC, ISP INVESTMENTS INC.
Application year: 1993
Main classification: A61K9
IPC codes: A01M21, A01N25, A01N33, A01N43, A01N57, A01N63, A61K8, A61K9, A61Q17