PESTICIDAL GRANULES CONTAINING FERTILIZER AND SURFACTANT

Abstract: A method for producing a dry bonded pesticidal granular surfactant/fertilizer delivery system comprising spray-coating from about 1 to about 99 weight percent dry water-soluble, nitrogen-containing fertilizer particles, preferably diammonium sulfate with the surfactant composition, admixing pesticide; and granulating the final delivery system; and the granules produced thereby.

Description: PESTICIDAL GRANULES CONTAINING FERTILIZER AND SURFACTANT 5. Field of the Invention The present invention relates to pesticidal granules containing rapidly dissolutioning or dispersing fertilizer and surfactant compositions. More particularly, the fertilizers are water-soluble nitrogen-containing and the surfactant 0 compositions comprise solid, nonionic surfactants. Background of the Invention It is well recognized by the agricultural industry that it is advantageous to the end-user to be able to formulate 5 active pesticides as water dissolutioning or dispersible compositions which can be easily mixed with water and applied by means of a spraying apparatus to a locus to be protected. Additionally, many pesticides, for example, fungicides, plant growth regulators, herbicides and systemic insecticides 0 or, in fact, any pesticide needing rain fastness or attendant soil or surface wetting/penetration require the presence of surfactant adjuvants for effective end-use applications. This is especially true for herbicides which realize greatly enhanced post-emergence weed control when applied with certain 5 nonionic surfactants. For example, studies such as "Surfactant Structure and Concentration Strongly Affect Rimsulfuron Activity" Green et al., Weed Technology Vol. 7:633-640, 1993 have indicated that sulfonyl urea herbicidal activity can be increased ten-fold with selection of appropriate nonionic surfactant adjuvants. The art has also recognized the particular importance of two of the adjuvant properties. They are first, the hydrophilic - hydrophobic 5. balance (H B) and secondly, the physical form of the initial surface deposit, ideally a moist gel. It has been theorized that with surfactants in the appropriate HLB range, the surfactant is hydrophilic enough to solubilize the herbicide in water and lipophilic enough to penetrate the cuticle of a 0 leaf. In moist gels, the surfactants are hypothesized to form onolayers on the leaf surfaces with the lipophilic portion along the waxes and the hydrophilic portion forming "hydrophilic channels" through surface imperfections such as cracks, punctures, and pores. These channels absorb water and 5 slightly swell to allow herbicides to diffuse through the cuticle into the cell walls. The surfactants preferred by the art and which can realize the above-described properties when admixed with pesticides in aqueous medium, are the nonionics. Most 0 preferably, the solid, nonionic surfactants are desired by the end-user, usually a farmer, for ease of handling such as when preparing a pesticidal spray tank mix. The solid nonionics are also preferred to eliminate the need for triple rinsing of the liquid surfactant containers, e.g., the 2.5 gallon jugs, 5 usually used to deliver liquid surfactant concentrates to farmers and to avoid the attendant jug disposal problem. However, solid nonionic surfactants tend to dissolve rather slowly; therefore, end-users must be especially careful to ensure complete dissolution of the surfactant so that proper pesticide to surfactant ratios are delivered to the locus 5. and/or that entrained undissolved particles do not interrupt the delivery process, e.g., by plugging spray nozzles. Often dry water-soluble nitrogen fertilizers such as urea, ethylurea, mono and diammonium phosphate; mono and diammonium sulfate, and mixtures thereof can enhance the 0 efficacy of pesticides, especially the herbicides. This significant increase in herbicide phytotoxicity in the presence of nitrogen fertilizers has been especially observed with the use of diammonium sulfate adjuvant. Large increases in herbicidal efficacy have been reported (Adjuvants and 5 Agrochemicals, Vol. II, Chapter 34) when diammonium sulfate was used as an adjuvant in combination with methylated seed oil, a known cuticle "softener". Glyphosate, one of the most frequently used herbicides worldwide, usually has diammonium sulfate added to its spray tank solution to enhance its 0 herbicidal efficacy. As an aside, diammonium sulfate appears to have at least two modes of action when coupled to glyphosates: firstly, by directly increasing the glyphosates phytotoxicity and secondly, by overcoming antagonism from certain cations. It has been theorized that the sulfate ions 5 precipitate calcium and sodium ions by forming calcium and sodium sulfates which have low water solubility. The ammonium ions form the more toxic glyphosate-ammonium complex and prevent formation of the less phytotoxic glyphosate - sodium complex during droplet drying. However, the delivery of a pesticide, the aforedescribed 5. solid, nonionic surfactant composition and the dry water- soluble fertilizer components individually to the customer for on-site blending or tank mixing oftti es results in an undesirable situation for the customer for he has to ensure that the amounts of the pesticide, surfactant composition and 0 fertilizer inserted into the spray tank are correct; the materials are compatible and properly dispersed; proper safety precautions are followed, for example, if one or more of the components dust; and that necessary additional adjuvants are immediately available if, through incompatibility or 5 otherwise, for example, problems with excessive foaming or precipitation were to occur. Even though all of the components are delivered as solids, a spill of a component delivered as a powder can also be exceedingly difficult to clean up. 0 In view of the above, suppliers to the agricultural market have attempted to pre-blend individual fertilizer, surfactant and other adjuvant components as an aid to the end- user farmer. However, significant differences in particle sizes among the individual components can result in separation 5 during shipping and/or storage. Furthermore, inherent tackiness or particle fines generated through attrition can result in compaction and/or caking before the customer can use the product blend. In view of the slow aqueous dissolution rate exhibited by many of the solid nonionics, it would also be desirable no increase the rate at which the solid surfactant dissolves in the end-user' s final liquid medium. Heretofore, attempts to control the times of solid surfactant solubilization have taken various forms, such as using incorporated binders, extrusion granulation, membrane encapsulation, or tableting, i.e., compression of the surfactant-containing compositions all of which possess attendant disadvantages. For example, encapsulation is highly dependent upon the quality of the encapsulating material and may release the compositions in discrete packages. The compaction process is an extremely difficult way to control the release of surfactant material for slight variations in composition properties, e.g., tackiness, particle size, etc. can have dramatic impact on the dissolution rate even under fixed, uniform compacting pressure. Extrusion processing to prepare mel -admixed granules, such as is taught in EP 501,798A1, wherein pesticides, binders and diluents are extruded together, has the disadvantage of always intimately admixing all of the components thus inherently placing a restriction on the individual components that can be utilized in such a process. For example, in many situations, the individual components sought to be used are incompatible in intimate contact. Furthermore, in extruded granules, all of the material components will be exposed to the aqueous medium simultaneously, i.e., one cannot program for differing dissolution rates. As noted above, however, granule-type products, i.e., 5. multi-component particles are desirable in many end-use applications such as when they are to be used in pesticidal tank mixes for they are more stable during storage and transport than mere physical mixtures of the dry individual components and provide ease of handling. 0 It would be advantageous if a process means relatively insensitive to minor process or product variations were available to avoid the above-identified problems of the prior art to provide a single particle pesticide-fertilizer- nonionic surfactant carrier,* and to perhaps not only increase 5 the rate at which nonionic solid surfactants dissolve in aqueous medium, but also permit i) incompatible components to be incorporated into a single particle and ii) preferential or sequential exposure of selected components to the aqueous media. 0 For all of the above reasons, it would be highly desirable to be able to provide a dry solid granulated product comprising a water-dispersible pesticide, water-soluble solid fertilizer and solid, nonionic surfactant composition, which does not exhibit the undesirable traits associates with 5 heretofore prior art blend attempts as detailed above. Summary of the Invention It is an object of the present invention to realize a process for preparing pesticidal granules comprising a dry water-soluble nitrogen fertilizer coated by solid nonionic 5. surfactant compositions and granulated with pesticide adhered to the granule, and the resulting granule. This is accomplished by spray-coating the molten surfactant composition onto from about 1 to about 99 weight percent dry water-soluble, nitrogen-containing fertilizer, preferably 10 diammonium sulfate crystals, said percent based on the final weight of the dry bonded adjuvant granule, and granulating the composition in the presence of pesticide to incorporate same into the granule. 15. Detailed Description of the Invention It has been discovered that dry water-soluble nitrogen- containing fertilizers, preferably diammonium sulfate can provide excellent substrates for certain solid nonionic surfactants when the surfactant composition is dry bonded onto 20 from about 1 to about 99 weight percent (based on the total dry bonded particle weight) of the fertilizer by spray-coating the fertilizer with the molten surfactant and these particles provide excellent carrier systems for pesticides. The time for complete dissolution in water of the solid, nonionic 25 surfactant compositions can ofttimes be significantly reduced. These coated pesticide-fertilizer carrier systems also realize many additional advantages over similar blends of these materials in the prior art. At the outset, being a hard coated, granular type product, the instant pesticide- fertilizer carrier systems are exceptionally stable and 5. relatively unaffected by attrition during storage and shipping. These unique delivery systems permit components, normally incompatible with the pesticide and/or nitrogen- containing fertilizer to be physically incorporated in the granule. For example, if an adjuvant is incompatible with the 0 fertilizer, it can be adhered to the granule; if incompatible with the pesticide, it can be added prior to the spray coating, i.e., made part of the substrate. If it is desired to have adjuvants that require a longer exposure time to a given aqueous medium for optimum efficiency as an inherent 5 part of the granule, for example, guar particles that require additional hydration time; pH buffers, etc., they can be preferentially or sequentially released by not having the adjuvant incorporated uniformly throughout the particle as would occur using the processing of the prior art, but rather 0 having the adjuvant adhered to the outer surfactant coating of the granule. By "spray-coated" is meant that the solid surfactant is melted and coated upon a substrate comprising the fertilizer while still in the molten state. This is done by spraying the 5 molten surfactant onto the substrate, most preferably the diammonium sulfate particles in a coating blender. Complete coating of the substrate particles is not always necessary but, rather, the degree of completeness of the coating is often determined by specific requirements such as the need to isolate the fertilizer from other added incompatible 5. adjuvants. The sprayed material, while still-in a sticky state is then continuously tumbled to partially agglomerate or granulate the individual particles while preferably the pesticide is added and bonded so as to yield dry bonded flowable granules. 0 The solid, nonionic surfactants that can be used in the process of this invention are those known in the art which are solid or of a hard, nontacky wax consistency at room temperature. Among the preferred nonionics are the following: 5 A) Amides such as: i) Alkanolamides of the formula - 0 !l - R' R C N' 20 "" "" • R" wherein R' and R" each can be -H, -CH 2 CH 2 OH, or -CH 2 - CH-OH; CH 3 25 ii) ethoxylated alkanolamides of the formula - 0 (CH 2 -CH 2 -0),-H II A R - C - N lα iii) ethylene bisamides of the formula 0 R - C . H N-CH,-CH 2 -N ' H " ^^ C-R; 0 B) Esters such as: 5 i) fatty acid esters of the formula - 0 II R - C - 0 - R. 0 ii) glycerol esters of the formula - 0 R - HC - 0 - CH 2 - CH - CH 2 - 0 - R. I OH? mm. iii) ethoxylated fatty acid glycol and polyethylene glycol esters of the formula - 0 SL II R - C - 0 (CH 2 CH 2 0) x -R.; iv) sorbitan esters of the formula - 5 HO OH Nf CH - CH 2 - 0 - C - R; and 40 I OH 45 v) ethoxylated sorbitan esters of the formula H- (0CH-CH 2 ) n -0-^__ 0- (CH 2 CH 2 0) x -H ■' O ' ' v 0 CH-CH 2 -0-C-R 10 0- (CH 22 CCHH, 2 00)) y C) Ethoxylates such as: 15. i) alkylphenol ethoxylates of the formula - R - ^ ' .. - (OCH 2 CH 2 ) n OH; ii) alcohol ethoxylates of the formula - 25. R - 0 - (CH 2 CH 2 0) n H; iii) tristyrylphenol ethoxylates of the formula (O CH,CH,) n OH 10 CH 3 - CH 15. ' C S iv) mercaptan ethoxylates of the formula - R - S - (CH 2 CH 2 0) n H; 40 D) End-capped and EO/PO block copolymers such as 4 i) alcohol alkoxylates of the formula - CH 3 I R-(OCH,CH a ) x - (O - CH - CH 2 ) m - OH; ii) ethylene oxide/propylene oxide block copolymers of the formula - iP_ CH 3 HO - (CH 2 CH 2 0) x (CH 2 -CH-0) m - (CH 2 CH 2 0) y - H; iii) reverse copolymers of the formula - 15 CH 3 CH 3 HO(CH-CH 2 0) m - (CH 2 CH 2 0) x - (CH 2 -CH 0) . H; 20. iv) chlorine capped ethoxylates of the formula - R - (0CH 2 CH 2 ) X C1; and 21 v) tetra-functional block copolymers of the formula - CH, CH. 30 H (0CH-CH-), - (OCH CH,), (CH-CH 0)_.' - (CH-CH-O)„.H NCH-CH-N H (0CH.CH 3 ) y - (OCH CH,)^ " (CH-CHO) ! . - (CH 3 CH-θ) y .H 15 I ' CH, CH- or U2 CH- CH, I (OCH CH-). (OCH, CH,), (CH-CH-O) (CH, CHO) \ NCH,CH,N 45. H (OCH CH,) ! - (OCH, CH,) y ^(CH,CH,0) y . - (CHjCHOh. CH, CH, 50 wherein R is a fatty alkyl group, preferably a C s - C 22 fatty alkyl group, most preferably a C β - C lβ fatty alkyl group; R, is -H or a fatty alkyl group, preferably -H 5. or a Cj ■ C 22 fatty alkyl group, most preferably - H or a C„ - C lβ fatty alkyl group; x * χ ' i Y> y' and n are each independently moles of ethylene oxide preferably 1 to 300; most preferably 1 to 150; and _LP_ m, m' , 1 and 1' are each independently moles of propylene oxide, preferably 1 to 300; most preferably 1 to 150; with the proviso that the fatty alkyl group and/or the number or arrangement of the ethylene 15. oxide and/or propylene oxide units are such that the surfactant composition is a solid at room temperature (24 * C), preferably a solid at 50 * C. Mixtures of the above surfactants are acceptable and, in fact, mixtures of the above surfactants with other nonionics 20 that alone are liquid even at room temperature may be acceptable provided that the amount or nature of the liquid surfactant is such that the final particulate product does not exhibit tackiness at room temperature. Preferably, tackiness is not exhibited even at 50 * C. 25 The more preferred solid nonionic surfactants are the aforedescribed alkyl alcohol ethoxylates and alkylphenol ethoxylates. The solid, nonionic surfactant composition of the instant granules should be from about 1 to about 99 weight percent, preferably from about 3 to about 95 weight percent based on 5. the total granule formulation weight. The most preferred solid nonionic surfactant is dinonylphenol ethoxylate {) 100 EO) for it has been discovered that this compound possesses the ability to provide excellent wetting characteristics together with a high melting point. 0 Furthermore, the material exhibits an ability to dissolve in aqueous medium without formation of a gel phase. The amount of the dry water-soluble nitrogen-containing fertilizer to be spray-coated by the solid nonionic composition can be from about 1 to about 99 weight percent, 5 preferably from about 1 to about 95 weight percent based on the total weight of the final spray-coated composition. The pesticides contemplated for use in the granules of this invention are those active ingredients well known to be of value to agriculture and are normally distributed to loci 0 via aqueous spray means such as herbicides, fungicides, bactericides, insecticides, insect antifeedants, acaricides, miticides, nematocides, and plant growth regulants. Preferred pesticides are the herbicides selected from the group consisting of the herbicidal sulfonyl ureas, imidazolines, and 25 glyphosates. The active ingredients should be present in the granules in pesticidally effective amounts, preferably from about 0.01 to about 90 weight percent, most preferably from about 0.03 to about 80 weight percent based on the total granule formulation weight. The essence of the preferred embodiment of the instant 5. invention lies in the discovery that if solid nonionic surfactant compositions are spray-coated upon dry, water- soluble nitrogen-containing fertilizers such as diammonium sulfate, the dissolution rate of the dry surfactant particulate composition in aqueous solution can be greatly 10. enhanced. It is also hypothesized that in addition to the action of the fertilizer per se upon the dissolution rate of the solid, nonionic surfactant composition, the coating/granulation process tends to entrap air within the coated granules thereby increasing the surface area ultimately 15 exposed to the aqueous medium which increases the dissolution rate (as opposed to compaction and extrusion processes which tend to compress air out of the particles) . Also, the pockets of entrapped air function as flotation aids which assist in keeping the coated granules from settling. 20 The preferred process of the instant spray-coating invention comprises the steps of: a) adding the dry water-soluble nitrogen-containing fertilizer, preferably diammonium sulfate to a blender chamber; 25 b) mixing said fertilizer to ensure uniform distribu ion; c) melting the initially solid nonionic surfactant composition, preferably at a temperature of from about 65 * to about 95'C. (149 - 203 * F) ; d) spraying the molten surfactant composition onto 5. the fertilizer particles in said blender chamber; e) blending continuously to effect a uniform coating and granulation of the fertilizer particles; f) admixing pesticide particles while the surfactant composition is still tacky; and 0 g) cooling the pesticide-containing granules, preferably to less than 50 * C (122 * F) . Preferably, the fertilizer particles are initially blended for at least 10 minutes before the spraying step to ensure that the initial crystal or particle sizes are 5 uniformly distributed throughout the batch. The preferred spray blender-mixers are those of the Mark VI design manufactured by Continental Rollo or an equivalent. Also preferably, to aid in providing a uniform granulation, the mixture should continue to be blended for at 0 least three additional minutes after the spraying has ceased. If it is desired to have any additional components adhere to the surface of the coated granules, e.g., if an additional additive is a fine powder and one desires to reduce dusting in the final product, the material can also be added while the 5 coated granules are still tacky to obtain adherence, i.e., the material can be added before the granules are completely cooled. Examples of such optional additional components include anti-foam agents, flow agents, anti-caking agents, stabilizers, inert fillers, gas-generating agents, dyes, and/or any adjuvants particular to the specific end-use 5. application of the resulting product. Optional adjuvants can be added from about 0 to about 20 weight percent of the granular composition. Inert ingredients can be added up to about 80 weight percent. Aside from being able to deliver to the end-user a 0 complete accurately measured, optimized and compatible pesticidal formulation in a single granule, one of the distinct advantages of the instant spray-coated, i.e., multi- layered particle is that it frees the preparer from many of the restrictions normally imposed upon multi-component systems 5 manufacturers. For example, additional adjuvant components which normally would be incompatible with the fertilizer, specifically the diammonium sulfate can be made a part of the coated granule by introducing the component after the pesticide granulation process is essentially completed, but 0 while the multi-layered material is still tacky so that the adjuvant can be adhered to the outer surface, i.e., the component would only be in contact with the pesticide and the nonionic composition layer. Another advantage realized by this adherence contact 5 procedure is that in addition to the pesticide, it allows other material to be placed on the outside of the spray-coated granule, thus giving the adhered material preferential or advanced exposure to the aqueous media. Thus, one can also selectively sequence the exposure times of certain components of the granule. The fertilizer of the instant process preferably should be of a coarse grade,* most preferably 95 weight percent of the material should have an average particle size diameter of from about 200 to about 600 microns, i.e., 95 weight percent should pass through a 30 mesh (U. S. Standard) screen and not pass through a 70 mesh (U. S. Standard) screen. Elimination of fines is preferred to minimize compaction or agglomeration of the fertilizer particles during the coating process. The granules may be used as is or, if preferred, screened to a desired particle size. The following specific examples are further illustrative of the present invention, but it is understood that the invention is not limited thereto. All amounts of various ingredients are by weight or weight percent unless otherwise specified. In all of the following Examples, the dissolution rates were determined as follows: A calculated amount of product such that the surfactant weight remained at 2.0 grams is added into a 250 ml beaker filled with 98 ml of deionized water at room temperature while stirring with a magnetic stirrer set to a speed of about 30-50% full scale and a stopwatch started. When complete dissolution is observed, i.e., the solution becomes completely clear, the time is recorded. 5. Examples I-II A flaked dinonylphenol ethoxylate ()l00 EO) (sold under the Rhone-Poulenc trademark Igepal DM-970 FLK) is blended with a sufficient amount of a liquid isodecyl alcohol ethoxylate (4 EO) (sold under the Rhone-Poulenc trademark Rhodasurf DA-530) 0 to produce a non-tacky, solid mixture with a 85:15 respectively weight ratio surfactant Composition A (said blend also sold by Rhone-Poulenc under the trademark AgRHδ DS 420) . Although the isodecyl alcohol ethoxylate has an adverse effect on the melting point of the solid dinonylphenol ethoxylated 5 surfactant, its presence is useful for the improved wetting characteristic it provides, i.e., the lower surface tension realized in the final aqueous solution as a result of its incorporation. At room temperature, dry diammonium sulfate is added to 0 the dry Composition A prepared above in a Sigma Blade Mixer in a weight ratio of approximately 85:15 weight percent sulfate to surfactant. Blending is unable to be accomplished because the materials compress together and cake. The test is run again utilizing solely the flaked 5 dinonylphenol ethoxylate ()l00 EO) , i.e., Igepal DM-970 FLK in lieu of Composition A. Again, the blending is unsuccessful because, even at room temperature, the surfactant and diammonium sulfate compact to form cakes. Example III 5. Diammonium sulfate is charged into a Continental Rollo mixer Mark VI blender. The sulfate is rotationally blended for about 10 minutes. A solid nonionic surfactant composition comprising an 85:15 weight ratio of dinonylphenol ethoxylate () 100 EO) (Igepal DM 970) and isodecyl alcohol ethoxylate (4 0 EO) (Igepal DA 530) respectively, (said nonionic surfactant composition blend sold under the Rhone-Poulenc trademark AgRHδ DS 420) is heated at a temperature of about 85 * C until the surfactant composition is melted. The molten surfactant is then sprayed onto the rotating diammonium sulfate through fine 5 sized 8008E spray tips. The mixture is blended continuously for three additional minutes to ensure uniform granulation. The mixture is then cooled to about 45" C at which time an antifoam agent is blended into the mixture (and where indicated, this is followed by citric acid and a flow aid) for 0 three minutes. The coated granular product is collected through a #8 (U. S. Standard) mesh screen. In these and the following examples, the weight percentages as indicated are based on the total weight of the final granule formulation. H Table I Dinonylphenol Isodecyl Alcohol Ethoxylate () 100 EO) Ethoxylate (4 EO) Ammonium Antifoa Dissolution Sample F a ed m a polyorganosiloxane sold under the Rhone-Poulenc trademark Rhodorsil Silicone EP 6703 .15. ** 1.30% citric acid and 0.26% flow aid (an amorphous precipitated silica sold under the Rhone-Poulenc Trademark Tixosil 38 AB) are added. The resulting dissolution time of the solid nonionic surfactant composition indicates the significantly enhanced 20 dissolution rates that can be unexpectedly realized by this invention, i.e., by the spray-coating of diammonium sulfate with the molten nonionic surfactant composition. Sxample IV 2H 84.05 weight percent diammonium sulfate is charged into a Continental Rollo mixer Mark VI blender. The sulfate is rotationally blended for about 10 minutes. 15 weight percent of a solid nonionic surfactant composition comprising a 85:15 weight ratio of dinonylphenol ethoxylate () 100 EO) (Igepal DM 30 970) to isodecyl alcohol ethoxylate (4 EO) (Igepal DA 530) respectively, (said nonionic surfactant composition blend sold under the Rhone-Poulenc trademark AgRHδ DS 420) is heated at a temperature of about 85 * C until the surfactant composition is melted. The molten surfactant is then sprayed onto the 35 rotating ammonium sulfate through five sized 8008E spray tips. The mixture is blended continuously for three additional minutes to ensure uniform granulation. The mixture is then cooled to about 45 * C at which time 0.2 weight percent of antifoam Rhodorsil Silicone EP 6703 is blended into the mixture for three minutes. Lastly, 0.75 weight percent of an _ anti-caking or free flow aid (Tixosil 38AB) is blended in for a few minutes. The coated granular product is collected through a #8 mesh sieve. The dissolution times of the resulting coated granules are less than half that of the solid nonionic surfactant composition alone. Example V The process of Example IV is followed utilizing the following weight percentages: ammonium sulfate - 93.15%; AgRHδ 5 DS 420 - 6.0%; Rhodorsil EP 6703 - 0.1%; and Tixosil 38 AB - 0.75%. As in Example IV, the dissolution times of the resulting coated granules are again less than half that of the solid nonionic surfactant compositions alone. 0 In addition to the above-identified advantages of potentially increased surfactant dissolution rates and the avoidance of compaction problems associated with attempts to intimately admix diammonium sulfate with the solid surfactants of the instant invention, the spray-admixed compositions of 5 this invention do not suffer from particle separation that can occur with simple solid blends of the same materials. In addition to the aforementioned enhanced dissolution; incompatibility avoidance; and preferential dissolution advantages, the coated products of this invention also realize a very uniform granule size together with excellent attrition 5, resistance. Serendipitously, the process is significantly less energy intensive and more capital cost effective than other melt-admixing processes, e.g., the extrusion processes of the prior art . 12. Examples VI - XV Twenty five pounds of Adjuvant A is prepared by charging 93.15 weight percent diammonium sulfate into a Continental Rollo Mixer Mark VI Blender. The sulfate is rotationally blended for about 10 minutes. 6.0 weight percent of a solid 15 nonionic surfactant composition comprising an 85:15 weight ratio of dinonylphenol ethoxylate () 100 EO) (Igepal DM 970) to isodecyl alcohol ethoxylate (4 EO) (Igepal DA 530) respectively, (said nonionic surfactant composition blend sold under the Rhone-Poulenc trademark AgRHδ DS 420) is heated at 20 a temperature of about 85 * C until the surfactant composition is melted. The molten surfactant is then sprayed onto the rotating diammonium sulfate through five sized 8008E spray tips. The mixture is blended continuously for two additional minutes to ensure uniform granulating, at which time herbicides a-re identified and, in the amounts listed below, are added. The material is tumble blended an additional three minutes to adhere the particulate pesticide to and incorporate them in the granules. The mixture is then cooled to about 45 * C, at which time 0.8 oz . of antifoam Rhodorsil Silicone EP 6703 is blended into the mixture for three minutes. Lastly, 6.0 oz. of an anti-caking or free flow aid (Tixosil 38 AB) is blended in for a few minutes. The pesticide-adhered granules are cooled and collected through a sieve. The following table illustrates the enhanced phytotoxicity realized by the use of the dry bonded pesticidal-adjuvant systems of the instant invention prepared as above described compared to that realized by standard liquid adjuvant-pesticide blends. The carrier for the compositions listed in Table II is water at ten gallons per acre. Kinetic (a trademark of Helena Chemical Co.) is a proprietary liquid surfactant adjuvant system comprising a polyorganosilicone and an ethyleneoxide/propyleneoxide block copoly er. Dynamic (a trademark of Helena Chemical Co.) is a proprietary liquid adjuvant system comprising methylated seed oil (MSO) and a polyorganosilicone. C.O.C. is a crop oil concentrate usually about 83 weight percent paraffinic crop oil and 17 weight percent emulsifier. T f le II Rate er % Control Days before 22 days) Visual Activity 100 5 0 95 10 5 100 95 10 0 100 5 95 Δ 100 2.5 5 . 95 14 Soybeans Dry Bonded 2.50 lbs. 100 3 Fert/Adjuvant J2, Pursuit 4.00 oz. Butyrac 200 3 00 oz. Beacon is a trademark of Ciba Geigy for a sulfonyl urea formulation. Accent, Classic and Pinnacie are trademarks of DuPont for sulfonyl urea formulations. Pursuit is a trademark of American Cyanamid for an lmidazoline formulation. _0 Poast Plus is a trademark of BASF for a proprietary cyclohexanedione formulation. Butyrac 200 is a trademark for a 2,4 DB formulation sold by Rhone-Poulenc Inc. 5 The above results illustrate the significantly enhanced herbicidal activity that can be realized via the use of the dry bonded pesticidal-adjuvant granules of the instant invention over the activity levels when standard liquid adjuvant systems are used. Examples XVI - XVII The following examples illustrate the enhanced phytotoxicity realized by the use of a glyphosate herbicide incorporated into the granulated products of the surfactant- 5 fertilizer carrier systems of this invention prepared as described in Examples VI - XV with the following changes to the pesticidal granular composition: 84.05 weight percent diammonium sulfate; 15.0 weight percent AgRHδ DS 420; 1.6 oz. Rhodorsil Silicone EP 6703; and 6.0 oz . of Tixosil 38 AB. The 10 herbicide used is Roundup which is a trademark of Monsanto for a glyphosate herbicidal formulation. Quest is a proprietary ammonia-based water conditioner of Helena Chemical Co. The carrier for the compositions is again ten gallons of water per acre . 15. Table in The above results illustrate the greatly enhanced herbicidal activity achieved via the use of the dry bonded 30 pesticidal-adjuvant granules of this invention when the pesticide is a glyphosate herbicide. The outstanding activity of these dry bonded granules are the result of the combined properties of high surfactant loadings; high ammonium ion levels; and rapid aqueous dispersement . These factors, together with the fact that 1) the HLB is about 16, i.e., within the art-recognized preferred range of 12-17 and 2) the compositions dry initially to a moist gel on leaf surfaces (an ideal condition as previously noted for increased pesticide 5 leaf penetration) combine to make these dry bonded granules powerful products for the pesticide end-user. The final granular product is such that it produces very little foam; low dust levels and odor; is non-compacting; and spills are easily swept up. The dry bonded granular pesticide delivery 10 systems of this invention enable a rapidly dispersing, completely optimized and balanced pesticidal-adjuvant- fertilizer composition to be prepared and, therefore, combines performance, convenience, and safety to the end-user in one granular product -- an ideal situation. 15 Although the present invention has been described and illustrated with reference to specific examples, it is understood that modi ications and variations of composition and procedure are contemplated within the scope of the following claims: 22. 25

Claims: We claim: 1. A method for producing a dry bonded granular pesticide system comprising spray-coating from about 1 to about 99 weight percent dry, water-soluble nitrogen-containing 5 fertilizer with from about 1 to about 99 weight percent of a solid, nonionic surfactant composition and admixing from about 0.01 to about 90 weight percent pesticide while the surfactant composition is still tacky; the weight percentage based on the total weight of the spray- 0 coated composition. 2. The method of claim 1 wherein the fertilizer is present from about 1 to about 95 weight percent of the spray- coated granular composition. 3. The method of claim 1 wherein said fertilizer is 5 diammonium sulfate . 4. The method of claim 2 wherein said fertilizer is diammonium sulfate. 5. A method for producing a dry bonded granular pesticide system comprising: 20 spray-coating from about 1 to about 99 weight percent dry water-soluble, nitrogen-containing fertilizer with from about 1 to about 99 weight percent of a solid, nonionic surfactant composition selected from the group consisting of: 25. i) alkanolamides of the formula 0 . R' R C ^ ' 5 "■ R » wherein R' and R" each can be -H-, -CH 2 CH 2 OH, or -CH 2 - CH-OH; CH 3 i£ ii ) ethoxylated alkanolamides of the formula 0 (CH 2 -CH 2 -0) x H II R - C - N \ ^ (CH.-CH.-Oj y H; iii) ethylene bisamides of the formula 15. 0 c. - H _ N-CH.-CH.- H C-R; 21 I! 0 iv) fatty acid esters of the formula 25. 0 II R - C - O - R.; v) glycerol esters of the formula 1 O R - ICI - O - CH 2 - CH - CH 2 - O - R-; 15 OH; vi) ethoxylated fatty acid glycol and polyethylene glycol esters of the formula 0 II 4£ R - C - O (CH-CH-O) X -R.; vii) sorbitan esters of the formula H OH Vlll ethoxylated sorbitan esters of the formula H- (OCH 2 CH 2 ) n -0 .0- (CH 2 CH 2 0) x -H A \> CH-CH 2 -0-C-R; O- (CH,CH-0). ix; alkylphenol ethoxylates of the formula R - -'( / - (0CH 2 CH 2 ) n 0H; x) alcohol ethoxylates of the formula R - O - (CH 2 CH 2 0) n H; χ ι; tristyrylphenol ethoxylates of the formula (0 CH 2 CH 2 ) n OH xii) mercaptan the formula R - S - (CH-CH 2 0) n H; xiii) alcohol alkoxylates of the formula CH 3 I R-(OCH 2 CH 2 ) x - (0 - CH - CH 2 ) m - OH; xiv) ethyleneoxide/propyleneoxide block copolymers of the formula CH 3 HO - (CH,CH 2 0) x (CH 2 -C IH-0) m - (CH 2 CH 2 0) y - H; xv) reverse copolymers of the formula ια CH, CH 3 I " I H0(CH-CH 2 0) m - (CH 2 CH 2 0) x - (CH 2 -CH 0), H; 15 xvi) chlorine capped ethoxylates of the formula R - (0CH 2 CH 2 ) X C1; xvii) tetra-functional block copolymers of the 20 formula CH 3 CH, I i H (OCH.CH,), - (OCH CH.)„ (CH-CH 0)„' - (CH-CH-O) X .H 25. „NCH-CH.N H (OCH.CH.),. - (OCH CH,), ' ' (CH-CH0), . . - (CH-CH-O) y .H ! i CH, CH, iα or CH, CH, H (OCH CH,),, - (OCH, CH-), (CH.CH,0) x . - (CH, CHO)„. NCH,CH,N H (OCH CH.) ! - (OCH, CH-) y (CH-CH-O) γ . - (CH-CHO)-. 40 CH, CH,,*and xviii) mixtures thereof wherein R is a fatty alkyl group; R, is -H or a fatty alkyl group; x, x' , y, y' and n are each independently moles of ethyleneoxide; and , m' , 1 and 1' are each independently moles of propyleneoxide,* and with the proviso that the fatty alkyl group and/or the number or arrangement of the ethyleneoxide and/or propyleneoxide units are such that the surfactant composition is solid at 24'C; and admixing from about 0.01 to about 90 weight percent pesticide while the surfactant composition is still in a tacky state,* (all weight percents based on the total spray-coated granular composition weight) . 6. The method of claim 5 wherein R fatty alkyl groups are from C 6 to C 22 ; Ri is H or the fatty alkyl groups are from C 6 to C 22 ; x» x' « Y > Y' • and n are each independently from 1 to 300; and , ' , 1, and 1' are each independently from 1 to 300. 7. The method of claim 6 wherein R is C 8 to C lβ alkyl; R- is H or C„ to C 18 alkyl; x, x' y, y' and n are each independently from 1 to 200; m, m' , 1, and 1' are each independently from 1 to 200. 8. A method for producing a dry bonded granular pesticide system comprising a ) mixing dry water-soluble nitrogen-containing fertilizer particles in a blending chamber; b) melting a solid nonionic surfactant composition; c) spraying the molten surfactant composition onto said fertilizer; d) blending continuously to achieve a uniform coating and granulation of the fertilizer particles; e) admixing pesticide particles while the surfactant composition is still tacky; and f) cooling the pesticide-containing granules wherein said fertilizer comprises from about 1 to about 99 weight percent of the granule composition; said nonionic surfactant comprises from about 1 to about 99 weight percent; and said pesticide comprises from about 0.01 to about 90 weight percent (all weight percents based on the total spray-coated granular composition weight) . 9. The method of claim 8 wherein said fertilizer is present from about 1 to about 95 weight percent of the coated composition. 10. The method of claim 8 wherein said fertilizer is diammonium sulfate. 11. The method of claim 9 wherein said fertilizer is diammonium sulfate. 12. A method for producing a dry bonded granular pesticide system comprising a) mixing dry water-soluble nitrogen-containing 5 fertilizer particles in a blending chamber; b) melting a solid nonionic surfactant selected from the group consisting of i) alkanolamides 0 IH ^ R' R C N ■ " ~~~~~~~~ R" wherein R' and R" each can be -H, -CH 2 CH 2 OH, or - 15 CH 2 - CH-OH; CH 3 ii) ethoxylated alkanolamides of the formula iii) ethylene bisamides of the formula 0 ii R - C H 25. ~ ^ ^-N-CH 2 -CH 2 -N-: H" " ^^ C-R; 0 30 iv) fatty acid esters of the formula 0 II R - C - 0 - R * 35 v) glycerol esters of the formula 0 II R - C - O - CH 2 - CH - CH 2 - 0 - R- OH ; vi) ethoxylated fatty acid glycol and polyethylene glycol esters of the formula 0 II R - C - 0 (CH 2 CH 2 0) x -R. ; vii) sorbitan esters of the formula OH viii) ethoxylated sorbitan esters of the formula H-(OCH 2 CH 2 ) n -0 O- (CH 2 CH 2 0) y ix) alkylphenol ethoxylates of the formula R - C ' ' ' (OCH 2 CH 2 ) n OH; Rι x) alcohol ethoxylates of the formula R - 0 - (CH 2 CH 2 0) n H; xi ) tristyrylphenol ethoxylates of the formula (0 CH 2 CH 2 ) n OH CH 3 C ^ - ' CH 3 — _ ; xii) ercaptan ethoxylates of the formula R - S - (CH 2 CH 2 0) n H; xiii) alcohol alkoxylates of the formula CH 3 R-(0CH 2 CH 2 ) X - (0 - CH - CH 2 ) ra - OH; xiv) ethyleneoxide/propyleneoxide block copolymers of the formula CH 3 I HO - (CH 2 CH 2 0) x (CH 2 -CH-0) m - (CH-CH 2 0) y - H; xv) reverse copolymers of the formula CH 3 CH 3 I HO(CH-CH-O) m - (CH 2 CH 2 0) x - (CH 2 -CH O) l H; xvi) chlorine capped ethoxylates of the formula R - (0CH 2 CH 2 ) X C1; xvii) tetra-functional block copolymers of the formula CH, CH, H (OCH-CH,,, - !OCH CH,), (CH-CH 0)„' - (CH,CH,0),.H NCH,CH,N H (OCH-CH.) . - (OCH CH,) (CH,CHO),. - (CH,CH,0)...H 10 CH, CH, or CH, CH, 15 H (OCH CH,), (OCH, CH,). (CH,CH,θ),. - (CH, CHO)„. / \ ' NCH.CH.N 20 (OCH CH-) (OCH, CH,) (CH,CH,0) . - (CH j CHO),. I CH, CH,,*and xviii) mixtures thereof 25. wherein R is a fatty alkyl group; R. is -H or a fatty alkyl group; x, x' , y, y' , and n are each independently moles of ethyleneoxide; and 30 , m' , 1, and 1' are each independently moles of propyleneoxide; and with the proviso that the fatty alkyl group and/or the number or arrangement of the ethyleneoxide and/or propyleneoxide units are 35 such that the surfactant composition is solid at 24'C. c) spraying the molten surfactant onto the fertilizer; d) blending continuously to achieve a uniform coating and granulation of the fertilizer particles,* e) admixing pesticide particles while the surfactant composition is still tacky; and f) cooling the pesticide-containing granules wherein said fertilizer comprises from about 1 to about 99 weight percent of the granular composition; said nonionic surfactant comprises from about 1 to about 99 weight percent; and said pesticide comprises from about 0.01 to about 90 weight percent (all weight percents based on the total spray-coated granular composition weight) . 13. The method of ciaim 12 wherein the fertilizer is present from about 1 to about 95 weight percent based on the coated composition. 14. The method of claim 12 wherein R fatty alkyl groups are from C 6 to C 22 R, is -H or the fatty alkyl groups are from C 6 to C 22 ; x» x' • y* y' • ant -**- n - re each independently 1 to 300; and m, m' , 1, and 1' are each independently 1 to 300. 15. The method of claim 14 wherein R is C, - C. β alkyl; Ri is -A or C β - C lβ alkyl; x, x' , y, y' , and n are each independently from 1 to 200; and m, m' , 1, and 1' are each independently from 1 to 200. 16. The method of claim 8 wherein i) the nonionic surfactant is melted at from about 65' C to about 95 * C; and 5 ii) the pesticidal granules particles are cooled to less than about 50 * C. 17. The method of claim 12 wherein i) the nonionic surfactant is melted at from about 65 * C to about 95 * C; and 0 ii) the pesticidal granules particles are cooled to less than about 50 * C. 18. The dry bonded pesticide granules produced by the process of claim 1. 19. The dry bonded pesticide granules produced by the process 5 of claim 3. 20. The dry bonded pesticide granules produced by the process of claim 5. 21. The dry bonded pesticide granules produced by the process of claim 8. 20 22. The dry bonded pesticide granules produced by the process of claim 10. 23. The dry bonded pesticide granules produced by the process of claim 12. 25.

Inventors: HAZEN JAMES LYLE, HAZEN, JAMES, LYLE
Applicants: RHONE POULENC INC, RHONE-POULENC INC.
Application year: 1996
Main classification: A01N25
IPC codes: A01N25, A01N57, B01J2, C05C3, C05G3