ACRYLIC COATED GRANULAR PESTICIDAL COMPOSITIONS AND METHOD FOR CONTROLLING THE RATE OF TOXICANT RELEASE OF A PHOSPHORUS PESTICIDE-CONTAINING COMPOSITION

Abstract: There are provided acrylic polymer coated pesticidal compositions which exhibit reduced mammalian dermal toxicity and which comprise granular carriers impregnated or coated with a phosphorus-containing pesticide, the carrier-­ pesticide entity being coated with an acrylic polymer.

Description: TITLE: ACRYLIC POLYMER COATED GRANULAR PESTICIDAL COMPOSITIONS It is known that a number of phosphorus pesticidal compounds, such as 2-(diethoxyphosphinyl imino)-1, 3-dithiolane, 2-(diethoxyphosphinylimino)-4 methyl-1,3-dithiolane, 2-(diethoxyphosphinylimino)-1,3- dithietane, O,O-diethyl S-(ethylthiomethyl)phosphorodithioate and O,O-diethyl S-tt(l,l-dimethylethyl)thiogmethyl -phosphorodithioate, are highly effective for the control of broad spectrum of insects and/or nematodes which attack and destroy agriculturally important food and fodder crops. It is, therefore, of advantage to utilize such compounds in various compositions useful in agriculture. Unfortunately, these otherwise highly effective pesticides are extremely toxic when introduced into the human circulatory system as by ingestion, inhalation, or dermal absorption. Thus, the use of compositions containing the above referred-to compounds for the control of insect pests represents a distinct hazard to individuals engaged in the use and application thereof. Similar hazards are encountered by those who are engaged in storing, transporting and distributing to the ultimate user such compositions. Practical use aspects of the above referred 0 pesticide compounds for intended pest control often dictate the use of various granular carrier compositions in which the pesticidal compound is adsorbed or absorbed onto or into the carrier composition. These granular compositions not only provide a more dilute composition of tWhe active pesticide for appropriate applications in agronomic uses but also serve to reduce the potential hazard in use of the pesticide through dermal absorption. Even though such formulated compositions tend to reduce the potential hazard of dermal absorption of the above referred-to pesticides, it is highly desirable to reduce the potential hazard even more. It is, therefore, an object of the invention to provide a granular formulation composition containing a phosphorus pesticide which exhibits reduced mammalian dermal toxicity, while retaining its presticidal effectiveness. To these ends, it has been found that, when solid granular compositions containing phosphorus pesticides are treated, as by spraying for instance, with certain acrylic latices, or with solutions of certain acrylic polymers in organic solvents, the resultant acrylic polymer coated compositions possess advantageously a two to three fold margin of safety due to their lowered mammalian dermal toxicity as compared to similar, uncoated compositions, while their pesticidal activity and physical integrity remains unchanged. These effects may be accomplished in a straightforward manner by applying certain acrylic latex compositions or solutions of certain polymers in an organic solvent to the surfaces of said impregnated pesticidal granules. More specifically, the invention in one aspect is a solid particulate composition comprising particles of an inert sorptive or non-sorptive carrier impregnated or coated with a phosphorus pesticide, and optionally cuat and blended with a finely divided sorptive substrate, characterized in that the carrier pesticide entity is coated with an acrylic polymer selected from the group consisting of a (1) hard, thermoplastic acrylic polymer having an intrinsic viscosity of from 0.75 dl/g to 3.1 dl/g at 300C. in tetrahydrofuran, (2) hard, self-crosslinking thermoplastic acrylic polymers having an intrinsic viscosity of from 1.0 dl/g to 2.0 dl/g at 30or. in dimethylformamide and (3) acrylic polymers having an intrinsic viscosity of from 0.05 dl/g to 0.1 dl/g at 30 C. in butanol. The invention also provides a method for controlling the rate of toxicant release of a toxicant containing - particulate composition; comprising applying to said composition, in amounts ranging from, 0.5% to 5%, by weight, of the total composition, an acrylic polymer selected from the group consisting of (1) hard thermoplastic acrylic polymers having an intrinsic viscosity of from 0.75 dl/g to 3.0 dl/g at 0 30 C. in tetrahydrofuran, (2) hard self-crosslinking thermoplastic acrylic polymers having an intrinsic viscosity of from 1.0 dl/g to 2.0 dl/g at 30 C. in dimethylformamide, and (3) acrylic polymers having an intrinsic viscosity of from 0.05 dl/g to 0.1 dl/g at 300C. in butanol; wherein said solid particulate composition comprises particles of an inert, coarse or funely divided, sorptive or non-sorptive carrier impregnated or coated with said toxicant. According to the process of the invention, in preferred embodiments, the compositions of the granular formulation, prior to acrylic polymer coating, are yepaxd by impregnating a toxicant ranging from about 2% to about 25%, by weight, and , preferably, from 2.5% to 20%, by weight, said toxicant being 2-(diethoxy phosphinylimino)-l, 3-dithiolane, 2(diethoxyphosphinyl imino)-4-methyl-l, 3-dithiolane 2-(diethoxyphosphinyl imino)-l, 3-dithietane, 0,O-diethyl-S-(ethylthiomethyl)- phosphorodithioate, 0, O-diethyl S-t [(l,l-dimethyl- ethyl)thiomethyljphosphorodithioate, and equivalents thereof, with a suitable granular carrier. Illustrative of the'latter carrier is either (a) a sorptive material, such as attapulgite or montmorillonite (clays), brick chips, pumice, talc, volcanic cinders, corncob grits, or (b) a non-sorptive material, such as sand or limestone chips. If a sorptive material is selected, a deactivator such as ethylene glycol, di-, tri- or tetraethylene glycol and mixtures thereof can be added to neutralize intrinsic acidity in amounts ranging from about 3% to about 6%, by weight, of said compositions. In this event, the amount of granular carrier is decreased by an amount equal to that of the deactivator added to said composition. Advantageously, the above described granular composition may be blended and/or coated with from about 0.5%, by weight, to about 2%, by weight of composition of a finely divided sorptive substrate, such as calcined powdered clays, diatomaceous earth, calcium silicate, fumed silica, and fumed silica which has been made hydrophobic by the replacement of most of the hydrophilic hydroxyl group, which normally populate the silica surface, with trimethylsiloxyl groups as well as mixtures of said substrate. It has been found that the addition of said sorptive substrate to the granular formulations aids in maintaining the free-flow-form- ation of agglomerates in same, particularly subsequent to treatment with a sprayed acrylic polymer, defined hereinbelow with particularity. It is a good practice to coat impregnated granular formulations, hereinabove set forth, by any suitable means, such as by spraying with an acrylic latex. The coating is accomplished by spraying either an aqueous emulsion of an acrylic polymer or a solution of an appropriate acrylic polymer in amounts sufficient to provide an acrylic polymer coating of from about 0.5% to about 5%, by weight, and more preferably, from about 1.5% to about 4%, by weight, of the overall granular formulation. Examplary of the above mentioned acrylic latices are (a) thermoplastic acrylic emulsion polymers with a solids content of from about 38% to about 43% by weight, and having an intrinsic viscosity range of from 0.75 to 3.1 dl/g at 300C. in THF (tetrahydrofuran), (b) crosslinking acrylic emulsion polymers with a solids content of about 45-46 %, by weight, and having an intrinsic viscosity range of from 1.0 to 2.0 and, preferably, about 1.4 dl/g at 300C. in DMP (dimethyl- formamide), and (c) solutions of acrylic polymers in tetrahydrofurfuryl alcohol, wherein said acrylic polymers have an intrinsic viscosity range of from aboutO.05 to 0.1 dl/g and, preferably, about .085 dl/g at 300C. in butanol. It is an advantage in carrying out the process of the invention to prepare the coated granular compositions in a straightforward manner involving a plurality of steps. For instance, from about 2% to about 30% by weight, and preferably from about 2.5% to about 20% by weight, of formulation of a toxicant selected from the above identified group, for instance, O,O-diethyl S-t[(lsl-dimethylethyl)thiogmethyl? -phosphorodithioate, is mixed with from about 3% to about 6%, by weight, of formulation of a deactivator selected from the group consisting of ethylene glycol, di-, tri- or tetraethylene glycol and mixtures thereof. The weight percent of the overall mixture is based on the weight of the carrier. This mixture is then sprayed on a granular carrier selected from the group consisting of clays, such as attapulgite and montmorillonite clays, brick chips, pumice, talc, volcanic cinders, corncob grits, sand and limestone chips, wherein said carrier is used in amounts from about 62%, by weight, to about 94% and, preferably; from about 68% to about 92%, by weight of formulation. After the spraying has been completed, agitation of the mixture is continued until all of the liquid is absorbed. Thereafter, if so desired, from about 0.5% to about 2%, by weight, of a finely divided sorptive substrate is added and agitation of the mixture continued until a uniform blend is obtained. The latter sorptive substrate is illustratively calcined powdered clays, diatomaceous earth, calcium silicate, fumed silica and fumed silica which has been made hydrophobic as by the replacement of most of the hydrophilic hydroxyl groups which normally populate the silica surface with trimethyl sSlcxyl groups. The formulations so-prepared are then agitated by suitable means and sprayed with either one of a group of certain acrylic latices (an aqueous emulsion of an acrylic polymer) or a solution of said acrylic polymer is a solvent, such as tetrahydrofurfuryl alcohol, in amounts sufficient to provide an acrylic polymer coating of, preferably, from about 0.5% to about 5%, by weight, and, more preferably, from about 1,5% to about 4% by weight, of said granular formulations. The latter latices may be selected from hard thermoplastic acrylic emulsion polymers with a solids content ranging from about 38% to about 43% by weight, and having an intrinsic viscositysange of f m 0.75 to 3.1 dl/g at 300C. in TEF (tetrahydrofuran), from hard self-crosslinking acrylic emulsion polymers with a solids content of about 45-46% by weight, and having an intrinsic viscosity range of from 1.0 to 2.0 and, preferably, about 1.4 dl/g at 30 C. in dimethylformamide (DMF), and from solutions of acrylic polymers in tetrahydrofurfuryl alcohol, wherein said acrylic polymers have an intrinsic viscosity range of form 0.05 to 0.1 dl/g, and preferably, 0.085 dl/g at 30 C. in butanol. If desired, the above formulations may be heated to accelerate and increase the hardening of said coatings. It is found that, by utilizing the teaching of the present invention, a number of compositions can be prepared within which it is possible to select one wherein the toxicant is released rapidly into the surrounding environment over a relatively short period of time; or to alteruatively select a composition which will release said toxicant slowly over a prolonged period of time. Thus, it is possible to adjust, within certain practical limits, if so desired, the controlled release of toxicant from the novel compositions of the present invention by the selection of suitable formulations. The coated granular pesticidal compositions also exhibit reduced mammalian dermal toxicity. The present invention is further illustrated by the following examples in which,unless otherwise stated, the percentages set forth are by weight. EXAMPLE 1 Preparation of a granular formulation containing 15% by weight of O,O-diethyl S-{[(1,1-dimethylethyl)thio]methyl}- phosphorodithioate. A. 78.5 gms. of granular (25/50) montmorillonite having the composition set forth below are charged to a rotating type blender and agitated. While being agitated, the granules are sprayed with a mixture of the insecticide: O,O-diethyl S-I(I,I-dimethylethyl)thi03 methyls phosphorodithioate (17.5 gms. 88.57% real = 15.5 g. real) and a deactivator comprising a mixture of ethylene, di, triand tetraethylene glycol (4.0 gms.) After the spraying has been completed, blending is continued until all the liquid is absorbed. There is obtained 100 gms. of a granular formulation containing 15.5 w/w of the above insecticide. Montmorillonite Analysis Component % by weight, range Silica (SiO2) 68-72.5 Ferric oxide (Fe203) 5-7 Aluminum oxide (A1203) 11-15 Calcium oxide (CaO) 0.012-1.5 contd. Magnesium oxide (MgO) 0.8-1.6 Sodium oxide (Na20) 0.08-0.4 Potassium oxide (K20) 1.1-1.6 Phosphoric acid (P205) 0.1-0.2 Cr, Cu, Mn, Ni, Ti trace Ignition loss 3-7.5 B. Following above method, but substituting 78.5 gms. of attapulgite having the analysis set forth below, containing 15.5 w/w of the above insecticide is prepared. Attapulgite Analysis Component % by weight Silica 64.37 Aluminium 12.46 Ferric oxide 5.93 Magnesium oxide 5.28 Calcium oxide 0.99 Sodium oxide 0.05 Potassium oxide 1.58 Titanium dioxide 0.73 Loss on ignition 8.21 EXAMPLE 2 Preparation of acrylic polymer coated granular pesticidal formulations a. A granular insecticidal formulation (100 g) prepared by the method of Example 1A above is tumbled in a rotating type blender and sprayed with a hard, thermoplastic acrylic emulsion polymer with a solids content of 38% and with an intrinsic viscosity of 3.1 dl/g at 30or. in THF (10 ml of latex is used). There is obtained 110 g of free-flowing and dry granules containing 14.09%, by weight, of toxicant. b. A sample of the above formulation is stored at 450C. for 2 hours. c. A granular insecticidal formulation (100 g) prepared by the method of Example 1A above is sprayed as above with a mixture of a hard thermoplastic acrylic emulsion polymer, solids content 43%, by weight, and with an intrisic viscosity of 0.75 dl/g at 30 C. in THF and dibutyl phthalate (6 ml of a 60:40 mixture). There is obtained 106 g. of formulation containing 14.6% by weight of toxicant. By the methods of a, b and c above, granular formulations are prepared, containing 15.5% by weight, of 20.5% by weight, of O,O-diethyl S-t[(l,l-dimethylethyl)- thio3methylss -phosphorodithioate, respectively. EXAMPLE 3 Preparation of acrylic polymer coated granular pesticidal formulations Procedure A granular insecticidal formulation (100 g) prepared by the method of Example 1A, above, and a finely divided hydrophobic silica (0.5 g; 0.5%) in which most of the surface hydroxyl groups have been replaced by trimethylsiloxyl groups, are mixed and blended for 5 minutes prior to being sprayed with the respective coatings a. A granular formulation (100.5 g) prepared by the above procedure is agitated and sprayed with a hard polymer self-crosslinking acrylic emulsion/with a solids content of 45%, by weight, and with an intrinsic viscosity of 1.4 dl/g at 300C. in DMF (4 ml of latex used for coating). The thus obtained formulation (104.5 g; 14.83% real) is free-flowing, dry, and shows no tendency to form agglomerates; b. The procedure of a above is followed except that 6 ml. of latex are used to coat the granules (106.5 g; 14.55% real); or c. A granular formulation (100.5 g.) prepared by the above procedure is agitated and sprayed with a hard self-crosslinking acrylic emulsion polymer with a solids content of 45%, by weight, and with an intrinsic ciscosity of 1.4 dl/g at 30 C. in DMF (6 ml of latex used for coating). The thus obtained formulation (106.5 g; 14.55% real) is free-flowing dry, and shows the presence of only trace amount of agglomerates. By the methods of a, b or c above, a granular formulation is prepared which contains 15.5% by weight, or 20.5% by weight of O,O-diethyl S-0t(l,l-dimethylethyl) thio3methyl -phosphorodithioate, respectively. EXAMPLE 4 Preparation of acrylic polymer coated granular pesticidal formulation Procedure A granular insecticidal formulation (100 g) prepared by the method of Example 1A, above, and a finely divided hydrophobic silica in which most of the surface hydroxyl groups have been replaced by trimethylsiloxyl groups (1.0 g; 1%) are blended for 5 minutes prior to being sprayed with the respective coatings. a. A granular formulation (101 g) prepared by the above procedure is tumbled in a rotating type of blender and sprayed with a hard, self-crosslinking acrylic emulsion polymer, with a solids content of 45% by weight, and with an intrinsic viscosity of 1.4 dl/g at 30 C. in DMF (4 ml of latex used). The thus obtained composition (105 g; 14.76% real) is free-flowing, dry, and shows no tendency to form agglomerates; b. A granular formulation (101 g) prepared by the above procedure is tumbled and sprayed with a hard, self-crosslinking acrylic emulsion polymer with a solids content of 45%, by weight, and with an intrinsic viscosity of 1.4 dl/g at 300C. in DMF (6 ml of latex used). The thus obtained composition (107 g; 14.48% real) is free-flowing, dry, and does not form aggregates. EXAMPLE 5 Preparation of acrylic polymer coated granular presticidal formulations Procedure There are admixed 100 gms. of a granular insecticidal formulation prepardd by the method of Example 1A, above, together with 0.5 gm of a finely divided hydrophobic silica in which most of the surface hydroxyl groups have been replaced by trimethylsiloxyl groups. The admixing takes place within 5 minutes prior to being sprayed with the respective coatings. a. A granular formulation (100.5 g.) prepared by the above procedure is agitated and sprayed with a hard thermoplastic acrylic emulsion polymer with a solids content of 43% by weight, and with an intrinsic viscosity of 0.75 dl/g at 300C. in THF (6 ml of latex used). The thus obtained composition (106.5 g; 14.55% real) is dry and forms only a few agglomerates. b. As under a except that 1.0 g (1%) of the above hydrophobic silica is used in the formulation. The thus-obtained composition (107 g; 14.48% real) is dry and forms no agglomerates. EXAMPLE 6 Preparation of a granular formulation containing 20% by weight of O,O-diethyl S-{[(1,1-dimethylethyl)- thio methy?-phosphorodithioate Granular (25/50) montmorillonite clay (66.2 g) is agitated in a blender and while being agitated, the granules are sprayed with a mixture of O,O-diethyl S-{[(1,1- dimethylethyl)thio]phosphorodithioate (22.8 g; 90.38% real =20.6 g. real) and a deactivator comprising a mixture of ethylene, di-, tri- and tetraethylene glycol (4.0 g). After the spraying step has been completed, finely divided hydrophobic silica in which most of the surface hydroxyl groups have been replaced by trimethyl siloxHrl groups (1.0 g; 1%) is added and blending is continued for 5 minutes. The thus-obtained blend is tumbled and sprayed with a hard, self-crosslinking acrylic emulsion polymer with a solids content of 45% by weight and with intrinsic viscosity of 1.4 dl/g at 300C. in DMF (6 ml of latex used). The composition is free-flowing and dry. EXAMPLE 7 Preparat on of a granular formulation containing 10% by weight of O,O-diethyl S-(ethylthiomethyl)phosphorodi thioate a. Brick chips (79.07 g) are charged to a rotating type blender. While being agitated, the chips are sprayed with the insecticide: O,O-diethyl S-(ethylthiomethyl)phosphorodithioate (11.93 g of 88% real 10.5 g real, and diethylene glycol (5.0 g). Next, the so-treated chips are sprayed with a 37.5% w/w solution of an acrylic polymer in tetrahydrofurfuryl alcohol (4.0 g.) to provide a polymer coating for said chips. The acrylic polymer is characterized by having an intrinsic viscosity of .085 dl/g at 30 C. in butanol. There is obtained 100 g of a granular formulation containing 10% w/w of the above insecticide (with a 5% overage). The above formulation has an LD50 of > 200 mg/kg by the method of Example 9, whereas a similar, but uncoated, sample has an LD of 110 mg/kg. b. By the method of a, but substituting 0,0 diethyl S I, (l,l-dimethylethyl)thiogmethyifphosphoro- thioate (10.5 g. real) for the above insecticide, a granular formulation can be prepared. c. The preparation under a is repeated except that the sprayed brick chips are blended for 5 minutes with 0.5% by weight, of a finely divided hydrophobic silica in which most of the surface hydroxyl groups have been replaced by trimethylsiloxyl graips, and the thus prepared blend is then sprayed with a hard thermoplastic acrylic emulsion polymer with a solids content of 38% and with an intrinsic viscosity of 3.1 g dl/g at 30 C. in THF, to provide 1.9%, by weight, of formulation of said polymers. The thus obtained composition has a dermal LD50 of from > 120 to < 200 mg/kg by the method of Example 9. The properties of the acrylic resins employed in the above Examples 2a, 2b and 7c, for instance, are further characterized below. The resin, manufactured by the Rohm and Hass Co. is sold under the trademark, RHOPLEX z B-85. It has the following typical physical properties: Appearance White milky liquid Solids 38.0 + 0.5 percent pH (as shipped) 9.5 to 10.0 Weight per gallon 8.9 libs. Dry bulking vanue (gal/lb.) 0.102 (calculated) Tukon hardness (KHN) 18 Colloidal charge Anionic Minimum film-formulation te, perature < 90 C In Examples 2c, 5a and 5b, above, the acrylic resin is manufactured by Rohm and Haas Co. and is sold under the trademark RHOPLEX 9 B-88. It has the follow- ing typical physical properties: Appearance White Milky liquid Solids content 42 to 43% Viscosity Less than 100 cps. pH (as shipped) 8.5 to 9.0 Ionic nature Nonionic Minimum film-forming temperature Greater than 900C. Tukon hardness (approx.) 18 KIlN In Examples 3a, 3b and 4a, above, the acrylic resin manufactured by the Union Carbide Co. and is sold under the trademark UCAR Latex 189. It has the following typical physical properties: Polmer Type Hard, self-cross linking acrylic Emulsifier Anionic Total Solids 45% by wt. Viscosity (Brookfield, Model LVT, spindle No. 2;60 rpm) < lOOcp pH at 250C 4.0 Apparent Specific Gravity at 20/20 C 1.07 Weight per Gallon at 200C 8.9 Ib Particle size (microns) 0.3 Surface Tension (dynes per cm.) 38 In Examples 3c, 4b and 6, above, the acrylic resin is manufactured by the Union Carbide Co. and is sold under the UCAR z Latex 879. It has the following typical physical properties: Total Solids, % by weight 46 Brookfield Viscosity (maximum), Model LVT, Spindle No. 1,60 rpm,cps 100 pH at 25OC 4.5 Apparent Specific Gravity at 20/20 C 1.07 Weight per Gallon at 20 C 8.90 Surface Tension, dynes per cm at 30% total solids 50 In Example 7a and 7b, the acrylic resin is manufactured by the American Cyanamid Co. and is designated as XG4011 Acrylic Resin as having the following typical physical properties: : Appearance Clear, viscous liquid Solids, % by weight 75 2 Solids, % by weight 70 + 2 Solvent N-Butanol Viscosity, Gardner-Holdt, 25 C. Z5Z7 Color, Gardner, 1963, maximum 1 Acid number, (resin solids) 100-120 Pounds per gallon, approximate 8.5 Flash point (Tag open cup) ,1720F Intrinsic Viscosity in Butanol at 309C. .085 EXAMPLE 8 General method for the evaluation of dermal toxicity of the formulations of the present invention using male albino rabbits as the test animals. Materials. a. Five male albino rabbits weighing approximately 2.2 to 3.5 kilogram are selected for each dosage level. The hair is shaved from the entire trunk. b. Saran tubing or 'Winylite" film W1900, 30.5 cm (12") wide, 0.04 millimeter in thickness and long enough to fit around the rabbit. c. One felt cloth bandage measuring approximately 22.9 x 45.7 cm (9" x 18"). d. Four pieces of 3.8 cm (1.5") adhesive tape approximately 35.6 cm (14") long. Procedure a. The granular material is placed in the center of the plastic film and is moistened with water. b. The rabbits underside is moistened with water and the animals are placed belly down on the material. c. The plastic is then brought up and around the animal and secured at each end with strips of adhesive tape. The felt cloth is then placed under the belly and brought up around the animal and secured to the body with the remaining two strips of adhesive tape. Evaluation Twenty-four hours after dosing, the "cuff" is removed and any remaining material is brushed away. If the test material cannot be removed, the animal is fitted with a fiber collar which prevents the animal from licking the treatment area. The animals are observed for 14 days, post dosing, noting signs of toxicity, skin irritation and mortality. At the end of 14 days, the animals are sacrificed and weighed. From the data thus obtained, the dermal 5O values (mg/kg body weight) are calculated from the formulations (compositions) of Examples 2 to 6, and are summarized in Table I below, along with the LD50 value of the toxicant itself and a granular (non-coated) formulation thereof. TABLE I Dermal toxicity of coated granular compositions containing O,O-diethyl S- dimethylethyl)thiogmethyss phosphorodithioate Composition LD50 mg/kg 0,0-diethyl S-{[(1,1-dimethylethyl)thio]methyl}phosphorodithioate (technical) 1-2 Non-coated, granular; 15% toxicant. < 20 Example 2a > 80 Example 2b ;80 Example 2c > 80 < 40 Example 3a > 80 Example 3b > 80 Example 4a ,80 Example 4b > 80 Example 5a > 80 < 40 Example 5b > 80 > 40 Example 6 > 80 < 40 It can be seen from Table I above, that the exemplified coated granular compositions of the present invention are at least two to three-fold less toxic as are the comparable non-coated compositions. EXAMPLE 9 Southern corn rootworm soil residual test. One quart (950 ml) of moist (about 25% of moisture holding capacity) potting soil is placed in a stainless steel beaker approximately 22 cm deep x 18 cm diameter. A weigbed amount of granular is distributed over the soil. The beaker is then capped and rotated on a mechanical mixer for 2 minutes (60 revolutions). Tow l-ounce (29.7 ml) jars of soil are removed for 0 days mortality evaluation with southern corn rootworm (Diabrotica undecipunctata howardi) larvae. The remainder of the treated soil is divided between 2 wide-mouth pint (475' ml) treated paper containers. Each container of soil received 100 ml of tap water, bringing the soil to near field moisture holding capacity. A regime of moistening and drying continues throughout the test period. The treated soils plus the untreated control are held in the holding room at about 26.7 C. At weekly intervals the duplicate containers of soil are removed, the soil thoroughly mixed, moistened to about 25% moisture holding capacity, and two l-ounce (29.7 ml) jars of soil are removed for bioassay with southern corn rootworm larvae. The data obtained are summarized in Table II below. TABLE II Evaluation of the soil residual activity of acrylic polymer coated pesticidal granules, containing 15% by weight of 0,0-diethyl S-{[(dimethylethyl)thio]methyl} phosphorodithioate against southern corn rootworm larvae. EMI21.1 <SEP> Concentration <SEP> Residual <SEP> Activity <SEP> (average <SEP> of <SEP> two <SEP> replicates) <tb> Example <SEP> mg. <SEP> a.i <SEP> /950 <SEP> ml** <SEP> Percent <SEP> kill, <SEP> days <SEP> past <SEP> start <SEP> of <SEP> week <tb> <SEP> soil <SEP> 0 <SEP> 7 <SEP> 21 <SEP> 42* <SEP> 70 <SEP> 91 <SEP> 131 <tb> control <SEP> - <SEP> 0 <SEP> 0 <SEP> 30 <SEP> 5 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> 1 <SEP> 50 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 30 <SEP> 0 <SEP> 0 <tb> uncoated <SEP> 2 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 67 <SEP> 0 <tb> <SEP> 4 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <tb> <SEP> 1 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 44 <SEP> 0 <tb> 2a <SEP> 2 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 78 <SEP> 0 <tb> <SEP> 4 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 50 <tb> <SEP> 1 <SEP> 20 <SEP> 100 <SEP> 100 <SEP> 95 <SEP> 10 <SEP> 0 <SEP> 0 <tb> 3a <SEP> 2 <SEP> 90 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 90 <SEP> 44 <SEP> 00 <tb> <SEP> 4 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 17 <tb> <SEP> 1 <SEP> 50 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 67 <SEP> 0 <tb> 3b <SEP> 2 <SEP> 70 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 0 <tb> <SEP> 4 <SEP> 80 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 83 <tb> <SEP> 1 <SEP> 85 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 11 <SEP> 0 <tb> 3c <SEP> 2 <SEP> 80 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 78 <SEP> 0 <tb> <SEP> 4 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <tb> * After this day only single tests are run ** Corresponds to 1.12, 2.24 and 4.48 kg/ha, respectively TABLE II (continued) EMI22.1 <SEP> Concentration <SEP> Residual <SEP> Activity <SEP> (average <SEP> of <SEP> two <SEP> replicates) <tb> Example <SEP> mg. <SEP> a.i <SEP> /950 <SEP> ml** <SEP> Percent <SEP> kill, <SEP> days <SEP> past <SEP> start <SEP> of <SEP> week <tb> <SEP> soil <SEP> 0 <SEP> 7 <SEP> 21 <SEP> 42* <SEP> 70 <SEP> 91 <SEP> 131 <tb> <SEP> 1 <SEP> 85 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 90 <SEP> 0 <SEP> 0 <tb> 4a <SEP> 2 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 56 <SEP> 0 <tb> <SEP> 3 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 83 <tb> <SEP> 1 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 105 <SEP> 70 <SEP> 0 <SEP> 0 <tb> 4b <SEP> 2 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 67 <SEP> 0 <tb> <SEP> 3 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 83 <tb> <SEP> 1 <SEP> 45 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 40 <SEP> 22 <SEP> 0 <tb> 5a <SEP> 2 <SEP> 75 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 70 <SEP> 11 <SEP> 0 <tb> <SEP> 3 <SEP> 80 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 50 <tb> * After this day only single tests are run ** Corresponds to 1.12, 2.24 and 4.48 kg/ha, respectively Advantageously, from the biological data presented in Table II above, it can be seen that certain of the coated granular formulations may be utilized to provide short term controlled release of toxicant, especially at the lower rates applied (e.g. 3a, 4b and 5a; at 1 mg. a.i., 6 to 10 weeks); while others provide long term controlled release of toxicant, especially at the higher rates applied (e.g. 3b, 3c, 4a and 4b; at 4 mg. a.i., 1319 weeks).

Claims: CLAIMS: 1. A solid particulate composition comprising particles of an inert sorptive or non-sorptive carrier impregnated or coated with a phosphorus pesticidal, and optionally coated and blended with a finely divided sorptive substrate, characterized in that the carrier pesticide entity is coated with an acrylic polymer selected from the group consisting of a (1) hard, thermoplastic acrylic polymer having an intrinsic viscosity of from 0.75 dl/g to 3.1 dl/g at 30 G. in tetrahydrofuran, (2) hard, self-crosslinking thermoplastic acrylic polymers having an intrinsic viscosity of from 1.0 dl/g to 2.0 dl/g at 30 C. in dimethylformamide and (3) acrylic polymers having an intrinsic viscosity of from 0.05 dl/g to 0.1 dl/g at 30 C. in butanol. 2. A composition according to Claim 1, characterized in that said carrier is selected from the group consisting of attapulgite and montmorillonite clays, brick chips, pumice, talc, volcanic cinders, corncob grits, sand and limestone chips, and is employed in amounts ranging from 62% to 94% by weight, of the overall composition; and when a sorptive carrier is employed, a deactivator selected from the group consisting of ethylene glycol, di-, tri- and tetraethylene glycol and mixtures thereof is incorporated in said composition in amounts ranging from 3% to 6% by weight, of total composition to neutralize the intrinsic acidity of said carrier, provided that the percent by weight amount is lowered with an amount equal to that of the deactivator employed; said pesticide is selected from the group consisting of 2-(diethoxyphosphinylimino)-1,3-dithiolane, 2-(diethoxyphosphinylimino)-4 methyl-l,3-dithiolane, 2-(diethoxyphosphinylimino)l,3dithietane, O,O-diethyl S-(ethylthiomethyl)-phosphorodithioate and O,O-diethyl S- {[(1,1-dimethylethyl)thio]-methyl}- phosphorodithioate, and is employed in amounts ranging from 2% to 25%, by weight, of the composition; said sorptive substrate when employed, is selected from the class consisting of a calcined clay, diatomaceous earth, calcium silicate, fumed silica and fumed silica which has been made hydrophobic via replacement of most of the hydrophilic hydroxyl groups by populating the surface of said silica with trimethylsiloxyl groups, and is employed in amounts ranging from 0.5% to 2%, by weight, of the total composition; and said acrylic polymer is selected from the group consisting of a hard, thermoplastic acrylic polymer having an intrinsic viscosity range of from 0.75 dl/g to 3.0 dl/g at 30 C. in tetrahydrofuran, hard, self-crosslinking thermoplastic acrylic polymers having an intrinsic viscosity ranging from 1.0 dl/g to 2.0 dl/g at 300C. in dimethylformamide and acrylic polymers having an intrinsic viscosity ranging from 0.05 dl/g to 0.1 dl/g at 300C. in butanol and is employed in amounts ranging from 0.5% to 5%, by weight, of the total composition. 3. A composition according to Claim 1, comprising 71.36%, by weight, of montmorillonite clay; 15.91% by weight, of 88.57% real O,O-diethyl S-{[(1,1-dimethylethyl)thio]methyl} -phosphorodithioate; 3.63% by weight, of ethylene di-, triand tetraethylene glycol deactivator mixture; coated with 9.1%, by weight, of the total composition of a hard, thermoplastic acrylic polymer latex 43%. by weight, real having an intrinsic viscosity ranging from 0.75 dl/g to 3.1 dl/g at 30 C. in tetrahydrofuran. 4. A composition according to Claim 1, comprising 75-77%, by weight, of montmorillonite clay; 17.5% by weight of 88.57% real O,O-diethyl s-f E(l,l-dimethylethyl)- thioqmethylWphòsphorodithioate; 4.0% by weight, of an ethylene di-, tri- and tetraethylene glycol deactivator mixture; 0.5% by weight, of fumed silica made hydrophobic via replacement of most of the hydrophilic hydroxyl groups populating the surface of said silica with trimethylsiloxyl groups; coated with 1%, by weight, to 3% by weight, of the total composition of a hard thermoplastic selfcrosslinking acrylic polymer latex 45% by weight, real having an intrinsic viscosity of 1.4 dl/g at 300C. in dimethylformamide. 5. A composition according to Claim 1, comprising 71.36%, by weight, of attapulgite clay; 15.91% by weight, of 88.57% real diethyl S-{[(1,1-dimethylethyl)thio]methyl} phosphorodithioate; 3.63% by weight, of a di- and triethylene glycol deactivator mixture; coated with 9.1% by weight, of the total composition of a hard thermoplastic acrylic polymer latex 43, by weight, real having an intrinsic viscosity of from 0.75 dl/g to 3.1 dl/g at 30 C. in tetrahydrofuran. 6. A composition according to Claim 1, comprising 75-77%, by weight, of attapulgite clay; 17.5% by weight, of 88.57% real diethyl S-{[(1,1-dimethylethyl)thio]methyl}- phosphorodithioate; 4.0% by weight of a di- and triethylene glycol deactivator mixture; 0.5% by weight to 1.0% by weight, of a fumed silica made hydrophobic via replacement of most of the hydrophilic hydroxyl groups populating the surface of said silica with trimethylsiloxyl groups; coated with 1% by weight, to 3%, by weight, of the total composition of a hard thermoplastis self-crosslinking acrylic polymer latex 45% by weight, real having an intrinsic viscosity of 1.4 dl/g at 300C. in dimethyl- formamide. 7. A composition according to Claim 1, comprising 79.07% by weight, of brick chips, 11.93% by weight, of 88% real O,O-diethyl S-(ethylthiomethyl)phosphorodithioate, 5%, by weight, of diethylene glycol deactivator mixture; coated with 4% by weight, of a 37.5% solution of an acrylic polymer in tetrahydrofurfuryl alcohol; wherein said acrylic polymer has an intrinsic viscosity of .085 dl/g at 30 C. in butanol. 8. A method for controlling the rate of toxicant release of a toxicant containing - particulate composition; comprising applying to said composition, in amounts ranging from 0.5% to 5%, by weight, of the total composition, an acrylic polymer selected from the group consisting of (1) hard thermoplastic acrylic polymers having an intrinsic viscosity of from 0.75 dl/g to 3.0 dl/g at 300C. in tetrahydrofuran, (2) hard self-crosslinking thermoplastic acrylic polymer having an intrinsic viscosity of from 1.0 dl/g to 2.0 dl/g at 30 C. in dimethylformamide, and (3) acrylic polymers having an intrinsic viscosity of from 0.05 dl/g to 0.1 dl/g at 300C. in butanol; wherein said solid particulate composition comprises particles of an inert, coarse or finely divided, sorptive or non-sorptive carrier impregnated or coated with said toxicant.

Inventors: PASARELA, NUNZIO ROBERT
Applicants: AMERICAN CYANAMID COMPANY
Application year: 1979
Main classification: A01N25
IPC codes: A01N25, A01N57