Polymers for increasing the soil mobility of low-solubility insecticides

Abstract

What is described is use of a polymeric solubilizer for increasing the soil mobility of a sparingly soluble insecticide, said polymeric solubilizer having the property that the active insecticidal ingredient in a 1% by weight aqueous solution of the polymeric solubilizer at 25° C. and 1.01325 bar has a solubility at least forty times higher than under the same conditions in pure water, and wherein the active ingredient:solubilizer weight ratio is ≦1.

Claims

1. A method for improving the soil mobility of a sparingly soluble insecticide, wherein a combination of the insecticide, a polymeric solubilizer, and an adjuvant, in an aqueous application form is applied to the soil to be treated, wherein the polymeric solubilizer has the property that the active insecticidal ingredient in a 1% by weight aqueous solution of the polymeric solubilizer at 25° C. and 1.01325 bar has a solubility at least forty times higher than under the same conditions in pure water, and wherein the weight ratio of active ingredient to solubilizer is ≦1, and wherein the solubilizer is selected from groups A1, B1, D and combinations thereof: A1. hyperbranched polycarbonates in which the hyperbranched polycarbonate is bonded to at least one linear or comb-type polymer and/or at least one functional C.sub.1-C.sub.24 unit comprising a carboxylic acid group, a sulfonic acid group, a sulfenic acid group, a sulfinic acid group, a sulfuric ester group, a phosphonic acid group, an amino group or at least two hydroxyl-C.sub.2-C.sub.10-alkyl groups; B1. vinyllactam copolymers obtained from B1-1. 60-99% by weight (based on the overall copolymer) of 5-7-membered 1-vinyl-2-lactam and B1-2. 1 to 40% by weight of at least one monomer selected from the group of the B1-21 C.sub.8-C.sub.30-alkyl esters of monoethylenically unsaturated C.sub.3-C.sub.8-carboxylic acids, wherein the percentages by weight of the individual components add up to 100% by weight; D. copolymers based on ethylenically unsaturated dicarboxylic mono- and diesters, obtained from D1 at least one monomer from the group of olefins, vinyl ethers and styrene and D2 at least one monomer from the group of mono- and diesters of ethylenically unsaturated dicarboxylic acids, wherein the alcohol group of the ester has a structure of the formula (V)
—(R.sup.10—O).sub.n—(R.sup.11—O).sub.p—R.sup.12  (V) wherein: R.sup.10 is 1,2-propylene or 2,3-propylene; R.sup.11 is ethylene; R.sup.12 is H, unbranched or branched C.sub.1-C.sub.40-alkyl, phenyl, phenyl substituted by C.sub.1-C.sub.20-alkyl, benzyl, benzyl substituted by C.sub.1-C.sub.20-alkyl; n is an integer from 0 to 140 and p is an integer from 0 to 100, wherein the sum of n and p is at least 1, wherein the insecticide is selected from the group consisting of fipronil, allethrin, alpha-cypermethrin, beta-cyfluthrin, bifenthrin, bioallethrin, 4-chloro-2-(2-chloro-2-methylpropyl)-5[(6-iodo-3 -pyridinyl)methoxyl]-3 (2H)-pyridazinone (CAS-RN: 120955-77-3), chlorantraniliprole, chlorfenapyr, chlorpyrifos, cyantraniliprole, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, etofenprox, fenoxycarb, flufenoxuron, hydramethylnon, imidacloprid, indoxacarb, metaflumizone, permethrin, pyriproxifen, tebufenozide and tralomethrin.

2. The method according to claim 1, wherein the insecticide is fipronil.

3. The method according to claim 1, wherein the solubilizer is selected from group A1.

4. The method according to claim 1, wherein the solubilizer is selected from group B1.

5. The method according to claim 1, wherein the solubilizer is selected from group D.

6. The method according to claim 1, wherein a mixture of two or more polymeric solubilizers is used.

7. The method according to claim 1, wherein the weight ratio of active ingredient(s) and solubilizer(s) is from 1:1 to 1:200.

8. The method according to claim 1, wherein the combination of the insecticide and a polymeric solubilizerfurther comprises one or more adjuvants selected from the group consisting of: Z1 tristyrylalkyl ether sulfates or phosphates; Z2 nonionic surfactants based on perfluoroalkyl ethoxylate Z3 a mixture of 83% highly refined petroleum oil based on paraffin and 17% alkylarylpolyoxyethylene glycols; Z4 polyethers or organomodified tri- and polysiloxanes; Z5 a nonionic surfactant mixture of alkyloxypolyethyleneoxyethanols of the formula CH.sub.3CH[(CH.sub.2).sub.nCH.sub.3][O(C.sub.2H.sub.4O).sub.mH]where n=9-15 and m=3-40; Z6 a silicone surfactant mixture of 100% 2-(3-hydroxypropyl)heptamethyltrisiloxane, ethoxylated acetate, allyloxypolyethylene glycol monoallylacetate and polyethylene glycol diacetate; Z7 a biodegradable, low-foaming nonionic surfactant comprising primary alkyl polyoxyethylene ethers, free fatty acids and adjuvants; Z8 a nonionic surfactant mixture of fatty acid and alcohol ethoxylates based on soybeans; Z9 an anionic surfactant mixture comprising 58% ammonium n-alcohol ether sulfate; Z10 an anionic surfactant mixture comprising 58% ammonium nonylphenol ether sulfate; Z11 a mixture of polyalkylene oxide-modified polydimethylsiloxane and nonionic surfactants; Z12 a nonionic detergent composed of 100% polyoxyethylene (10)-isooctyl cyclohexyl ether; Z13 alkoxylated fatty alcohols and/or fatty acids, which may additionally each be etherified, sulfonated or phosphonated; and combinations thereof.

9. A method for controlling soil-dwelling invertebrate pests, wherein a) at least one sparingly soluble active insecticidal ingredient selected from the group consisting of fipronil, allethrin, alpha-cypermethrin, beta-cyfluthrin, bifenthrin, bioallethrin, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone (CAS-RN: 120955-77-3), chlorantraniliprole, chlorfenapyr, chlorpyrifos, cyantraniliprole, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, etofenprox, fenoxycarb, flufenoxuron, hydramethylnon, imidacloprid, indoxacarb, metaflumizone, permethrin, pyriproxifen, tebufenozide, and tralomethrin; and b) at least one polymeric solubilizer which has the property that the active termiticidal ingredient in a 1% by weight aqueous solution of the polymeric solubilizer at 25° C. and 1.01325 bar has a solubility at least forty times higher than under the same conditions in pure water, and is selected from the group of the solubilizers A1 and B1: A1. hyperbranched polycarbonates in which the hyperbranched polycarbonate is bonded to at least one linear or comb-type polymer and/or at least one functional C.sub.1-C.sub.24 unit comprising a carboxylic acid group, a sulfonic acid group, a sulfenic acid group, a sulfinic acid group, a sulfuric ester group, a phosphonic acid group, an amino group or at least two hydroxyl groups; B1. vinyllactam copolymers obtained from B1-1. 60-99% by weight (based on the overall copolymer) of 5-7-membered 1-vinyl-2-lactam and B1-2. 1 to 40% by weight of at least one monomer selected from the group of the B1-21 C.sub.8-C.sub.30-alkyl esters of monoethylenically unsaturated C.sub.3-C.sub.8-carboxylic acids, wherein the percentages by weight of the individual components add up to 100% by weight, in a weight ratio (a:b) ≦1 in an aqueous application form are applied to or into a soil used by the pests.

10. The method according to claim 9, wherein the pests are ants and/or are present on the soil of a sugarbeet crop.

11. The method according to claim 9, wherein the pests are termites, and wherein the insecticidal active ingredient is a termiticide.

12. The method according to claim 11, wherein the soil is present under a building or within a radius of 10 m thereof.

13. The method according to claim 11, wherein the termiticide is applied in trenches with a depth of 1-3 inches.

14. The method according to claim 11, wherein the concentration of the termiticide in the aqueous application form is at least 1000 ppm.

15. The method according to claim 9, wherein the insectididal active ingredient is fipronil.

16. The method according to claim 9, wherein the polymeric solubilizer is A1.

17. The method according to claim 9, wherein the sparingly soluble active insecticidal ingredient, the polymeric solubilizer and if appropriate one or more adjuvants are used as the formulation.

18. The method according to claim 9, wherein the polymeric solubilizer and/or one or more adjuvants are added as a tank mix to the aqueous application form.

Description

EXAMPLES

(1) Abbreviations

(2) AIBN: azobis(isobutyronitrile) AMPS: 2-acrylamido-2-methylpropanesulfonic acid DBTL: dibutyltin dilaurate IP: isopropanol IPDI: isophorone diisocyanate IT: internal temperature LA: lauryl acrylate MA: maleic anhydride NaA: sodium acrylate PEGMEMA 475: polyethylene glycol monomethyl ether methacrylate (M=475 g/mol) S: styrene T: feed time TBPPiv: t-butyl perpivalate TMP×15.7 PO: reaction product of trimethylolpropane with a 15.7 molar excess of propylene oxide VP: vinylpyrrolidone
Materials Used a) Active termiticidal ingredients

(3) Fipronil was used as a commercial SC formulation, Termidor® (comprising 96 g/l of Fipronil, BASF SE), or as a technical grade active ingredient with a purity of approx. 90%. b) Solubilizers

(4) Solubilizers of group B1:

(5) TABLE-US-00001 Composition [% by weight] Designation VP LA NaA AMPS S1 90 10 — — S2 80 20 — — S3 70 30 — — S4 78 20 2 — S5 70 20 10  — S6 76 20 2 2

(6) Solubilizers of group D:

(7) S7: MA/S (50:50 mol %), 50% of the MA units having been esterified with a C.sub.13 fatty alcohol alkoxylate.

(8) Solubilizers of group A (A1):

(9) Solubilizer S8 (hyperbranched polycarbonate based on diethyl carbonate and the reaction product of trimethylolpropane with a 15.7 molar excess of propylene oxide functionalized with PEG chains (degree of functionalization 100%))

(10) Solubilizer S9 (hyperbranched polycarbonate based on diethyl carbonate and the reaction product of trimethylolpropane with a 15.7 molar excess of propylene oxide functionalized with a comb-type PVP-co-Plaurylacrylate-co-PEGMEMA copolymer (degree of functionalization 50%))

(11) Solubilizer S10 (hyperbranched polycarbonate core based on diethyl carbonate and the reaction product of trimethylolpropane with a 15.7 molar excess of propylene oxide functionalized with PEG-b-polycaprolactone block copolymer (degree of functionalization 100%) c) Adjuvants

(12) Soprophore 4D384:

(13) ##STR00007##

(14) Break Thru® S 240 (Evonik): nonionic surfactant based on modified polysiloxane polyethers

(15) Synthesis Examples for Solubilizers

Example 1

Solubilizer S1 (N-vinylpyrrolidone/lauryl acrylate copolymer [90/10% by weight])

(16) The initial charge (350 g of isopropanol, 10 g of N-vinylpyrrolidone) was sparged with nitrogen and heated to an internal reactor temperature of 80° C. Subsequently, the addition of feeds 1-3 was commenced. Feed 1 (400 g of isopropanol, 40 g of lauryl acrylate) was added within 5.5 h, feed 2 (300 g of isopropanol, 350 g of N-vinylpyrrolidone) within 6 h, and feed 3 (19 g of ε-butyl perpivalate 75%, 100 g of isopropanol) within 6.5 h. The mixture was polymerized further for another 2 h. Subsequently, the isopropanol was distilled off and the reaction mixture was subjected to a steam distillation. After distillation, the polymer solution was diluted with 200 g of water.

(17) This afforded a polymer with a K value of 14 and a molar mass M.sub.n of 4400 g/mol and M.sub.w of 7600 g/mol.

(18) The solubilizers S2 and S3 were prepared correspondingly: S2: 80 g of lauryl acrylate and feed 2 with 310 g of N-vinylpyrrolidone M.sub.n=2500 g/mol and M.sub.w=5000 g/mol, K value=12 S3: 120 g of lauryl acrylate and feed 2 with 270 g of N-vinylpyrrolidone M.sub.n=1300 g/mol and M.sub.w=2900 g/mol, K value=7

Example 2

Solubilizer S4 (VP/LA/sodium acrylate copolymer [78/20/2])

(19) The initial charge (19.13 g of feed 1) was sparged with nitrogen and heated to an internal reactor temperature of 80° C. Subsequently, the addition of feeds 1-4 was commenced. Feed 1 (400 g of isopropanol, 80 g of lauryl acrylate) was added within 5.5 h, feed 2 (300 g of isopropanol, 312 g of VP) and feed 3 (50 g of H.sub.2O, 21 g of 37.5% by weight solution of sodium acrylate) within 6 h, and feed 4 (100 g of isopropanol, 19 g of t-butyl perpivalate) within 6.5 h. The mixture was then polymerized further for 2 h. The isopropanol was distilled off and the reaction mixture was subjected to a steam distillation. After distillation, the polymer solution was diluted with 200 g of water.

(20) This afforded a polymer with a K value of 12 and a molar mass Mn=2300 g/mol.

(21) Solubilizer S5 was prepared correspondingly: S5 (VP/LA/NaA [70/20/10]) Copolymer

(22) Analogously to example 2, with 280 g of VP and 105 g of a 37.5% by weight sodium acrylate solution.

(23) This afforded a polymer with a K value of 12 and a molar mass Mn=2100 g/mol.

Example 3

Solubilizer S6 (VP/LA/AMPS-Na/NaA 76:20:2:2)

(24) The initial charge (250 g of isopropanol, 25 g of N-vinylpyrrolidone, 25 g of lauryl acrylate) was sparged with nitrogen and heated to an internal reactor temperature of 75° C. Then feed 1 (350 g of isopropanol, 165 g of N-vinylpyrrolidone, 25 g of lauryl acrylate), feed 2 (222 g of water, 28 g of AMPS sodium salt, pH7) and feed 3 (27 g of water, 13 g of sodium acrylate) were added within 3 h. Feed 4 (47.5 g of water, 2.5 g of 2,2′-azobis(2-methylpropionamidine) dihydrochloride [WAKO® V 50, Wako Chemicals]) was added within 4.5 h. After continued polymerization for 1 h, feed 5 (10 g of water, 0.65 g of 2,2′-azobis(2-methylpropionamidine) dihydrochloride [WAKO® V 50]) was added, and polymerization was continued for 2 h. The isopropanol was distilled off and the reaction mixture was subjected to a steam distillation.

(25) This afforded a polymer with a K value of 22 and a molar mass M.sub.n of 9700 g/mol and M.sub.W of 31 300 g/mol.

Example 4

Solubilizer S7 (Maleic Anhydride/Styrene (50/50) Copolymer Partly Esterified with C13 Fatty Alcohol Alkoxylate)

(26) The initial charge (100 g of MA/S copolymer [SMA® 100 F, Sartomer], 575 g of C.sub.13 fatty alcohol alkoxylate) was sparged with nitrogen and heated to an internal reactor temperature of 150° C. The reaction mixture was then stirred at this temperature for 4 h.

(27) This afforded a polymer with a K value of 12 and a molar mass Mn=2300 g/mol.

Example 5

Solubilizer S8 (Hyperbranched Polycarbonate Based on Diethyl Carbonate and the Reaction Product of Trimethylolpropane with a 15.7 Molar Excess of Propylene Oxide, Functionalized with Peg Chains (Degree of Functionalization 100%)).

(28) 5.1 Hyperbranched polycarbonate core with terminal hydroxyl groups 2298 g of TMP×15.7 PO, 284 g of diethyl carbonate and 2 g of DBTL catalyst were initially charged and heated to boiling. The boiling reaction mixture was stirred (approx. 14 h) until the boiling temperature of the reaction mixture had fallen as a result of the evaporative cooling of the ethanol released to a constant temperature of approx. 143° C. The reflux condenser was then replaced by a distillation apparatus and the ethanol formed in the reaction was distilled off, in the course of which the temperature of the reaction mixture was increased to 230° C. The ethanol was collected in a cooled round bottomed flask and weighed, and the conversion was thus determined as a percentage relative to the theoretically possible full conversion. After the attainment of a conversion of 89%, dry nitrogen was passed through the reaction mixture at a temperature of 160° C. for 1 hour, in order to remove residual amounts of monomers still present. Thereafter, the mixture was cooled to room temperature.

(29) The polymer formed (Mn=2400 g/mol; Mw=4600 g/mol; OH number: 87 mg KOH/g of polymer) was obtained in the form of a yellow, highly viscous liquid which was not water-soluble. 5.2 Hyperbranched polycarbonate core, functionalized with PEG chains (degree of functionalization 100%) 5.2.1 123.5 g of polyethylene glycol monomethyl ether (Mn=500 g/mol) were initially charged and freed of water residues at 80° C. under reduced pressure. After cooling to room temperature, the mixture was placed under nitrogen and the polymer was dissolved in 123.5 g of butyl acetate. 50.0 g of isophorone diisocyanate were then added and the mixture was heated to 50° C. Addition of 19 mg of zinc neodecanoate dissolved in 1 ml of butyl acetate started the reaction which was conducted at 50° C. over the course of 3.5 h down to an NCO content of 2.87%. Subsequently, the reaction was ended by cooling to −20° C. The reaction product was used directly in stage 5.2.2 without further workup. 5.2.2 30.1 g of the hydrophobic hyperbranched polycarbonate core from stage 5.1 was initially charged and admixed under nitrogen with 71.0 g of the reaction mixture 5.2.1. The mixture was then heated to 80° C. and the reaction was started by adding 7 mg of DBTL dissolved in 1 ml of butyl acetate. After the complete conversion of all NCO groups (NCO content 0%), the mixture was cooled and the solvent was removed under reduced pressure. Finally, the solubilizer S8 (Mn=5070 g/mol) was obtained in the form of a yellow, highly viscous liquid which was completely water-soluble.

Example 6

Solubilizer S9 (Hyperbranched Polycarbonate Based on Diethyl Carbonate and the Reaction Product of Trimethylolpropane with a 15.7 Molar Excess of Propylene Oxide, Functionalized with a Comb-Type PVP-co-PLauryl Acrylate-co-PEGMEMA Copolymer (Degree of Functionalization 50%)).

(30) 6.1 Hyperbranched polycarbonate core with terminal hydroxyl groups 1149 g of the trifunctional alcohol TMP×15.7 PO, 144 g of diethyl carbonate and 1 g of DBTL catalyst were reacted as in synthesis example 5.1. The polymer formed (Mn=4200 g/mol; Mw=14 500 g/mol; OH number: 85 mg KOH/g of polymer) was obtained in the form of a yellow, highly viscous liquid which was not water-soluble. 6.2 Hyperbranched polycarbonate core functionalized with a comb-type PVP-co-PLauryl acrylate-co-PEGMEMA copolymer (degree of functionalization 50%) 6.2.1 100.0 g of THF were initially charged under nitrogen and then heated under reflux. Within 3 h, a mixture 1 of 155.9 g of lauryl acrylate, 144.2 g of N-vinylpyrrolidone and 163.3 g of PEGMEMA 475, dissolved in 200.0 g of THF, and simultaneously, within 4 h, a mixture 2 of 8.8 g of AIBN and 27.8 g of mercaptoethanol, dissolved in 200.0 g of THF, were added slowly to the mixture with the aid of two metering pumps. After addition of mixture 2 had ended, the reaction mixture was heated under reflux for a further 18 h. Subsequent monitoring of the residual monomers by means of GC showed a content of lauryl acrylate of <1%, and so the mixture was cooled and the product (Mn=1000 g/mol) was directly used further in stage 2. 6.2.2 278.4 g of reaction mixture 6.2.1 were initially charged and freed of the THF solvent under reduced pressure. After cooling to room temperature, the mixture was placed under nitrogen and the residue was dissolved in 140.0 g of butyl acetate. Then 20.0 g of isophorone diisocyanate were added and the mixture was heated to 50° C. Addition of 21 mg of zinc neodecanoate dissolved in 1 ml of butyl acetate started the reaction which was conducted at 60° C. over the course of 6 h and at room temperature for a total of 16 h down to an NCO content of 1.16%. The reaction was ended by cooling to −20° C. The reaction product was used directly in stage 3 without further workup. 6.2.3 6.0 g of the hydrophobic hyperbranched polycarbonate core 6.1 were initially charged and dissolved in 6.0 g of butyl acetate under nitrogen. The mixture was then admixed with 19.2 g of reaction mixture 6.2.2 and heated to 80° C., and the reaction was started by adding 13 mg of DBTL dissolved in 1 ml of butyl acetate. On completion of conversion of all NCO groups (NCO content 0%), the mixture was cooled and the solvent was removed under reduced pressure. Finally, the solubilizer S9 (Mn=8110 g/mol) was obtained in the form of a yellow, highly viscous liquid which was completely water-soluble.

Example 7

Solubilizer S10 (Hyperbranched Polycarbonate Core Based on Diethyl Carbonate and the Reaction Product of Trimethylolpropane with a 15.7 Molar Excess of Propylene Oxide, Functionalized with PEG-b-Polycaprolactone Block Copolymer (Degree of Functionalization 100%)).

(31) 7.1 Hyperbranched polycarbonate core with terminal hydroxyl groups 1149 g of the trifunctional alcohol TMP×15.7 PO, 144 g of diethyl carbonate and 1 g of DBTL catalyst were converted as in synthesis example 2. The polymer formed (Mn=4200 g/mol; Mw=14 500 g/mol; OH number: 85 mg KOH/g of polymer) was obtained in the form of a yellow, highly viscous liquid which was not water-soluble. 7.2 Hyperbranched polycarbonate core functionalized with PEG-b-polycaprolactone block copolymer (degree of functionalization 100%) 7.2.1 150.0 g of polyethylene glycol monomethyl ether (Mn=500 g/mol) were initially charged and freed of water residues at 90° C. under reduced pressure. After cooling to room temperature, the mixture was placed under nitrogen and the polymer was admixed with 205.0 g of ε-caprolactone. The mixture was heated to 90° C. and the ring-opening polymerization of the caprolactone was started by adding 355 mg of butyltin tris(2-ethylhexanoate). The mixture was heated at 90° C. for a further 18 h and, after the reaction had ended, cooled to room temperature. The OH-terminated block copolymer thus obtained (Mn=1180 g/mol) was used directly in stage 2 without further purification. 7.2.2 200.0 g of block copolymer 7.2.1 were initially charged, placed under nitrogen and admixed with 34.1 g of isophorone diisocyanate. The mixture was heated to 50° C. Addition of 30 mg of zinc neodecanoate dissolved in 1 ml of butyl acetate started the reaction which was conducted at 50° C. over the course of 4 h down to an NCO content of 2.23%. Subsequently, the reaction was ended by cooling to −20° C. The reaction product was used directly in stage 7.2.3 without further workup. 7.2.3 7.0 g of the hydrophobic hyperbranched polycarbonate core 7.1 were initially charged and dissolved in 10.0 g of butyl acetate under nitrogen. The mixture was then admixed with 20.0 g of reaction mixture 7.2.2 and heated to 80° C., and the reaction was started by adding 27 mg of DBTL dissolved in 1 ml of butyl acetate. On completion of conversion of all NCO groups (NCO content 0%), the mixture was cooled and the solvent was removed under reduced pressure. Finally, the solubilizer S10 (Mn=13 190 g/mol) was obtained in the form of a yellow, highly viscous liquid which was completely water-soluble.

Application Examples

Example 8

Solubilization of Fipronil (Technical Grade Active Ingredient, Purity 89.8%) with Commercial Adjuvants and Solubilizers Used in Accordance with the Invention

(32) TABLE-US-00002 Adjuvant Fipronil solubility Adjuvant conc. in % in ppm None 0 2.2 Soprophor 4D384 1.0 5.9 GK 2303/012 1.0 11 Break Thru S 240 1.0 10 Triton X-100 1.0 13 Silwet L77 1.0 52.3 Wettol LF 700 1.0 10 Lutensol ON 70 1.0 63.2 Rhodapex CD-128 1.0 11.3 Plurafac LF 901 1.0 78.3 Solubilizer Fipronil solubility Solubilizer conc. in % in ppm S5 VP:lauryl acrylate:sodium 1.0 156.8 acrylate 70:20:10 (% weight) S4 VP:lauryl acrylate:sodium 1.0 189.2 acrylate 78:20:2 (% weight) S1 VP:lauryl acrylate 1.0 119.6 90:10 (% weight) S2 VP:lauryl acrylate 1.0 197.7 80:20 (% weight) S3 VP:lauryl acrylate 1.0 189.4 70:30 (% weight) S6 MSA/styrene/Plurafac 1.0 143.2 LF 401 S7 VP/LA/AMPS-Na/Na 1.0 115.8 acrylate 76:20:2:2 (% weight) S9 1.0 179

(33) The fipronil concentration was determined by means of UV spectroscopy at 278 nm; to this end, the absorption of the polymer (1% by weight in water) was first determined alone. Subsequently, an excess of fipronil was added and the mixture was stirred at room temperature overnight. The centrifuged solution was analyzed once again at 278 nm in the UV instrument. After subtracting the appropriate solubilizer spectrum and comparing by means of a fipronil calibration curve produced beforehand, it was possible to determine the concentration of dissolved fipronil.

(34) Test Setup

(35) A glass column composed of six segments with a length of 27.5 cm, a diameter of 5 cm and a surface (a cross section) of 19.6 cm.sup.2 was, with the aid of a vibrator, filled with soil (LUFA 2.3 (sandy Loam) [USDA], pH 7.2, air-dried, TOC 1%, density 1.24 g/cm.sup.3, max WHC 28.9 g/100 g).

(36) Inventive and comparative formulations were applied to this column (60 ml, comprising 37.5 mg of fipronil (625 ppm) with or without appropriate amounts of solubilizer). After application, a further 40 ml of water were applied.

(37) HPLC-MSD was used to measure how much in % of the amount of fipronil originally applied (625 ppm, 37.5 mg) was present in the segments of the column (0-2.5 cm, 2.5-7.5 cm, 7.5-12.5 cm, 12.5-17.5 cm and 17.5-22.5 cm).

(38) The soil mobility relative to the Termidor SC commercial product was calculated by the following method:
Soil mobility=(fipronil content [%] in segment 1)×2.5+(fipronil content [%] in segment 2)×7.5+(fipronil content [%] in segment 3)×12.5+ . . . +(fipronil content [%] in segment 6)×27.5/(fipronil content [%] in segment 1 Termidor SC)×2.5+(fipronil content [%] in segment 2 Termidor SC)×7.5+(fipronil content [%] in segment 3 Termidor SC)×12.5+ . . . +(fipronil content [%] in segment 6 Termidor SC)×27.5)
Tankmix Formulations (Table 1)

(39) An appropriate amount of fipronil (as Termidor® SC) was added to an aqueous solution of polymer with or without adjuvants, such that the concentration of fipronil was 625 ppm. 60 ml of each solution obtained were applied to the column described.

(40) The soil mobility was calculated as described above—the reference used was again Termidor SC:

(41) TABLE-US-00003 TABLE 1 Tankmix tests Fipronil Soil Soil Soil Soil Soil Soil (625 ppm) depth depth depth depth depth depth Mobility Ex Polymer and (cm) (cm) (cm) (cm) (cm) (cm) relative to No. concentration solubilizer Adjuvant Conc. 0-2.5 2.5-7.5 7.5-12.5 12.5-17.5 17.5-22.5 22.5-27.5 Termidor SC V1 — — — 83 17 0 0 0 0 100 V2 300 ppm S1 — 94 5 1 0 0 0  84  9 625 ppm S3 — 65 30 5 0 0 0 133 10 625 ppm S8 — 72 25 3 0 0 0 120 11 625 ppm S2 — 66 27 6 1 0 0 136 12 0.19% S8 Soprophor 4D384 0.062%  37 41 18 4 0 0 .sup. 125 * 13 0.50% S2 — 53 40 7 0 0 0 154 14 1.00% S2 — 38 53 9 0 0 0 179 15 3.00% S2 — 24 47 25 2 1 1 240 16 1.00% S2 Soprophor 4D384 0.50%  33 46 17 3 1 0.4 215 17 1.00% S2 Soprophor 4D384 .sup. 1% 49 33 11 7 1 0.4 197 18 1.00% S2 Break Thru S240 .sup. 2% 30 44 20 4 1 0.9 229 19 1.00% S2 Soprophor 4D384 1.0% + 1.0% 63 25 7 4 1 0 156 and Break Thru S240 V3 — — Soprophor 4D384 625 ppm 80 20 0 0 0 0 104 V4 — — Soprophor 4D384 0.2% 77 23 0 0 0 0 108 V5 — — Soprophor 4D384 0.5% 73 24 3 0 0 0 119 V6 — — Soprophor 4D384 .sup. 1.5 + 1.5% 33 45 19 3 0 0 210 and Break Thru S240 V7 — — Break Thru S240 3 43 44 11 2 0 0 181 20 3 S2 Soprophor 4D384 .sup. 0.5 39 42 16 3 0 0 197 21 3 S2 Soprophor 4D384 2 17 42 23 16 2 0 287 22 3 S2 Soprophor 4D384 3 17 33 27 19 3 1 313 23 .sup. 0.5 S2 Soprophor 4D384 3 25 51 15 7 2 0 237 24 .sup. 0.5 S2 Break Thru S240 3 36 53 10 1 0 0 187 * based on a different standard

(42) TABLE-US-00004 TABLE 1a Tankmix tests Soil Soil Soil Soil Soil Soil Fipronil depth depth depth depth depth depth Mobility Ex Polymer (1250 ppm) (cm) (cm) (cm) (cm) (cm) (cm) relative to No. concentration solubilizer Adjuvant Conc. 0-2.5 2.5-7.5 7.5-12.5 12.5-17.5 17.5-22.5 22.5-27.5 Termidor SC 12a 0.19% S8 Soprophor 0.062 22 40 28 10 0 0 159 * 4D384 * based on a different standard

(43) TABLE-US-00005 TABLE 2 Examples 25-35 Soil mobility studies of formulation concentrates Active % found in segments between . . . cm Rel. ingredient Ex. 0- 2.5- 7.5- 12.5- 17.5- 22.5- mobility content Composition of the formulation No. 2.5 7.5 12.5 17.5 22.5 27.5 % (fipronil) (without active ingredient) V8 34 51 15 0 0 0 194 96 g/l Soprophor BSU 200 g/l + Soprophor 4D384 300 g/l + DMSO 300 g/l + γ-butyrolactone ad 1l (system without solubilizer) DC type 25 29 47 23 1 0 0 216 50 g/l S2 200 g/l + Soprophor 4D384 300 g/l + DMSO 300 g/l + γ-butyrolactone ad 1l DC type 26 18 40 35 6 0 0 263 50 g/l S8 200 g/l + Soprophor 4D384 300 g/l + DMSO 300 g/l + γ-butyrolactone ad 1l SL type 27 13 37 41 9 0 0 290 50 g/l S8 400 g/l + Soprophor 4D384 200 g/l + DMSO 250 g/l + γ-butyrolactone ad 1l SL type 28 20 49 30 0.26 0 0 236 96 g/l S8 400 g/l + Soprophor 4D384 200 g/l DMSO 250 g/l + γ-butyrolactone ad 1l DC type 29 22 55 24 0 0 0 227 96 g/l S8 400 g/l + Soprophor 4D384 300 g/l + DMSO 200 g/l + γ-butyrolactone ad 1l DC type 30 14 38 38 10 0 0 287 50 g/l S9 400 g/l + Soprophor 4D384 300 g/l + DMSO 200 g/l + γ-butyrolactone ad 1l SL type 31 19 40 39 2 0 0 258 96 g/l S9 400 g/l + Soprophor 4D384 300 g/l + DMSO 200 g/l + γ-butyrolactone ad 1l DC type 32 20 43 35 1 0 0 245 96 g/l S9 200 g/l + Soprophor 4D384 300 g/l + DMSO 300 g/l + γ-butyrolactone ad 1l DC type 33 20 43 36 1 0 0 249 96 g/l S9 300 g/l + Soprophor 4D384 300 g/l + DMSO 250 g/l + γ-butyrolactone ad 1l DC type 34 61 33 6 1 0 0 146 96 g/l S8 200 g/l + Soprophor 4D384 0 g/l + DMSO 250 g/l + γ-butyrolactone ad 1l DC type 35 47 41 9 3 0 0 175 96 g/l S8 400 g/l + Soprophor 4D384 0 g/l + DMSO 250 g/l + γ-butyrolactone ad 1l SL type V9 66 34 10 0 0 0 161 96 g/l Soprophor 4D384 400 g/l + DMSO 250 g/l + γ-butyrolactone ad 1l DC type 36 14 40 31 15 0 0  176* 96 g/l S8 250 g/l + Suprophor 4D384 60 g/l SC type 37 12 37 37 14 0 0  182* 96/l S8 220 g/l + Soprophor 4D384 80 g/l SC type *based on a different standard

(44) TABLE-US-00006 TABLE 2a Examples 38-39 Soil mobility (1250 ppm Fipronil applied) Active % found in segments between . . . cm Rel. ingredient Ex. 0- 2.5- 7.5- 12.5- 17.5- 22.5- mobility content Composition of the formulation No. 2.5 7.5 12.5 17.5 22.5 27.5 % (fipronil) (without active ingredient) 38 10 29 32 27 2 0 208* 96 g/l* S8 250 g/l + Suprophor 4D384 60 g/l SC type 39 10 28 31 30 1 0 211* 96 g/l  S8 220 g/l + Soprophor 4D384 80 g/l SC type *based on a different standard

(45) TABLE-US-00007 TABLE 3 Examples 40-42 Soil mobilitystudies of SC concentrates with Li 10 soil Active % found in segments between . . . cm Rel. ingredient Ex. 0- 2.5- 7.5- 12.5- 17.5- 22.5- mobility content Composition of the formulation No. 2.5 7.5 12.5 17.5 22.5 27.5 % (fipronil) (without active ingredient) 40 3 11 18 21 26 20 161 96 g/l SC formulation 41 4 12 15 20 28 22 163 96 g/l SC formulation 42 4 11 17 22 23 23 162 96 g/l SC formulation V10 17 31 23 15 9 5 103 96 g/l Termidor SC V11 16 35 23 15 8 3 98 96 g/l Termidor SC V12 16 35 22 15 8 5 100 96 g/l Termidor SC (Clay 6%, silt 13%, sand 81%, org. L 0.9%, pH 5.9 [CaCl.sub.2], max WHC: 24.2 g/100 g) (625 ppm of Fipronil applied) SC-formulation of example 39

(46) The examples demonstrate that addition of inventive solubilizers, especially in concentrations greater than the active ingredient concentration, causes a significant increase in the soil mobility, which can be improved a little further by adjuvants. The improved soil mobility occurs both in tankmix systems (Ex. 9-24) and in ready-to-use formulations (Ex. 25-35) which comprise an inventive polymeric solubilizer.