AGROFORMULATION COMPRISING COPOLYMERS CONTAINING HYDROXYBUTYL VINYL ETHER AS ASSOCIATIVE THICKENER

Abstract

Provided herein is an agrochemical composition comprising a pesticide and at least one water-soluble copolymer (P) including at least one monomer (A), selected from the group consisting of (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide or N-methylol(meth)acrylamide; at least one macromonomer (B), at least including a macromonomer (B1)

H.sub.2CC(R.sup.1)R.sup.2O(R.sup.3O).sub.a(R.sup.4O).sub.b[(R.sup.4O).sub.c(R.sup.5O).sub.d]H; and(B1)

at least one anionic monoethylenically unsaturated monomer (C), including at least one acidic group selected from COOH, SO.sub.3H, PO.sub.3H.sub.2, and salts thereof.

Further provided herein is the production of a spray mixture, including the contacting of a pesticide, the water-soluble copolymer (P), and water; and also a method for controlling phytopathogenic fungi, unwanted plant growth, unwanted insect infestation or mite infestation, and/or for regulating plant growth. The agrochemical composition acts on a pest, its environment, a crop plant to be protected from the pest, on the soil, the unwanted plant, the crop plant, and/or its environment.

Claims

1. An agrochemical composition comprising a pesticide and at least one water-soluble copolymer (P), wherein the copolymer (P) at least comprises: 30 to 99.99 wt % of at least one monomer (A), selected from the group consisting of: (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide and N-methylol(meth)acrylamide; 0.01 to 15 wt % of at least one macromonomer (B), macromonomer (B) at least comprising a macromonomer (B1) comprising H.sub.2CC(R.sup.1)R.sup.2O(R.sup.3O).sub.a(R.sup.4O).sub.bH; and 0.1 to 69.99 wt % of at least one anionic monoethylenically unsaturated monomer (C), comprising at least one acidic group selected from the group consisting of: COOH, SO.sub.3H, PO.sub.3H.sub.2, and salts thereof; wherein: R.sup.1 comprises one of H and methyl, R.sup.2 comprises one of a single bond and a divalent linking group OR.sup.35, wherein R.sup.35 is an alkylene group having 1 to 6 carbon atoms, R.sup.3 comprises, independently at each occurrence, one of ethylene groups CH.sub.2CH.sub.2, 1,2-propylene groups CH.sub.2CH(CH.sub.3), and alkylene groups R.sup.4, wherein at least 90 mol % of the radicals R.sup.3 are ethylene groups, R.sup.4 comprises, independently at each occurrence, alkylene groups CR.sup.6(R.sup.7)CR.sup.8(R.sup.9), wherein the radicals R.sup.6, R.sup.7, R.sup.8 and R.sup.9 independently of one another are one of H, a linear branched alkyl radical having 1 to 8 carbon atoms, and a branched alkyl radical having 1 to 8 carbon atoms, wherein not all the radicals are H and the sum of the carbon atoms in the radicals R.sup.6, R.sup.7, R.sup.8 and R.sup.9 is 2 to 8, R.sup.5 comprises an ethylene group CH.sub.2CH.sub.2, a is a number from 10 to 150, b is a number from 5 to 30, c is a number from 0 to 2, d is a number from 0 to 20, and wherein the respective amounts of the monomers are based in each case on a total amount of all the monomers in the copolymer (P).

2. The agrochemical composition according to claim 1, wherein d is a number from 1 to 15.

3. The agrochemical composition according to claim 2, wherein the copolymer (P) comprises at least one additional macromonomer (B2) comprising H.sub.2CC(R.sup.1)R.sup.2O(R.sup.3O).sub.a(R.sup.4O).sub.bH, wherein a molar fraction x of the macromonomers (B1) relative to a sum of (B1) and (B2) is 0.1 to 0.99.

4. The agrochemical composition according to claim 1, wherein R.sup.1 is H, R.sup.2 is OR.sup.35, and R.sup.3 is CH.sub.2CH.sub.2.

5. The agrochemical composition according to claim 1, wherein a is a number from 20 to 28, b is a number from 8 to 20, and d is a number from 2 to 5.

6. The agrochemical composition according to claim 1, wherein one of 2 and 3 of R.sup.6, R.sup.7, R.sup.8 and R.sup.9 are H, and a sum of the carbon atoms in R.sup.6, R.sup.7, R.sup.8 and R.sup.9 is one of 2 and 3.

7. The agrochemical composition according to claim 1, wherein a sum of b and c in R.sup.4O is selected such that a sum of all the carbon atoms of all of R.sup.6, R.sup.7, R.sup.8 and R.sup.9 present is 25 to 50.

8. The agrochemical composition according to claim 1, wherein the copolymer (P) comprises at least two different monomers (C).

9. The agrochemical composition according to claim 1, wherein the copolymer (P) comprises at least one monomer (C) of the formula (I)
CH.sub.2CH.sub.2C(O)XR.sup.10SO.sub.3H(I), wherein: X is one of N and O; and R.sup.10 comprises one of CH.sub.2, CH.sub.2CH.sub.2, C(CH.sub.3).sub.2, CHCH.sub.3, CH(CH.sub.3)CH.sub.2, CH.sub.2CH(CH.sub.3), and C(CH.sub.3).sub.2CH.sub.2, CH.sub.2C(CH.sub.3).sub.2.

10. The agrochemical composition according to any claim 1, wherein the copolymer (P) comprises at least one monomer (C) having a COOH group.

11. The agrochemical composition according to claim 1, wherein the copolymer (P) has a weight-average molecular weight of at least 1,000,000 g/mol.

12. The agrochemical composition according to claim 1, wherein the copolymer (P) has a weight-average molecular weight of 100,000 to 600,000 g/mol.

13. The agrochemical composition according to claim 1, further comprising at least one nonionic surfactant.

14. The agrochemical composition according to claim 13, wherein the nonionic surfactant is one of an alcohol alkoxylate and a polyalkylene oxide.

15. A method for producing a spray mixture, the method comprising combining a pesticide, a water-soluble copolymer (P), as defined in claim 1, and water.

16. A method for controlling at least one of phytopathogenic fungi, unwanted plant growth, unwanted insect infestation, and mite infestation and for regulating plant growth, the method comprising applying the agrochemical composition defined in claim 1 on at least one of a pest, its environment, a crop plant to be protected from the pest, on soil, an unwanted plant, and an environment of the unwanted plant.

17. The agrochemical composition according to claim 10, wherein the COOH group is (meth)acrylic acid.

Description

EXAMPLES

[0187] Polymer A: 48 wt % 2-acrylamido-2-methylpropanesulfonate; 50 wt % acrylamide; 2 wt % hydroxybutyl vinyl ether alkoxylated with 20-30 ethylene oxide units, 10-20 butylene oxide units, and 1-10 ethylene oxide units; Mw>1 000 000 g/mol.

[0188] Polymer B: 45 wt % 2-acrylamido-2-methylpropanesulfonate; 50 wt % acrylamide; 5 wt % hydroxybutyl vinyl ether alkoxylated with 20-30 ethylene oxide units, 10-20 butylene oxide units, and 1-10 ethylene oxide units; Mw>1 000 000 g/mol.

[0189] Polymer C: 40 wt % 2-acrylamido-2-methylpropanesulfonate; 50 wt % acrylamide; 10 wt % hydroxybutyl vinyl ether alkoxylated with 20-30 ethylene oxide units, 10-20 butylene oxide units, and 1-10 ethylene oxide units; Mw>1 000 000 g/mol.

[0190] Comparative polymer D: 50 wt % 2-acrylamido-2-methylpropanesulfonate, 50 wt % acrylamide; Mw>1 000 000 g/mol.

[0191] Polymer E: 40 wt % 2-acrylamido-2-methylpropanesulfonate; 50 wt % acrylamide; 10 wt % hydroxybutyl vinyl ether alkoxylated with 20-30 ethylene oxide units, 10-20 butylene oxide units, and 1-10 ethylene oxide units; Mw 100 000-500 000 g/mol.

[0192] Comparative polymer F: 50 wt % 2-acrylamido-2-methylpropanesulfonate, 50 wt % acrylamide; Mw>100 000-500 000 g/mol.

[0193] Polymer H: 48 wt % 2-acrylamido-2-methylpropanesulfonate; 45 wt % acrylamide; 5 wt % N-vinylpyrrolindone; 2 wt % hydroxybutyl vinyl ether alkoxylated with 20-30 ethylene oxide units, 10-20 butylene oxide units, and 1-10 ethylene oxide units; Mw>1 000 000 g/mol.

[0194] Surfactant A: nonionic C.sub.10-C.sub.15 alcohol ethoxylate, dynamic viscosity 75 mPas, miscible with water in any proportion.

[0195] Surfactant B: nonionic alkoxylate, containing polyethylene oxide and polypropylene oxide as block copolymer, M.sub.w 800 to 1100 g/mol.

[0196] Surfactant C: ethoxylated tallowamine; degree of ethoxylation 15-25 EO units per molecule.

[0197] Surfactant D: nonionic condensation product containing polyethylene oxide and polypropylene oxide as block copolymer; molar weight about 6500 g/mol; 50 wt % fraction of polymerized ethylene oxide.

[0198] Surfactant E: mixture of polyamine phosphate, naphtha, and polyoxyethylene fatty ammonium methosulfate, liquid at 25 C.

[0199] Solvent A: hydrocarbon mixture containing at least 99 wt % of aromatic hydrocarbons; naphthalene concentration less than 0.9 wt %.

[0200] Wetting agent A: benzenesulfonic acid-formaldehyde-phenol-urea condensate; sodium salt. Hyperbranched polymer: polymer of polytetrahydrofuran and citric monohydrate, modified with isophorone diisocyanate, methylpolyethylene glycol, and C.sub.16-C.sub.18 fatty alcohol polyethylene glycol, as disclosed in synthesis example 8 in PCT/EP2015/079344.

[0201] Filler A: magnesium aluminum silicate; smectite.

[0202] Thickener A: xanthan.

[0203] Biocide: mixture of 2.5 wt % 1,2-benzisothiazolin-3-one and 2.5 wt % 2-methyl-4-isothiazolin-3-one.

[0204] Defoamer: nonionic silicone oil, pH 5-8.

[0205] Fungicide A: 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol.

[0206] Herbicide A: dimethenamid-P.

[0207] Preparation of the polymers: the inventive and comparative polymers A to D and H in the experiments were prepared by gel polymerization as described above, in analogy to the published preparation process in examples 2 to 8 in WO 2010/133527.

[0208] The inventive and comparative polymers E and F were prepared by solution polymerization as described above.

[0209] Preparation of the monomers: the alkoxylated hydroxybutyl vinyl ethers used in the inventive and comparative polymers in the experiments were prepared by the preparation protocol described in the experimental section for preparing the macromonomers (B) in PCT/EP2014/076772.

Example-1: Reduction of the Fraction of Fine Droplets by High Molecular Mass Polymers

[0210] Four different aqueous solutions S1, S2, S3 and S4 each containing only one of the polymers A, B, C or comparative polymer D in that order were produced with a concentration of 50 ppm. The solutions were sprayed through an XR nozzle (XR-11004, Teejet) at a pressure of 2.78 bar. The fraction of fine droplets having a diameter of less than 100 m was measured by laser scattering, with detection by means of a CCD detector. The results have been set out in table 1.

TABLE-US-00001 TABLE 1 Water S1 S2 S3 S4* Fraction of fine 16.5 12.5 11.8 11 14.5 droplets in % *comparative experiment

Example-2: Reduction of the Fraction of Fine Droplets by Low Molecular Mass Polymers

[0211] Two different aqueous solutions S5 and S6 each containing only one of the polymers E or comparative polymer F in that order were prepared with a concentration of 50 ppm. The reduction in the fraction of fine droplets during spraying was carried out as in example 1. The results have been set out in table 2.

TABLE-US-00002 TABLE 2 Water S5 S6* Fraction of fine 16.5 14 16 droplets in % *comparative experiment

Example-3: Variation in the Alkoxylation Pattern of Copolymer (P)

[0212] Polymers G1 to G9 were prepared by gel polymerization. All contained 48 wt % of 2-acrylamido-2-methylpropanesulfonate, 50 wt % of acrylamide and 2 wt % of hydroxybutyl vinyl ether and had a weight-average molecular weight of 100 000 to 500 000 g/mol. The alkoxylation of the hydroxybutyl vinyl ether was altered in accordance with table 3, with the indices a, b and d corresponding to those in formula I and indicating the number of the ethylene oxide, butylene oxide and ethylene oxide units in that order.

[0213] The polymers were dissolved in water at a concentration of 50 ppm, and the droplet size during spraying was measured as in example-1. The results are set out in table 4, with all of the measurements having been standardized to water.

TABLE-US-00003 TABLE 3 Polymer Index a Index b Index d G1 24.5 16 0 G2 24.5 5 3.5 G3 24.5 16 10 G4 24.5 10 3.5 G5 24.5 16 3.5 G6 24.5 16 16 G7 12 16 16 G8 125 16 3.5 G9 24.5 22 3.5

TABLE-US-00004 TABLE 4 Investigation of solutions of polymers G1 to G9 Water G1 G2 G3 G4 G5 Standardized 100 68 70 71 65 72 fraction of fine droplets in % G6 G7 G8 G9 Standardized 69 70 58 62 fraction of fine droplets in %

Example-4: Concentration Dependence of the Reduction in the Fraction of Fine Droplets

[0214] Aqueous solutions S7 to S9 of polymer A with concentrations corresponding to table 5 were prepared.

TABLE-US-00005 TABLE 5 S7 S8 S9 Concentration of 50 70 90 polymer A in ppm

[0215] The reduction in the fraction of fine droplets during spraying was carried out as in example 1. The results have been set out in table 6.

TABLE-US-00006 TABLE 6 Water S7 S8 S9 Fraction of fine 15.3 14 12 10 droplets in %

Example-5: Cooperative Effect of Copolymer (P) and Nonionic Surfactants

[0216] An aqueous solution S10 of polymer E at a concentration of 50 ppm was admixed with different concentrations of surfactant A, and the reduction in the fraction of fine droplets during spraying was carried out as in example 1. The results have been set out in table 7.

TABLE-US-00007 TABLE 7 Concentration of surfactant A in wt % 0 1 2.5 5 10 Fraction of fine 14.8 9.5 9 10 11.5 droplets in %

Example-6: Cooperative Effect of Copolymer (P) and Nonionic Surfactants

[0217] An aqueous solution S11 of polymer A at a concentration of 50 ppm, containing 2000 ppm of surfactant B, was prepared and the reduction in the fraction of fine droplets during spraying was carried out as in example 1. The results have been set out in table 8.

TABLE-US-00008 TABLE 8 Water S11 Fraction of fine 17 14 droplets in %

Example-7: Reduction in the Fraction of Fine Droplets in SL Formulations

[0218] The aqueous solution formations SL-1 and SL-2 containing glyphosate, dicamba-BAPMA, surfactant C and polymer B or polymer C, and also the comparative formulation SL-1* without polymer, were prepared in accordance with the concentrations in table 9.

TABLE-US-00009 TABLE 9 Ingredient SL-1 SL-2 SL-1* Glyphosate in g/l 11.2 11.2 11.2 Dicamba-BAPMA 5.6 5.6 5.6 in g/l Polymer A in ppm 50 Polymer B in ppm 50 Surfactant C in g/l 3 3 3

[0219] The reduction in the fraction of fine droplets during spraying was carried out as in example 1. The results have been set out in table 10.

TABLE-US-00010 TABLE 10 SL-1 SL-2 SL-1* Fraction of fine 3 4 9 droplets in %

Example-8: Concentration Dependence of the Reduction in the Fraction of Fine Droplets in SL Formulations

[0220] The aqueous solution formulations SL-3, SL-4 and SL-5, containing glyphosate, dicamba-BAPMA and polymer A, and also the comparative formulation SL-2*without polymer, were prepared in accordance with the concentrations in table 11.

TABLE-US-00011 TABLE 11 Ingredient SL-3 SL-4 SL-5 SL-2* Glyphosate in g/l 11.2 11.2 11.2 11.2 Dicamba-BAPMA in g/l 5.6 5.6 5.6 5.6 Polymer A in ppm 50 70 90

[0221] The reduction in the fraction of fine droplets during spraying was carried out as in example 1. The results have been set out in table 10.

TABLE-US-00012 TABLE 12 SL-3 SL-4 SL-5 SL-2* Fraction of fine 6 3.8 2.1 8.3 droplets in %

Example-9: Concentration Dependence of the Reduction in the Fraction of Fine Droplets in Pesticide Suspensions

[0222] The aqueous suspensions SP-1 to SP-7, and also the comparative suspension concentrate SP-1* without the polymer of the invention, were produced with the ingredients corresponding to table 13. For this purpose, water, fungicide A, surfactant D, hyperbranched polymer and defoamer were mixed. The mixture was ground with a ball mill to a particle size of 2 m. Propylene glycol, biocide and thickener A were added. Mixing gave homogeneous suspensions. These suspensions were admixed with water and polymer A to give the suspensions SP-1 to SP-7 and SP-1*. Table 13 showed the final concentrations of the ingredients.

TABLE-US-00013 TABLE 13 Ingredient SP-1 SP-2 SP-3 SP-4 SP-5 SP-6 SP-7 SP-1* Fungicide A 0.375 0.375 0.375 0.375 0.375 0.375 0.375 0.375 in g/l Polymer A 35 17.5 8.75 4.5 2.2 1.1 0.5 in ppm Propylene 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 glycol in g/l Surfactant D 45 45 45 45 45 45 45 45 in ppm Hyperbranched 1 1 1 1 1 1 1 1 polymer in g/l Filler A 75 75 75 75 75 75 75 75 in ppm Thickener A 10 10 10 10 10 10 10 10 in ppm Biocide in 2 2 2 2 2 2 2 2 g/l Defoamer in 25 25 25 25 25 25 25 25 ppm Water to to to to to to to to 1 liter 1 liter 1 liter 1 liter 1 liter 1 liter 1 liter 1 liter *comparative experiment

[0223] The reduction in the fraction of fine droplets during spraying was carried out as in example 1, but a pressure of 4 bar was applied when spraying. The results have been set out in table 14.

TABLE-US-00014 TABLE 15 SP-1 SP-2 SP-3 SP-4 SP-5 SP-6 Fraction of 1.32 1.32 1.67 2.60 2.68 3.02 fine droplets in % SP-7 SP-1* Fraction of 3.13 3.33 fine droplets in % *comparative experiment

Example-10: Concentration Dependence of the Reduction in the Fraction of Fine Droplets in Emulsions

[0224] The aqueous emulsifiable concentrate EC-1 was prepared with the ingredients corresponding to table 16.

TABLE-US-00015 TABLE 16 Ingredient Herbicide A Surfactant E Solvent A Concentration in g/l 720 113 to 1 liter

[0225] Thereafter, EC-1 was diluted with 30 liters of water and polymer A was added up to a concentration of 233 ppm. The resulting spray mixture SB-8 was sprayed under a pressure of 4 bar through an ID nozzle (air injection nozzle ID). The fraction of fine droplets was otherwise determined as described in example 1. The results have been set out in table 17 in comparison with water.

TABLE-US-00016 TABLE 17 SB-8 Water Fraction of fine droplets in % 1.48 4.3

Example-11: Reduction in the Fraction of Fine Droplets in the Presence of Further Monomers

[0226] An aqueous solution S12 of polymer H with a concentration of 50 ppm was prepared, and the reduction in the fraction of the fine droplets during spraying was carried out as in example 1 in comparison with water, or in comparison with the aqueous solution S1 from example 1. The results have been set out in table 18.

TABLE-US-00017 TABLE 18 S1 S12 Water Standardized fraction of fine 77 69 100 droplets in %