AGROCHEMICAL FORMULATIONS

Abstract

Agrochemical composition comprising A) at least one pesticide A, B) at least one nonaqueous solvent S, C) a polymer P comprising units represented by formulae (I) and (II): Polymer P being a random polymer with respect to units (I) and (II); wherein Z (II) is a polymeric group comprising at least one type of vinyl monomer in polymerized form, where Z comprises as vinyl monomers at least one vinyl ester and optionally at least one N-vinyl lactam monomer; wherein said pesticide A and polymer P are completely dissolved in said solvent S at 20° C.

Claims

1. An agrochemical composition comprising A) at least one pesticide A, B) at least one nonaqueous solvent S, C) a polymer P comprising units represented by formulae (I) and (II): ##STR00006## polymer P being a random polymer with respect to units (I) and (II); wherein Z is a polymeric group comprising at least one type of vinyl monomer in polymerized form, where Z comprises as vinyl monomers at least one vinyl ester and optionally at least one N-vinyl lactam monomer; wherein said pesticide A and polymer P are completely dissolved in said solvent S at 20° C.

2. The agrochemical composition according to claim 1, wherein said vinyl ester is vinyl propionate, vinyl acetate, or a mixture thereof.

3. The agrochemical composition according to claim 1, wherein said N-vinyl lactam is selected from N-vinyl pyrrolidone, N-vinyl caprolactam, or a mixture thereof.

4. The agrochemical composition according to claim 1, wherein polymeric group Z comprises vinyl ester and N-vinyl lactam, wherein a weight ratio of vinyl ether to N-vinyl lactam is 1:3 to 3:1.

5. The agrochemical composition according to claim 1, wherein polymer P bears in the terminal positions of the polyoxyalkylene chain a hydroxy or a C.sub.1 to C.sub.22 linear or branched alkyl ether group.

6. The agrochemical composition according to claim 1, wherein polymeric group Z is 45 to 75 wt % of polymer P.

7. The agrochemical composition according to claim 1, the wherein a combined average number of units (I) and (II) per polymer molecule is 6 to 200.

8. The agrochemical composition according to claim 1, wherein polymer P is obtained by a free radical polymerization of a monomer mixture comprising i) an alcohol ethoxylate or polyethylene oxide, ii) a vinyl ester, and iii) optionally an N-vinyl lactam.

9. The agrochemical composition according to claim 8, wherein polymer P is obtained from a monomer mixture comprising i) 10 to 80% by weight of polyethylene glycol and/or alcohol alkoxylate (e.g. C.sub.8-22 alcohol ethoxylate), ii) 5 to 70% by weight of a vinyl ester, iii) 0 to 60% by weight of N-vinyl lactam (e.g. N-vinyl pyrrolidone), and iv) up to 20%, wherein the sum of component i) to iv) adds up to 100%.

10. The agrochemical composition according to claim 10, wherein said alcohol ethoxylate is based on a C.sub.8-C.sub.22 alcohol.

11. The agrochemical composition according to claim 1, wherein said polymer P is represented by formula (IV): ##STR00007## wherein each X is hydrogen or a C.sub.1-C.sub.22linear or branched alkyl group, m is a number from 5 to 150, n is a number from 1 to 30, polymer P being a random polymer.

12. The agrochemical composition according to claim 1, wherein said composition is a dispersible concentrate.

13. The agrochemical composition according to claim 1, wherein polymer P is present in the composition in an amount from 0.5 wt % to 60 wt %.

14. according to claim 1, comprising A) 3% to 30% of at least one pesticide A, B) 25% to 92% wt % at least one nonaqueous water miscible solvent S, C) 5 to 45 wt % of a polymer P, D) 0 to 30 wt % of nonionic and/or anionic surfactants different from polymer P, and E) 0 to 30 wt % of further additives.

15. A method for controlling phytopathogenic fungi and/or undesired plant growth and/or undesired attack by insects or mites and/or for regulating the growth of plants, where the composition as defined in claim 1 is allowed to act on the particular pests, their habitat or the plants to be protected from the particular pest, the soil and/or on undesired plants and/or the useful plants and/or their habitat.

Description

EXAMPLES

[0226] Materials Used

[0227] APEG 1: ethoxylated saturated linear C16C18 fat alcohol, degree of ethoxylation about 80, melting point about 56° C., HLB value about 18.5.

[0228] VP N-vinyl pyrrolidone

[0229] VAc vinyl acetate

[0230] Surfactant A alkoxylated branched C10-alcohol, degree of ethoxylation about 10 EA ethyl acetate solvent

[0231] tBPPiv tert. butyl perpivalate

[0232] Surfactant A Calcium dodecylbenzolsulfonate, 60 wt % in ethyl hexanol

[0233] Surfactant B Castor oil, ethoxylated

[0234] Surfactant C low foaming nonionic surfactant consisting of alkoxylated, predominantly unbranched fatty alcohols, and containing higher alkene oxides alongside ethylene oxide.

[0235] GPC: gel permeation chromatography

[0236] Preparation of Polymeric Additive A

[0237] Polyethylene glycol (0.44 kg, Mn 6000) was melted at 90° C. and 0.6 g of tert-butyl per-2-ethylhexanoate, dissolved in of tripropylene glycol, were added. 7.75 mol of vinyl acetate were added under stirring within 6 h (feed 1), as well as 7 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in tripropylene glycol, within 6.5 h (feed 2), and also, beginning 3 h after the start of feed 1, 0.23 kg of Surfactant A within 3.5 h (feed 3) were metered in in parallel continuously with constant flow rates at a temperature of 90° C. After the end of feeds 2 and 3 and subsequent stirring at 90° C. for a further hour, 6 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in tripropylene glycol, were added in 3 portions at 90° C. with further stirring for two hours in each case. A solids content of about 88% by weight was established by adding water. The resulting graft polymer (Polymeric additive A) had a K value of 17-19 (1 wt % polymer in aqueous sodium chloride (3 wt %) at 23 ° C.), Mw 36000, and Mn 20 000 (measured by gel permeation chromatography, PMMA standard).

[0238] Preparation of Polymeric Additive B

[0239] The reaction vessel containing 100 g APEG 1 and 25 g EA was gassed with nitrogen and heated to 77° C. Then one part of feed 2 (12.2 g tBPPiv, 50 g EA) was added and the mixture stirred for 15 min. Then feed 1 (160g VAc, 160 g VP, 120 g EA, 2.2 g 2-mercapto ethanol) and the rest of feed 2 were introduced in the reaction mixture. Feed 1 was introduced in 5 h, feed 2 was introduced in the course of 5.5 h. The reaction mixture was then kept at 77° C. for additional 3 h. Then feed 3 (200 g EA) was introduced and the reaction mixture was cooled down. Thereafter the reaction mixture was subject to steam distillation and EA was distilled off. Thereafter, benzyl alcohol was distilled off. The resulting polymer solution of graft polymer (Polymeric additive B) was 70% w/w in benzyl alcohol (a clear yellow solution). GPC measurements showed Mn=2.894 g/mol and Mw=6.514 g/mol.

Examples DC 1 to DC 15: Dispersion Concentrates

[0240] The dispersion concentrates DC 1 to DC 15 were prepared by mixing the ingredients listed in the table 1 at 60° C. for 30 minutes. All mixtures yielded transparent solutions.

[0241] One of the challenges during the development of dispersion concentrates is to find compositions in which the dissolved active ingredients does not agglomerate and/or not crystalize out up on dilution with water. If a dispersion concentrate is not stable after dilution, it is not suitable for the commercial use because the forming large crystals will clog the spray equipment of farmers.

[0242] CIPAC MT 180 dispersion stability test was used to check stability of DC 1 to DC 15 after dilution in water. The results are given in table 1. As it seen in examples DC 1 to DC 10, DC 12 and DC 14, it is possible to obtain dispersion concentrates, which are stable after dilution water. If the claimed graft polymers are not used like in case of comparative examples DC 11 ,DC 13 and DC 15, the formulated active ingredients crystalize and flocculate. Those comparative compositions could not be used in spray applications. The experiments showed that the polymeric additives used according to the invention are suitable to improve the stability of dispersion concentrates of various pesticides after dilution.

TABLE-US-00001 TABLE 1 Dispersion concentrates and their stability upon dilution (“homog.” Shall mean “homogenous”) Ingredients DC 1 DC 2 DC 3 DC 4 DC 5 DC 6 DC 7 DC 8 DC 9 Fluxapyroxad  3.7% Metyltetraprole  3.7% Pyraclostrobin 10.0% 15.0% 10.0% 10.0% 10.0% 10.0% Mefentrifluconazol Saflufenacil  8.0%  8.0% Surfactant A  5.0%  5.0%  5.0%  5.0%  5.0%  5.0%  4.7% Surfactant B  5.0%  5.0%  5.0%  5.0%  5.0%  5.0%  4.7% Surfactant C 10.0% Polymeric additive A 30.0% 30.0% 30.0% 30.0% 30.0% 30.0% 30.0% 10.0% 28.0% Polymeric additive B Benzyl alcohol 50.0% N-acetyl morpholine 50.0% DMSO 50.0% N,N-dimethyl lactamide 55.0% 50.0% 55.2% Cyclohexanon 50.0% 52.0% 72.0% The dispersion stability was tested according to CIPAC MT 180. 1% w/w solutions of formulation were prepared in CIPAC D water Initial Homog. Homog. Homog. Homog. Homog. Homog. Homog. Homog. Homog. (Opaque- (Opaque- (Opaque- (Opaque- (Opaque- (Opaque- (Opaque- (Opaque- (Opaque- clear clear clear clear clear clear clear clear clear solution) solution) solution) solution) solution) solution) solution) solution) solution) 2 hours Homog Homog Homog Homog Homog Homog Homog Homog Homog (Opaque- (Opaque- (Opaque- (Opaque- (Opaque- (Opaque- (Opaque- (Opaque- (Opaque- clear clear clear clear clear clear clear clear clear solution) solution) solution) solution) solution) solution) solution) solution) solution) Comparative Comparative Comparative Ingredients DC 10 DC 11 DC 12 DC 13 DC 14 DC 15 Fluxapyroxad  4.7%  4.7%  3.7%  3.7% Metyltetraprole  3.7%  3.7% Pyraclostrobin  3.7%  3.7% Mefentrifluconazol  3.7%  3.7% Surfactant A  4.7%  4.7% Surfactant B  4.7%  4.7% Polymeric additive A 28.0% 28.0% Polymeric additive B 40.2% Benzyl alcohol 12.6% N,N-dimethyl lactamide 57.9% 85.9% 64.6% 92.6% 52.4% 80.0% Viscosity η(s) [mPas] .sup.1) — — — — 38    — The emulsion stability was tested according to CIPAC MT 180. 1% w/w solutions of formulation were prepared in CIPAC D water Initial Homog. Homog. Homog. Flocculated Homog. Flocculated (Opaque- (Opaque- (Opaque- active (Opaque- active clear clear clear clear solution) solution) solution)) solution) 2 hours <0.05 ml Flocculated Homogenous Flocculated Homogenous Flocculated Krist. active (Opaque- active (Opaque- active clear clear solution) solution) .sup.1) The viscosities were measured according to CIPAC MT 192 by using a rotational viscometer. The given values are the apparent viscosity which were determined at shear rate of 100 s-1.

Example 16: Biology (Green House)

[0243] The pesticidal activity was tested in the greenhouse on wheat variety Monopol®, which was infected with the fungi Puccinia Recondata/Tritici (PUCCRT). The plants were treated with formulations three days after the inoculation at the use rate of 600 ppm (Pesticide A Pyraclostrobin+Mefentrifluconazol) per ha (200 l water/ha). The percentage of the infected leaf surface areas (7 days after inoculation) are summarized in Green House Table 2.

TABLE-US-00002 TABLE 2 Green House Data Disease (%) at Disease (%) at 1000 ppm 125 ppm Formulation PUCCRT PUCCRT Untreated 80% 80% control DC 12  0%  2%

[0244] According to greenhouse trial test results which are presented in Table 2, the dispersion concentrate DC 14 comprising 40.2% of Polymeric additive B showed excellent fungicidal activity. DC Formulations according to the invention also showed better fungicidal activity compared to suspension concentrates having identical fungicide loadings and containing no polymer P.

[0245] The examples given in table 1, it was shown that the claimed polymeric additives are suitable to improve the stability of dispersion concentrates upon dilution and do not cause strong increase of their viscosity. It was shown that they increase the biological performance of pesticides if they are used in dispersion concentrates.