Patent Application
20080004177
In a 2.4 liter pressure vessel, L-lysine monohydrate (821 g) and sodium hypophosphite (0.1 g) were heated for approximately 50 hours to 140-155° C. under nitrogen atmosphere, while the internal pressure rose to 5 bar. To check the course of the reaction, the reaction phase was interrupted after about 16 hours and once again after about 8 hours, a sample being taken each time. For this purpose in each case the pressure vessel was let down and cooled to room temperature. After a reaction phase of about 50 hours in all at 140° to 155° C. the reaction mixture was depressurized, cooled to room temperature, admixed with 641 g of water and filtered. This gave a viscous orange product with a solids content of 49.6% by weight and a K value (1% in water) of 18.1.
A 2.5 liter pressure vessel was charged with L-lysine monohydrate (821 g, 5.0 mol) and sodium hypophosphite (0.1 g) and the mixture was placed under a nitrogen atmosphere. Thereafter, the vessel was sealed in a pressure-tight manner and heated for 6 hours to 200° C., during which process the internal pressure climbed to 11.2 bar. Thereafter, the pressure was released slowly to atmospheric pressure in order to remove water from the reaction mixture. The reaction temperature was maintained at 200° C. for 0.5 hour to remove remaining solvent and volatile products. Thereafter, the reaction mixture was stirred for 25 minutes at 200° C. under a pressure of 20 mbar. The viscous melt was cooled to 115° C., discharged from the vessel and cooled to 20 to 25° C. The molecular weight MW of the polymer was 4300 g/mol.
A 2.5 liter pressure vessel was charged with L-lysine monohydrate (656.8 g, 4.0 mol), aminocaproic acid (524.7 g, 4.0 mol) and sodium hypophosphite (0.1 g) and the mixture was placed under a nitrogen atmosphere. Thereafter, the vessel was sealed in a pressure-tight manner and heated for 7 hours to 196° C., during which process the internal pressure climbed to 8.2 bar. Thereafter, the pressure was released slowly to atmospheric pressure in order to remove volatile substances from the reaction mixture. The viscous melt obtained was discharged from the vessel and cooled to 20 to 25° C. The molecular weight MW of the polymer was 7400 g/mol.
In a 4-liter stirred vessel, 3000 g of prepared polylysine from Ex. 1 (25% strength aqueous solution) together with 540 g of 25% strength crosslinker (polyethylene glycol bisglycidyl ether with 14 ethylene glycol units) were heated to 72° C. within the course of 2 hours and subsequently, at 25° C., brought to pH 7 with hydrochloric acid. This gave a red viscous polymer. The product was subsequently diluted with water to a solids content of 19.8% by weight.
98.25 g of an aqueous 20% by weight strength copper sulfate solution (copper salt:copper sulfate pentahydrate) were weighed with stirring into a 500 ml glass flask and treated with 126.5 g of water. Thereafter, 25.2 g of an aqueous solution from Ex. 1 comprising 49.6% by weight of polylysine were stirred in in the course of 15 minutes, and stirring was continued for 1 hour. This gave a dark blue dispersion with a copper (ion) content of 2% by weight. The weight ratio of polymer to copper was 2.5.
98.25 g of an aqueous 20% by weight strength copper sulfate solution (copper salt:copper sulfate pentahydrate) were weighed with stirring into a 500 ml glass flask and treated with 94.3 g of water. Thereafter, 25.2 g of an aqueous solution from Ex. 1 comprising 49.6% by weight of polylysine were stirred in in the course of 15 minutes. 32.2 g of 25% strength ammonia were added to this solution, with stirring, and stirring was continued for 1 hour. This gave a blackish-blue solution with a copper (ion) content of 2% by weight. The weight ratio of polymer to copper was 2.5.
98.25 g of an aqueous 20% by weight strength copper sulfate solution (copper salt:copper sulfate pentahydrate) were weighed with stirring into a 500 ml glass flask and treated with 88.2 g of water. Thereafter, 63.1 g of an aqueous solution from Ex. 2 comprising 19.8% by weight of crosslinked polylysine were stirred in in the course of 15 minutes, and stirring was continued for 1 hour. This gave a blackish-green solution with a copper (ion) content of 2% by weight. The weight ratio of polymer to copper was 2.5.
Leaves of grapevines cv. “Müller-Thurgau” in pots were sprayed to runoff point with aqueous suspension with the active ingredient concentration stated hereinbelow. The suspension or emulsion was made with a stock solution with 1% product in water. To allow the longer-term action of the substances to be assessed, the plants were placed in the greenhouse for 7 days after the spray coating had dried on. Only then were the leaves inoculated with an aqueous suspension of Plasmopara viticola. Thereafter, the vines were placed first for 48 hours into a chamber at 24° C. and 100% atmospheric humidity and then for 5 days in the greenhouse at temperatures of between 20° C. and 30° C. After this time, the plants were returned into a humid chamber for 16 hours to accelerate the eruption of sporangiophores. The extent of disease on the undersides of the leaves was then determined visually.
The visually determined values for the percentage of diseased leaf areas were converted into efficacies as % of the untreated control:
The efficacy (E) is calculated using Abbot's formula as follows:
E=(1−α/β)·100
If the efficacy is 0, the infection level of the treated plant corresponds to that of the untreated control plants; if the efficacy is 100, the treated plants are not infected.
The results shown in Table 1 demonstrate that the formulations according to the invention, which only comprised 2% of copper, were more effective using the same amounts than the commercially available formulation Funguran®, which comprises 45% copper.
A growth assay was carried out with Septoria tritici as indicator fungus. The fungal growth was measured photometrically by the increase in absorption or light scattering as a function of mycelium density. The data obtained were converted into percent growth inhibition, the absorption of the untreated controls being defined as 0% inhibition and that of a killed spore suspension as reference as 100% inhibition.
The expected efficacies of combinations of active ingredients were determined using Colby's formula (Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide combinations”, Weeds, 15, pp. 20-22, 1967)) and compared with the observed efficacies.
Colby's formula:
E=x+y−x·y/100
The results of the experiments show that owing to the pronounced synergism, the mixtures according to the invention are considerably more effective than previously calculated using Colby's formula.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10349096.5 | Oct 2003 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP04/11586 | 10/15/2004 | WO | 00 | 4/10/2006 |
