The method of obtaining the fungicide copper chloroxine


C01G3/06 - Oxychlorides

 

(57) Abstract:

Describes how to obtain fungicide chloroxine copper reaction interaction of acidic chloride solution of divalent copper ion concentration of copper 160-170 g/l and pH of 1.05 to 1.15 with calcium carbonate in stoichiometric ratio with stirring in the presence of oxygen and a temperature of 15-30oC, before the addition of calcium carbonate is injected 7% potash by weight of calcium carbonate. Effect: method allows to obtain microparticles chloroxine copper in microdispersed form with a high degree of Solutii. The reaction by-products is calcium chloride and potassium chloride - ensures the stability of working solution lowers the freezing point of the colloidal system to -15oTo ensure adhesion of the fungicide. table 2.

The invention relates to the field of technology for fungicide - plant protection from diseases caused by fungi of the class Oomycetes.

As a similar approach of obtaining chloroxine copper in the form of a wettable powder [1] (Inorganic insecticides, fungicides and saiidi, Moscow: Goskomstat, 1960, S. 133), [2] (GOST 13200-75. Cloroxed the suspension of calcium carbonate at a temperature of 85oWith, in which is deposited the active substance - cloroxed copper (II). Cloroxed copper stands out from the mother liquor, washed and dried by spray drying at a temperature of 110-115oC. To obtain a formulation of the fungicide before drying to chloroxine copper added fillers, which ensure the stability of the working solution and adhesion to plants, then crushed to a size of 5-10 microns.

The method has several disadvantages:

stage receiving chloroxine copper is carried out at elevated temperature, which requires a considerable amount of energy;

stage washing and filtering leads to the formation of troublesome sewage;

according to technology there is a need to apply the stages of drying and grinding.

Fungicide obtained by the method [1,2], has a lack of fungicidal activity of the ED50(fungicidal activity of the ED50the concentration of fungicide required to inhibit the growth of 50% of the colony of fungi of Oomycetes that cause diseases of plants), (300 µg/ml), and low stability of the working solution in the application, which is explained by the size of the particles (5-10 µm) and heterogeneity.

Most blisk, class. C 01 G 3/06, 1996) is a one-step process of obtaining chloroxine copper in the colloidal form, which is based on a reaction between the acidic copper chloride solution with an aqueous suspension of calcium carbonate at a temperature of 25-30oC.

The method implements the possibility of obtaining colloidal particles with sizes: 90% of particles of not greater than 1 μm; 98% of particles of not greater than 3 μm.

However, the resulting size of the colloidal particles (from 1 to 3 μm), allows to obtain the fungicidal activity of the drug, 200 µg/ml.

In addition, the stability of 0.5% solution (0.5% solution of fungicide is a working solution in the application of the fungicide, the stability of the solution should be not less than 80% according to the requirements of THE 2443-007-07517261-98 on Caprica, 20% colloidal solution of copper oxychloride) below 80% due to the alleged destruction of the solvate shell colloidal particles with a simultaneous decrease in potential dilution with water formulation of the fungicide.

The purpose of the proposed invention to provide a fungicide with the active ingredient cloroxed copper in colloidal form with a particle size of not more than 0.5 μm, providing fungicidal activity of 100 ág/ml and stability of working age who I parameters of the colloidal system chloroxine copper, providing functional and operational characteristics of the fungicide in the reaction is added potassium carbonate, initiating the formation of stable solvate layer of microparticles, microheterogeneity colloidal systems with electrokinetic potential of more than 40 mV. Potassium carbonate is introduced prior to the introduction of calcium carbonate. Potassium carbonate and calcium carbonate are used in powder form.

Preparative form of fungicide consisting of active substance, stabilizer working fungicide, adhesive and protivotarannogo means is made in one stage, without the introduction of additional fillers and stabilizers.

The process of obtaining chloroxine copper 3 C satellite(OH)2CuCl23H2O based on a reaction between an acidic solution of chloride of copper powder with calcium carbonate occurring in the stoichiometric ratio of the reagents, but part of calcium carbonate (7-10% of the total mass) is replaced by carbon dioxide potassium, which is introduced into the reaction mixture prior to the introduction of calcium carbonate.

Introduction potash creates the conditions for a sharp increase in the number of emerging centreless growth of microcrystals.

Since potassium carbonate is soluble in the reaction medium substance, it provides high reaction rate of formation of microparticles of chloroxine copper in excess of the speed of their growth.

High solvation capacity monovalent potassium ions present in the mother solution in the reaction and after completion of the synthesis, creates the conditions for the occurrence of a solvate layer of microparticles having "barrier effect", increasing with increasing potential and preventing them together.

The force of repulsion of like charged particles of chloroxine copper prevents their aggregation.

Replacement parts of calcium carbonate to potassium carbonate also allows you to significantly improve coagulating electrolyte concentration due to sharp decrease clotting ability of monovalent ions of potassium in relation to the divalent ions of calcium.

Compliance with the reaction conditions (concentration of the starting components, pH, consistency and speed of introduction of the reagents, time of the synthesis process, the mixing mode and the continuous inflow of oxygen) allows you to get mikroC who has aggregative stability of the colloidal system. The reaction by-products is calcium chloride and potassium chloride - provide enhanced operational and functional characteristics of the fungicide. Potassium chloride ensures the stability of working solution for the application. In addition, the joint presence of calcium chloride and potassium chloride lowers the freezing point of the colloidal system to -15oWith easier storage conditions of the fungicide, and the presence of calcium chloride provides adhesion fungicide when applied without the introduction of the working solution additional substances adhesives.

Thus, the technical result of the proposed invention, is expressed in the following:

increased fungicidal activity(100 µg/ml) compared with the equivalent (300 µg/ml) 3 times, and with the prototype (200 μg/ml) 2 times;

increases the stability of working solution (over 85%);

extends the period of the protective action of fungicide due to the high adhesiveness and high domesticate 10-14 days;

providing a wide range of temperatures during storage by reducing the freezing temperature of fungicide to -15oC;

the costs for the preparation and production of the fungicide by adnotatione seat to establish the criterion of "novelty."

Due to the fact that the needs of agriculture in the contact fungicide with application as the active substance of chloroxine copper in pure form and in mixtures with other fungicides in thousands of tons, then the claimed technical solution meets the criterion of "industrial applicability".

The inventive method is carried out as follows.

In the static mixer is filled with a volume of acidic solution of chloride of copper required concentration, at a temperature of 15-30oWith constant stirring and bubbling with compressed air load calculated amount of potassium carbonate, then the appropriate amount of calcium carbonate. Loading is carried out gradually, in small portions, and, depending on the amounts of reactants, followed by foaming in varying degrees. The loading of each subsequent portion of the reagent is carried out after the termination of foaming. After loading the last portion of the reagent during the process of synthesis is chosen so that the concentration of copper ions (II) in the filtrate at the end of the synthesis process does not exceed 1 mg/l and pH of the effluent was in the range of from about 5.8 to 6.5. Mixing and barbeau is: a colloidal solution of light green with blue shade, representing the fungicide formulations form, consisting of the active substance (cloroxed copper in colloidal form) and fillers - potassium chloride and calcium chloride, which acts as a stabilizer of colloidal systems, adhesive and protivotarannogo tools.

Technological parameters and parameters obtained fungicide determined visually and instrumentally: appearance visually, the pH of the initial solution and the filtrate is measured using a pH meter; percentage content of active substance determine volumetric titrimetric method; the concentration of copper ions (II) in the filtrate - Stripping voltammetric method for polarography; the size of the microparticles - sedimentation method; fungicidal activity and stability of the working of 0.4% aqueous solution determined by the standard uniform methods; the magnitude and sign of the potential method of electrophoresis; temperature freezing with the freezer on the method of determination of frost resistance (in. A. Pisarenko, HP Zakharov "foundations of technical analysis"); the degree of foaming is determined by the fall time of the foam above the reaction mixture after the introduction portion of the reagent; adhesion determine the S="ptx2">

Main parameters and technological characteristics of the obtained product are shown in tables 1 and 2.

Example 1. Synthesis without the introduction of potash.

In 1 l of copper chloride solution containing 165 g/l of copper and having a pH of 1.1 at a temperature of 18-20oWith small portions with constant stirring and bubbling of compressed air injected 197 g of calcium carbonate. Foaming regulate the rate of introduction of calcium carbonate. The introduction of a new portion of the reagent is performed after termination of foaming. During the synthesis after the introduction of the last portion of calcium carbonate up to 9 hours. In the process of synthesis is formed pasty blue-green homogeneous fluid mass. After a specified time, stop stirring, conduct analysis of the filtrate on the content of ions of copper (II) monitor the pH of the filtrate, determine the percentage content of active substances and other technological characteristics.

Example 2. Synthesis with the introduction of 3% potash.

In 1 l of copper chloride solution containing 165 g/l of copper and having a pH of 1.1 at a temperature of 18-20oWith small portions with constant stirring lead 192 g of calcium carbonate. Next, the process carried out analogously to example 1. After the end of the synthesis process, perform a full inspection of the obtained product.

Example 3. Synthesis with the introduction of a 5% potassium carbonate.

In 1 l of copper chloride solution containing 165 g/l of copper and having a pH of 1.1 at a temperature of 18-20oWith small portions with constant stirring and bubbling of compressed air injected 13.3 g potassium carbonate, after the cessation of foaming also portions enter 187.1 g of calcium carbonate. Next, the process carried out analogously to example 1. The boot process similar to those shown in example 2, and is accompanied by a moderate foaming. Technological and functional characteristics of the resulting product is presented correspond to the fungicide requirements.

Example 4. Synthesis with the introduction of 7% potash.

In 1 l of copper chloride solution containing 165 g/l of copper and having a pH of 1.1 at a temperature of 18-20oWith small portions with constant stirring and bubbling of compressed air injected 19 g of potassium carbonate, after the cessation of foaming also portions enter 183,2 g of calcium carbonate. Next, the process carried out analogously to example 1. The process Haakim and functional characteristics presented to the fungicide.

Example 5. Synthesis with the introduction of 10% potassium carbonate.

In 1 l of copper chloride solution containing 165 g/l of copper and having a pH of 1.1 at a temperature of 18-20oWith small portions with constant stirring and bubbling of compressed air injected at 27.1 g of potassium carbonate, after the cessation of foaming also portions enter 177,3 g of calcium carbonate. Next, the process carried out analogously to example 1. The process is almost no different from the process described in example 4, a slight increase in the foam. The obtained product with the technological and functional characteristics, presented to the fungicide.

Example 6. Synthesis with the introduction of 15% potash.

In 1 l of copper chloride solution containing 165 g/l of copper and having a pH of 1.1 at a temperature of 18-20oWith small portions with constant stirring and bubbling compressed air is injected to 40.8 g of potassium carbonate, after the cessation of foaming also portions enter 167,5 g of calcium carbonate. Next, the process carried out analogously to example 1. The process of introducing carbon dioxide potassium is associated with very high foaming, which increases the timeout thick, it is difficult flowing mass of blue color, which causes some technological difficulties when unloading product from the reactor. All other product characteristics meet the requirements.

Example 7. Synthesis with the introduction of 7% potash with increased time of reaction.

In 1 l of copper chloride solution containing 165 g/l of copper and having a pH of 1.1 at a temperature of 18-20oWith small portions with constant stirring and bubbling of compressed air injected 19 g of potassium carbonate, after the cessation of foaming also portions enter 183,2 g of calcium carbonate. The course of the synthesis reaction for 15 hours. The residual concentration of copper ions in the mother solution, 1.0 mg/l, the pH of the filtrate to 6.2. As a result of exceeding the duration of stirring the reaction mixture decreases the stability of the working solution, because there is a tendency to increase the size of the microparticles of chloroxine copper (up to 3 μm). Presumably this phenomenon is associated with the destruction of the solvate shell around the colloidal particles, the reduction potential and aggregation of microparticles.

From the above examples and data tables, it follows that the methods according to the invention, predi form, characteristics, exceeding similar characteristics fungicide manufactured in a known manner.

Sources of information

1. Morozova M. A., Koltsov N. With. Chemistry and technology of chloroxine copper/ sat Inorganic insecticides, fungicides and saiidi. - M, 1960.

2. GOST 13200-75. Cloroxed copper, 90% wettable powder.

3. RU, patent 2121974, CL 01 G 3/06,1996.

The method of producing fungicide chloroxine copper, comprising the reaction of interaction of acidic chloride solution of divalent copper with calcium carbonate in stoichiometric ratio with stirring in the presence of oxygen and a temperature of 15-30o, Characterized in that use acidic solution of divalent copper ion concentration of copper 160-170 g/l and pH of 1.05-1.15 and before the addition of calcium carbonate is injected 7% potash by weight of calcium carbonate.

 

Same patents:

The invention relates to the chemical industry, in particular to methods for chemical plant protection products, namely, to obtain fungicide-of copper oxychloride (II) in the form of aqueous suspension

The invention relates to a method of producing chloroxine divalent copper, used in agriculture as a fungicide to combat widespread disease of green plants - blight

The invention relates to a method for the oxychloride of copper from spent acid and alkaline etching solutions production of printed circuit boards

The invention relates to the treatment of domestic wastewater and can be used for bacterial treatment at wastewater treatment plants municipal sewage systems and on local treatment facilities enterprises

The invention relates to the field of organic chemistry, in particular to a method for (N,N'-tetramethylethylenediamine) copper sulfate pentahydrate, which can be used as a growth promoter and plant productivity

The invention relates to agriculture, in particular to chemical agents stimulating the growth and nutrition of plants
The invention relates to the production of fertilizers

The invention relates to agriculture, in particular, compositions for stimulating the growth of agricultural crops

The invention relates to plant protection and can be used to obtain a fungicidal solution contact action for protection of plants from leaf diseases and fungal diseases

The invention relates to the means of chemical plant protection and can be used for the prevention and protection of plants from leaf and fungal diseases

The invention relates to agriculture, namely, to means for presowing treatment of seeds

FIELD: organic chemistry, fungicides.

SUBSTANCE: invention describes a fungicide mixture containing carbamate of the formula (Ia):

and copper-containing fungicide taken in synergistically active amount. Also, invention describes a method for control of phytopathogenic fungi and applying compounds for a synergistic mixture eliciting the fungicide properties. Fungicide mixtures provide inhibition of phytophthora infection in tomato plants.

EFFECT: improved method for control, valuable fungicide properties of mixtures.

8 cl, 6 tbl, 3 ex

FIELD: agriculture.

SUBSTANCE: claimed composition contains (g/t): benzimidasole derivatives (e.g. agrocite, bendan, usgene, fundasol) as protectant not less than 300; and target additives: carbamide 20-25; potassium monosubstituted phosphate 9-12; potassium chloride 7-10; copper sulfate 120-125; zinc sulfate 120-125; magnesium sulfate 120-125; cobalt sulfate 10-12; manganese sulfate 15-17; ammonium molybdate 16-18; and water 1000-1050. Composition for seed pretreatment contains abovementioned components in the same ratio and water soluble film-forming agent in amount of 10-12 g/t.

EFFECT: decreased protectant consumption.

5 cl, 2 ex

FIELD: agriculture.

SUBSTANCE: method relates to fungicide composition containing compound of formula I

1 and cupper chlorooxide in synergic ratio.

EFFECT: composition with high fungicide activity.

1 cl, 1 tbl, 1 ex

FIELD: pesticides, chemical technology.

SUBSTANCE: invention describes a method for preparing copper-containing liquid pesticide. Method involves formation of a hardened water-soluble complex copper-borate, its grinding to form granules and dissolving granules in water to obtain liquid pesticide comprising the copper concentration at least 0.20% but not above 1.00 wt.-%. Also, invention describes liquid pesticide prepared by indicated method and a set comprising granules of hardened water-soluble complex copper-borate and letter instructions for preparing the liquid pesticide. Method provides remaining copper in solution in dissolving the hardened complex copper-borate in water.

EFFECT: improved preparing method.

4 cl, 1 dwg

FIELD: agriculture.

SUBSTANCE: invention describes a composition used in stimulating growth and development of agricultural crops. The composition comprises molybdenum and copper compounds, alkanolamine, water and citric acid taken in the following mole ratio in mixture: molybdenum compounds : copper compounds : citric acid : alkanolamine = 1:(2-8):(1-10):(4-80), respectively, in the following ratio of components, wt.-%: mixture of molybdenum compounds, copper compounds, alkanolamine and citric acid in the mole ratio given above, 0.5-65, and water, the balance. The proposed composition is used for stimulating growth and development of agriculture crops, enhancing their quality and output and can be used for their leaf feeding and for presowing treatment of seeds.

EFFECT: valuable properties of composition.

2 tbl, 7 ex

FIELD: biochemistry, agriculture.

SUBSTANCE: claimed combinations contain compound of formula I and the second component selected from group including of penconazol, pyrqclostrobin, trifloxystrobin, famoxadon, zoxamide, benalaxyle, phosphorous acid, and copper hydroxide in synergetically effective ratio. Also described are fungicidal combinations containing compounds of formula Ia and the second component selected from abovementioned group.

EFFECT: synergetic fungicidal combinations with increased activity.

6 cl, 4 tbl, 2 ex

Up!