CS243558B1 - Alkyldithiocarbamide acids' concentrated fine-dispersed metal salts preparation method - Google Patents

Abstract

The invention relates to a method of preparing concentrated, Finely dispersed metal salts of alkyldithiocarbamic acids by reacting the water-soluble alkyldithiocarbamide salt acid with at least one water-soluble a salt of manganese and / or zinc and / or media. The main precipitation product the reaction is formed after removal of the salt in the reaction mixture as a by-product the boiling point reaction is added mixtures thereof with water below boiling point water, with limited miscibility with water and its specific weight the same temperature is lower or higher than its specific weight of water. After the eventual adding zinc and / or manganese salts and / or medium is mixed at atmospheric or boiling, from a vapor mixture at a lower pressure after condensation, water and substance are separated or a mixture of substances characterized by the foregoing properties go back to sleep, boiling and distilling mixture. The invention can be used in industrial applications practice.

Description

The invention relates to a process for the preparation of concentrated, finely dispersed metal salts of alkyldithiocarbamic acids.

Several organic sulfur compounds containing the group:

\

N-C-S

S are nowadays traditionally produced and used agrochemicals, such as many important fungicides (NABAM, AMBAM, MANEB, ZINEB, MANCOZEB, FERBAM, TERBAM, MARBAM, ZIRAM, PROPINEB, or MEZINEB, METIRAM), fumigants (VAPAM), nematocides (MYLON), dry seed dressing (THIRAM), respectively. Thiuram).

Some of these compounds have also found utility as nitrification inhibitors, industrial fungicides, rubber chemicals, human and veterinary therapeutics, microbial metal corrosion inhibitors, chemical analytical reagents and the like.

Their main representatives are dithiocarbamidates (dithiocarbamates) derived from the hypothetical ditocarbamic acid:

H 2 N-C-SH

WITH

By replacing the amino of the amino group with alkyl and the hydrogen of the dithiocarboxylic acid group with a metal, the agrochemical activity of these substances is usually significantly influenced.

The most important dithiocarbamate-type fungicides are MANEB (manganese 1,2-ethane-bisdithiocarbamate) (I)

S S

II II (—Mn — S — C — NH — CH2 — CH2 — NH — C — S-) _n (I)

ZINEB (Zinc 1,2-ethanebisdithiocarbamate) (II)

S S

II II (—Zn — S — C — NH — CH2 — CH2 — NH — C — S—) _n (Π)

MANKOZEB (zinc cation coordination compound with manganese 1,2-ethanebisdithiocarbamate) (III)

S S

II II (—Mn — S — C — NH — CH2 — CH2 — NH — C — S-) _n (Zn) _m

With considerable simplification, it can be said that they are prepared in two stages. In the first reaction of 1,2-ethanediamine (ethylenediamine), carbon disulphide and the corresponding alkali (NH 3, NaOH, KOH, Ca / OH / 2) in an aqueous medium, the corresponding water-soluble salt of 1,2-ethane-bis-dithiocarbamic acid is formed. in the next step it precipitates with manganese and / or zinc ion, most often an aqueous solution of sulfate or chloride.

NH2 - CH2 - CH2 - NH2 + 2 CS2 + 2 NH4OH -

WITH

II

CH2-NH-C-S-NH4 + 2 H2O CH2-NH-C-S-NH4

WITH

WITH

II S

CH2 — NH — C — S — NH2 || n | - (- nZnCl2 - (—Zn — S — C-NH-CH2 — CH2-NH — C — S- _n + 2 n NHiCl)

CH2-NH-C-S-NHi

The 1,2-ethane-bis-dithiocarbamic acid disodium salt (NABAM), the first of synthetically prepared bisdithiocarbamates, was first prepared in the laboratories of Rohm and Haas Co. in 1935 by HESTER. Some years later, HESTER and HILL (U.S. Pat. No. 2,317,765) as well as DIMOND, HEUBERGER, and HORSFALL (Phytopathology, 1943, 33, 1095) described the fungicidal properties of these compounds. These two have been found to be crucial for the development of 1,2-ethane-bis-dithiocarbamates as the most widespread fungicides of organic nature used in agricultural practice.

MOREHART and GROSSAN (Agriculs tural Experiment Station, University of Delaware, Bulletin No. 357, 1965) report on their development history.

Unlike NABAM, which is well soluble in water, from which it can also be crystallized as a defined compound (m.p. 80-81 ° C), the structure of MANEB, ZINEB and MANKOZEB is not fully elucidated today. According to recent studies, these have a polymeric character, which explains their very poor water solubility.

The dissertation thesis, Utrecht, April 1975] assumes for ZINEB such a polymer-coordination structure: VONK (Decomposition of Bisdithiocarbamates and their Metabolism by Plants and Microorganism.

C-N-R 7h-garbage-C

- S .Z (S $ / f / 4)

Zn

WITH

Zn with the preparation of metal salts of 1,2-ethane-bis-dithiocarbamic acid, in particular MANEB, ZINEB and MANKOZEB, has been disclosed in several scientific publications and patents. These include, for example: USA pat. no. 2,504,404, 2,855,418, 2,974,156, 3,379,610, 3,497,598, 3,856,836, 4,217,293, French Patents Nos. No. 1,158,574 and 1,234,005, British Pat. no. 1,107,568, German Pat. no. No. 2,710,469 and Belgian patent no. 890 669.

The batch preparation methods described therein differ in the preparation conditions, such as: the type of water-soluble salt of 1,2-ethanebisdithiocarbamic acid used as well as the type of water-soluble salt of manganese and / or zinc used for precipitation, the order of addition of reagents, their concentration, pH , temperature, type of stabilizing and other additives used, method of separating the reaction mixture, method of drying the product and the like.

According to NEWSOME (Ethylenebisdithiocarbamates and Their Degradation Products-Analytical Methods for Pesticides and Plant Growth Regulators, Vol. XI, Academic Press, Inc. 1980), 1,2-ethane-bis-dithiocarbamic acid derivatives are relatively unstable.

Among the degradation products were identified:

ethylene thiourea (C3H6N2S), ethylene urea (C3H6N2O),

2-imidazoline (C3H6N2], ethylene thiurammonosulfide (C4H4N2S3), ethylene bis-isothiocyanate (C4H4N2S and some others) (LUDWIG, RA-THORN, GD-UNWIN, CH: Can. J. Bot. 1955, 33, pp. 42-42) 59; CZEGLEDI-JANKO, G .: J. Chromatog. 1967, 31, pp. 89-95.)

As shown in their publications BONTOYAN and LOOKER (J. Agric. Food Chem. 1973, 21, pp. 338-341), MANEB appears to be less stable than zinc containing products.

ENGST and SCHNAAK (Z. Lebensm.-Unters. Forsch. 1967, 134, pp. 216-221) as well as HYLIN (Bull. Environ. Contam. Toxicol 1973, 10, pp. 227-233) found that by decomposing MANEB in in the aqueous environment, almost all of the above compounds are formed.

Several of the by-products can be formed in the reaction mixture already in the preparation of the metal salts of 1,2-ethane-bis-dithiocarbamic acid, especially when favorable conditions are created for the reaction to take place. For example, THORN and LUDWIG (J. Appl. Chem. 1962, 12, pp. 90-92) report that the action of atmospheric oxygen on aqueous solutions of NABAM in the presence of Mn ²⁺ salts (catalytic effect) produces ethylene thiurammonosulfide and ethylene thiourea.

The same substances have been identified in aqueous suspensions of MANEB and ENGST and SCHNAAK (Z. Lebensm.-Unters. Forsch. 1970, 143, stra243558 at 99). In addition, these authors have identified the presence of ethylene thiuram disulfide in the system.

The presence of ethylene thiourea in the reaction mixtures in the preparation of ZINEB, MANEB, and MANKOZEB was also confirmed by BONTOYAN and co-workers (J. Ass. Offic. Anal. Chem., 1972, 55, p. 923).

In order to inhibit the formation of undesirable byproducts in the process of producing dithiocarbamidates and to stabilize the reaction products, a number of compounds have been patented in the upcoming period. These include, but are not limited to: sodium or calcium sulfite (U.S. Pat. No. 2,665,285), hexamethylenetetramine-urotropin (U.S. Pat. No. 1,113,607; U.S. Pat. No. 2,974,156; French Pat. No. 1,234,005) , addition of various metal salts (Dutch Pat. No. 288,629); 1,3,5-tris (cyanomethyl) hexahydrotriazine and / or dinitroso-pentamethylenetetramine (British Pat. No. 1,119,029), o-, m-, or p-phenylenediamine (French Pat. No. 1,374,622), paraformaldehyde (French Pat. No. 1,344,342: U.S. Pat. No. 4,217,293), formaldehyde (U.S. Pat. No. 3,856,836 and No. 4,217,293), as well as some others.

According to some foreign works, in order to deepen the polymeric character of the structure of the metal salts of 1,2-ethane-bis-dithiocarbamic acid, in particular MANEB, and thereby increase the stability of these compounds, it is recommended that concentrated solutions of all reactants be used.

It is known from practical knowledge, as well as from scientific and patent literature, that in the conventional process for the preparation of metal salts of 1,2-ethane-bls-dithiocarbamic acid, the precipitation product is obtained in the form of a relatively very coarse, rapidly settling precipitate. in the next stages of the technological process further milling.

Dry as well as wet grinding of products of this type is a source of considerable increase in investment and energy intensity of the technological process and also creates favorable conditions for oxidative, hydrolytic and thermal degradation of the active substance.

Although the degree of dispersion of the precipitate reaction product particles can be significantly influenced by the conditions under which the metal salts of 1,2-ethane-bis-dithiocarbamic acid (No. AO No. 237 874) are prepared, the fineness of the product achieved does not directly meet the requirements in this respect. to final preparations.

At least the same problems in the conditions of technological operating practice are also associated with dewatering of the precipitation reaction products after removal of the salt formed in the reaction mixture as a byproduct of the precipitation reaction (usually ammonium, sodium, potassium or calcium salt of the anion - mostly sulphate, chloride or acetate). .

Low temperature stability (pyrolysis runs above 130-135 ° C, with products decomposing even at temperatures only slightly higher than the room temperature) in the presence of water and free metal cations as well as the fact that most metal salts of alkyldithiocarbamic acids form hydrates binding varying the amount of water in its crystal lattices usually imposes particular requirements on the drying of products of this type.

However, achieving the highest degree of dehydration of the products of the precipitation reactions is of great importance in terms of ensuring the necessary stability of the active ingredient in the final formulations during storage. For these reasons, the drying of these reaction products is often carried out in several stages, usually in a protective layer of inert gases and at considerably reduced pressures.

In this context, for example, a combination of a spray dryer dryer followed by dehydration of the thus dried material by gentle heating under intensive mixing under vacuum has been used in the field. It can also be seen from the above that dewatering of metal salts of alkyldithiocarbamic acids is an investment, operational and energy-intensive operation that places extremely high demands on the operation of the facility with more specialized and hardly accessible equipment and requires a high level of observance of technological discipline.

It has now been found that the vast majority of these drawbacks can be eliminated by preparing concentrated and finely dispersed alkyldithiocarbamic acid metal salts by reacting a water-soluble alkyldithiocarbamic acid salt with at least one water-soluble manganese and / or zinc salt and / or the medium of the invention.

The principle of the invention is that at least one of the substances whose boiling point of their mixture with water is below the same pressure conditions is added to the main precipitation product after removal of the salt formed in the reaction mixture as a byproduct of the precipitation reaction. is the boiling point of pure water, whereby such substance or mixture of substances is mixed with water to a limited extent.

Furthermore, for this substance or a mixture of such substances, its density at the same temperature is lower or higher than that of water.

Further, some of the zinc salts and / or the medium and / or manganese are optionally added to the main reaction product of the precipitation reaction, and some of the substances stabilizing the reaction product are also added. The mixture thus obtained is boiled at atmospheric pressure or below atmospheric pressure, water is separated from the mixture after condensation, the substance or mixture of substances characterized by said properties returning back to the center at which boiling and distillation takes place. .

In order to achieve a substantial simplification and thus to increase the efficiency of the technology for the preparation of concentrated, finely dispersed metal salts of alkyldithiocarbamic acids, the distillation of water can be carried out even in the presence of finalizing additives - substances modifying the properties of the active substance.

Among the substances which have been shown to be suitable for the preparation of concentrated, finely dispersed metal salts of alkyldithiocarbamic acids by the process according to the invention, even at atmospheric pressure, are for example: n-alkali (n-pentane, n-hexane), petroleum ether, cyclohexane, petrol , trichloromethane-chloroform, carbon disulphide and the like. For example, carbon tetrachloride-carbon tetrachloride, benzene, toluene, xylene and some other additives can be used under reduced pressure.

The process of preparing concentrated metal salts of alkyldithiocarbamic acids according to the invention can be theoretically explained as follows:

When two insoluble and chemically inert liquids (substance A and substance B) are heated together, each of them evaporates as if the other substance were not in the system. Thus, the partial pressures of their vapors are equal to the pressures of the pure components p ^with A and p ° _B. Assuming that Dalton's law applies to the gas mixture, we can write for the total pressure above the mixture of both liquids P:

P = ρ ° ° + p _{Λ B.}

Since the pressure of saturated pairs of pure components p ° _A and ρ ^σ Β does not depend on their amount, the total pressure over the mixture of liquids does not seem to depend on their ratio in the mixture.

As is known, the liquid boils when its saturated vapor pressure equals ambient - external pressure. Since the total pressure P is always greater than the value of the partial pressures of the individual pure components Ρ ° λ and P ° b, the boiling point of such a mixture is always lower than the boiling point of both pure components of the mixture. The boiling point of such a mixture remains constant until one of the components has completely evaporated. Then the temperature changes to the boiling point of the other component.

The process of preparing the concentrated and finely dispersed metal salts of the alkyldithiocarbamic acids of the invention is exemplified but not limited by the following examples.

Example 1

An aqueous solution of ammonium ethylene bisdithiocarbamidate was prepared by a modified FLENNR procedure (US Pat. No. 2,609,389) according to ZAVIZIN (Chim. Prom. 3, 174-175, 1972).

A sulfonation flask equipped with a reflux condenser, stirrer, glass and saturated calomel electrode, dropping funnels and thermometer, placed in a tempering water bath, was weighed 511.54 g of distilled water and 310.31 g of chemically purified and distilled carbon disulphide (PITRA, VESELÝ, Z. KAVKA, F .: Laboratory Treatment of Chemicals and Auxiliary Substances, SNTL - Prague 1969, page 80} coated with 26.76 g of distilled water.

115.57 g of pre-distilled 1,2-ethanediamine (ethylenediamine) were charged to the flask over 25 minutes while stirring and circulating the water through the reflux condenser, via an addition funnel opening below the level of the trap. During dosing of 1,2-ethanediamine, the temperature of the reaction mixture increased from 20.5 ° C to 38.5 ^° C, while the pH of the reaction mixture increased from the original 5.7 to 10.1 over the first five minutes and then gradually decreased up to 7.70.

After the entire 1,2-ethanediamine feed was fed in, a uniform addition of 25.16% ammonia water was started via the dropping funnel. 263.1 g of this ammonia water was charged over 15 minutes, the reaction mixture was heated to 42 ° C and the pH of the reaction mixture reached 8.6.

Upon completion of the ammonia water dosing, the reaction mixture was heated to about 40 ° C with stirring for two hours (the pH of the reaction mixture after the tempering was 8.9). The reflux condenser was then removed from the sulfonation flask and both dropping funnels and the reaction mixture were rapidly heated to 57 ° C with stirring to remove unreacted CS2.

After cooling the reaction product - a rye-colored clear solution, the active substance content was determined by chemical analysis. The result of the analysis showed that about 1.2 kg of a 36.4% aqueous ammonium 1,2-ethane-bisdithiocarbamate solution was prepared by the above procedure. The prepared aqueous solution of ammonium 1,2-ethane bisdithiocarbamate (EBDTK-NH4) was used in the preparation of concentrated metal salts according to the traditional method of the invention. Examples 2 and 3

In order to prepare comparative - control samples of concentrated metal - manganese salts of 1,2-ethane-bisdithiocarbamic acid (MANEB), the preparation of samples no. 2 and 3 proceeded in two different classical ways. In case of sample preparation no. 2, after the precipitation with distilled water, the washed active ingredient cake was dried in an atmospheric atmosphere at atmospheric pressure at 50-60 ° C. When preparing sample no. 3, the filter cake after washing with distilled water was dried in a laboratory-type vacuum cabinet-type vacuum oven at 40-45 ° C.

The preparation of the filter cake was as follows:

A beaker containing about 63.1 g of 36.4 percent aqueous solution of 1,2-ethane-bis-dithiocarbamate solution (EBDTK-NHI) was stirred with a glass rod poured, about 36.9 grams of an aqueous solution of MnSO comprising 13.86 ⁰ Mn. The reaction mixture was stirred for 5 minutes and then allowed to sediment freely for 30 minutes. Then, the clarified layer over the rye precipitate was decanted and the precipitate was poured about 200 cm ^{3 of} distilled water. After thorough mixing, the precipitate was allowed to sediment freely for 30 minutes.

After carefully decanting the clarified aqueous layer, the decantation of the precipitate with distilled water was repeated once more in a similar manner. After pouring the clarified aqueous layer after the second decantation, further portions of the aqueous phase were removed from the precipitate by filtration through pleated filter paper, using about 50 cm ^{3 of} distilled water to quantitatively transfer the precipitate to the filter and wash it.

The wet cake was then transferred (in the case of Examples 2 and 3, respectively) from the filter paper to a watch glass and further dried in air at atmospheric pressure and at atmospheric pressure, respectively. under vacuum (laboratory oil rotary vacuum pump) to constant weight of dried samples.

An average temperature of 52.7 ° C was measured when drying in an oven at atmospheric pressure (sample preparation 2), with the measured extreme values being: min. 48 ° C and max. 60 ° C. Drying was terminated after 1,650 minutes, when the sample exhibited a constant weight under the indicated drying conditions. A sample of untreated MANEB was prepared, which contained:

40.63 wt. % of total sulfur

10.33 wt. % of total nitrogen and

17.92 wt. % manganese.

The results of the chemical analysis indicated that, with respect to the sulfur content, the product obtained contained 84.05% of the active substance, with the active substance content based on Mn being 86.53%.

When preparing sample no. 2 by drying the washed filter cake in a cabin-type laboratory vacuum oven, drying under laboratory rotary pump vacuum was carried out at a temperature of 40 ° C to 45 degrees C. Drying under these conditions was terminated after 1,335 minutes, when the weight of the dried sample was constant. A sample of concentrated, untreated MANEB (manganese 1,2-ethane-bis-dithiocarbamate) thus prepared contained:

38.54 wt. % of total sulfur

10.66 wt. % of total nitrogen

17.98 wt. % manganese

On the basis of these chemical analysis results, it can be calculated that the active substance content (CaHeN2SiMn) with respect to the sulfur content of the reaction product was 79.73% and with respect to the manganese content was 86.82%.

Both products (sample No. 2 and 3) even after separation by stick between two papers mail of considerable coarse grain character.

Examples 4 to 10

In these laboratory experiments, the preparation of concentrated manganese 1,2-ethane-bis-dithiocarbamate (MANEB) was one of the possible methods of the invention.

In an analogous manner to that described in the examples no. 2 and 3, and using the same reactants, a wet cake washed with distilled water was also prepared in connection with these experiments.

Manganese 1,2-ethane-bis-dithiocarbamate.

Part of the washed wet cake was transferred to a round bottom flask of 500 ^cm3, provided with a central ground-NT 29 for the location of the distillation head with a condenser and one to two ground joints NT 14.5 location ground glass thermometers (temperature measurement in the vapor and optionally liquid phase) .

Next, the wet washed cake was weighed with one of the following tested additives within the meaning of the invention:

xylene, CsH 10 (pure);

petroleum ether (Aether petrolei, 30-70 ° C, as defined by TPD 33-045-62);

benzene, C 8 H 8 (pure);

n-hexane, CH 3 (CH 2) 4 —CH ₃ (pure, VEB JENAPHARM-LABORCHEMISTRY APOLDA, DDR); petrol (pharmaceutical);

toluene, C7H5 (pure, according to PND 36-038-67); cyclohexane, C6H12 (pure).

Thereafter, the boiling flask was placed in an electrically heated heating nest and a special distillation head with a water-cooled cooler was placed on the ground joint of NZ 29. The distillation head allowed the vapor to pass freely from the flask to the downstream condenser and further ensured the continuous distribution of liquid condensate in the separator under the downstream condenser, as well as a continuous effluent of the lighter organic liquid phase from the top of the divider to the boiling flask. After placing the thermometers in the ground-glass tubes (NZ 14.5) and opening the cooling water supply to the downstream cooler, the brewing vessel was heated.

243556

Overview of basic data on laboratory experiments - Examples no. 4 to 10

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Upon boiling, the heating was appropriately reduced. A vapor phase consisting of a pair of organic additive and water was condensed in a reflux condenser and continuously flowed into a separator separating the specifically heavier water from the organic additive. The separated organic additive drained through the overflow located at the top of the separator to go to the brewing flask.

The contents of the boiling flask were maintained at the boiling point until the volume of water condensate in the separator was changed. The heating was then stopped and after cooling the contents of the boiling flask, the solid phase consisting of concentrated 1,2-ethane-bis-dithiocarbamate manganese was separated from the liquid organic additive by filtration through folded filter paper. Residues of the liquid organic additive were removed by evaporation in an evacuated desiccator. A summary of the basic data on the laboratory experiments carried out (Examples 4 to 10) is shown in Table 1. First

If xylene (Example 4) and partly toluene (Example 9) were used, the product was thermally decomposed due to the boiling point of the organic additive or its mixture with water being too high. used under reduced pressure over the boiling mixture, optionally in admixture with another suitable substance within the meaning of the invention.

In this laboratory experiment, the same apparatus and procedure were used as in the previous examples no. 4-10. Pure pharmaceutical gasoline was used as an additive according to the invention. In contrast to the experiments presented in the examples no. Approximately 63.1 g of a 36.4% aqueous ammonium 1,2-ethane-bis-dithiocarbamate (EBDTK) solution was added to the washed wet filtercakes obtained by precipitation (according to Example 2 and 3) 4-10 before the addition of gasoline. -NH 4) with 36.9 g of an aqueous solution of MnSO 2 (13.86% Mn), still weighing in crystalline zinc sulfate.

The quantities by weight of the ingredients were as follows:

Ammonium 1,2,4-ethane-bis-dithiocarbamate 36,4% aqueous solution 63,19 g MnSO 3 aqueous solution (13,86% Mn) 36,85 g or for boiling with an additive - pure petrol, weigh:

52.8 g of wet water-washed filter cake

2.85 g ZnSO 3. 7 H2O, p. a.

169.5 g pharmacy gasoline.

The temperature of the liquid and vapor phases at the beginning of the distillation was 64.0 ° C and just before it was 66.6 ° C. During

045 minutes of distillation distilled 30.2 cm ^{3 of the} aqueous phase (the volume of the aqueous phase was no longer changed). The solid, finely dispersed, zinc cation coordination product with zinc 1,2-ethane-bis-dithiocarbamate (MANCOZEB), was separated from the continuous gasoline liquid phase by filtration through a pleated filter paper. Filtration gave 42.9 g of wet MANCOZEB, from which 24.5 g of highly concentrated, very fine MANCOZEB was obtained after evaporation of gasoline residues in an evacuated desiccator.

Chemical analysis of the product obtained revealed that it contained:

43.85 wt. % of total sulfur,

10.21 wt. % of total nitrogen,

19.88 wt. % manganese and 1.66 wt. % zinc.

Example 12

In order to obtain an objective picture of the particle size of the concentrated metal salts of alkyldithiocarbamic acids obtained by traditional methods as well as by the process according to the invention, microscopic measurements of several manganese 1,2-ethane-bis-dithiocarbamate samples [MANEB], zinc (ZINEBuj as well as samples) a zinc cation coordination compound with manganese 1,2-ethane-bis-dithiocarbamate (MANKOZEB).

The measurements clearly confirmed that during the dehydration of the washed samples of the metal salts of alkyldithiocarbamic acids in the presence of the additives according to the invention, the agglomerates are effectively separated into the form of primary particles. The ultimate consequence is the formation of substantially finer products, which usually no longer require further milling treatment. These claims are documented by the following photomicrographs of samples of concentrated MANEBs from the experiments described in Examples 6 and 9. 2, 3 and 8 (FIGS. 1 to 4).

Example 13

The assembly of the machinery described in this example, illustrating a process for preparing a concentrated and finely dispersed zinc cation coordination compound with manganese 1,2-ethane-bis-dithiocarbamate (MANKOZEB) according to the invention, is schematically shown in FIG. no. 5th

An aqueous 28.34% solution of 1,2-ethane-bis-dithiocarbamic acid (EBDTK-NH4) 101, a barium ammonium salt (EBDTK-NH4) 101 prepared as described in U.S. Pat. AO č. Whose density at 20 ° C was 1,099.9 kg.

. m ~ ³ , pH of the undiluted solution 8.9 and refractive index n20 ° C = 1.443, with every ^x 3? 5 8

100 wt. 49.12 wt. parts by weight of an aqueous manganese sulfate solution containing 12.26 wt. percent Mn 102.

After the addition of manganese sulfate, 0.1 wt. parts by weight of hexamethylenetetramine-urotropin 103 for every 100 wt. parts of the reaction mixture.

The reaction mixture - an aqueous suspension of a bright yellow color was stirred for about 15 minutes. Then, the suspension is collected in a stirred tank 2, from which it is conveyed by a centrifugal pump 3 for separation by means of a rotary vacuum filter 4, on which the raw filter cake is washed with water 104. The wet filter cake from the rotary vacuum filter 4 is collected in an annealing boiler 5 stirring, in which the filter cake was dispersed in about 3 times more water 104.

The dilute aqueous slurry of manganese 1,2-ethane-bisdiocarbamate (MANEB) prepared by the above process was pumped through the pump 6 to a rotary vacuum filter 7 which separated the solid-discontinuous phase from the filtrate-dilute aqueous solution (NH 2 SO 2 forming a continuous phase). suspension.

The filter cake on filter 7 was washed with an approximately 0.5% aqueous solution of urotropin 105. The wet filter cake from the rotary vacuum filter 7 is collected in containers 8, for each Mn ²⁺ weight slice in the wet cake the filter cake has overlaid 0, 55 wt. parts of crystalline ZnSCU. 7 H2O 106 and for each 100 parts by weight of the washed wet filter cake of MANEB, 0.45 wt. parts of urotropin.

The weight of the wet filter cake, crystalline zinc sulfate, and urotropin was transferred to a Lodige 9 oven into which a gas tank of 10 for each 100 wt. about 300 wt. parts of petrol.

After the dryer was closed with efficient stirring, the contents of the dryer were heated by circulating hot water and after reaching a temperature of about 65 ^° C, the dryer contents began to boil, condensing gasoline vapor and water in the cooler 11. from which the specifically lighter gasoline forming the topsheet flowed continuously to the dryer 9 and the water 104 forming the bottomsheet flowed through the divider 13.

When the condensate downstream of the cooler 11 no longer contained any water, a poor gasoline flow to the dryer closed and began to collect in the gasoline tank 10.

In this way, the gasoline was distilled off from the material forming the drier retainer 9. After removal of the last residues of the additive used, the concentrated and very finely dispersed coordination compound from the manganese 1,2-ethane-bis-dithiocarbamate 108 containing 31 wt. parts by weight of 1,2-ethane-bis-dithiocarbamate ion 8 wt. parts of bound manganese and 1 wt. part of zinc, through the outlet opening in the bottom of the dryer, was discharged from the dryer 9 with stirring.

Example 14

In this example, a schematic diagram of a mechanical engineering apparatus illustrating the use of a process for preparing a concentrated and very finely dispersed coordination zinc cation compound with manganese 1,2-ethane-bis-dithiocarbamate (MANKOZEB) is shown schematically in Figure 3. 6th

Crude 1,2-ethane-bis-dithiocarbamate (MANEBj) was prepared in precipitation boiler 1 in a similar manner to the previous example 13, which was freed from ammonium sulfate, a salt formed in the reaction mixture such as by-product of the precipitation reaction.

Concentrated aqueous suspension washed

Manganese 1,2-ethane-bis-dithiocarbamate is diluted by the addition of an additive (e.g. gasoline, cyclohexane, benzene, etc.) 107 and transferred to the desiccation boiler 3 through the appropriate pipeline to which it is added for each part by weight of manganese in the reaction 0.55 wt. parts of crystalline ZnSOi. 7 HaO 106 and 0.075 wt. parts of hexamethylenetetramine - urotropin 103.

After adding the additive from the reservoir 8, the distillation boiler 3 is closed and, with stirring, its contents are heated by heating with low pressure steam or hot water so that the suspension boils, the mixture of additive vapor and water vapor condensing in the cooler 4.

The condensate consisting of a mixture of two intermixed liquids is distributed in a separator 5, whereby an additive characterized by a lower specific gravity than water forms in the separator an upper layer, and flows through the side overflow into bed 3 where the reaction mixture boils.

After all the water has been distilled off, the low additive flow from the separator 5 to the distillation boiler 3 is closed and part of the reaction mixture is distilled off into the additive collection tank 8. The thickened suspension of MANKOZEB in the additive is then discharged from the boiler 3 into a Lůdige 6 dryer. 0.11 wt. parts of dry dispersant 109 consisting of 50% Slovasol SF and 50% SiO2 and 0.2 wt. parts of powdered thickened sulphite stillage 11a each by weight of manganese in the reaction mixture.

The additive residues are then distilled off from the reaction mixture under reduced pressure and by heating the dryer with hot circulating water in a duplicator, effectively homogenizing the contents of the dryer. The distilled additive after condensation in the cooler 7 is collected in the additive container 8.

Example 15

The wet, washed manganese (ethylene bis) dithiocarbamidate dihydrate filter cake, prepared as described in Examples 2 and 3, was poured in a screened boiling flask (see Examples 4-10), so that the amount of gasoline was about 7 times the filter cake.

The flask was placed in an electrically heated "nest", with a special distillation attachment with a bad cooler (the function of the attachment explained in Examples 4 to 10) was placed on its central bump NZ 29 and into the side necks of the brewing flask terminated with ground glass joints (NZ 14.5). ), a ground-glass joint was introduced to allow temperature monitoring of the liquid and vapor phases.

After 6 hours of distillation, the amount of water in the reflux condenser was no longer changed, the solids composition in the brewing flask corresponding to anhydrous manganese ethylene bis (dithiocarbamidate) (MANEB). The temperature of the liquid and vapor phases was between 64 and 67 ° C during the distillation.

The heating was then stopped and after cooling, the petrol suspension of anhydrous MANEB was separated by filtration.

Furthermore, 10 parts by weight of the anhydrous MANEB obtained in the above manner were suspended in an aqueous solution containing 0.5% by weight. parts ZnSO4 in 10 wt. parts of water. The suspension thus prepared was stirred for 1 hour at room temperature (25-20 ° C). Thereafter, the aqueous suspension was overlaid again with pure pharmacy gasoline and the water contained in the reaction system was separated by distillation with gasoline - in a manner similar to the previously described dewatering of the washed filter cake of manganese ethylenebis-dithiocarbamidate dihydrate.

After the distillation of the water was complete, the gasoline slurry was separated by filtration, and the gasoline residues were removed from the filter cake by evaporation in an evacuated desiccator. By sieving the product thus prepared, 9.1 wt. The product was thoroughly washed with a mixed solution of methanol and distilled water and dried at 50 ° C and a pressure of 5 mm. The product thus prepared contained 1.9% Zn, 20.3 percent Mn, 56% CS2, 10.2% N, 17.6% C and 2.3% H.

Claims (1)

SUBJECT A process for the preparation of concentrated, finely dispersed metal salts of alkyldithiocarbamic acids by reacting a water-soluble acid with at least one water-soluble salt of manganese and / or zinc and / or a medium characterized in that after removal of the salt formed in the reaction mixture as byproduct at least one of a group of substances having a boiling point of their mixture with water below the boiling point of water at the same pressure is added in wet conditions, such substance or mixture of substances being limitedly miscible with water and having a specific gravity below or higher than is the specific gravity of water, more preferably some of the zinc salts and / or medium and / or manganese are added to the main reaction product of the precipitation reaction, and some of the substances stabilizing the reaction product are also added, the mixture thus obtained at atmospheric or lower pressure . before the atmospheric pressure is brought to boiling, water is separated from the mixture of the vapors after their condensation and the substance or mixture of substances characterized by said properties is returned to the environment in which the mixture is boiling and distilling, whereby boiling and distillation presence of substances modifying the properties of the final product.