DE1468511B - Metal-manganese mixed salts of ethylene bisdithiocarbamic acid - Google Patents

Description

The present invention relates to water-insoluble mixed salts of ethylene bisdithiocarbamic acid with manganese and with cobalt or copper, iron, lead, mercury, nickel and zinc, with the Molar ratio of manganese to metal is between 40:60 and 90:10, as well as a method for Production of such salts which are suitable as fungicides.

Salts of ethylene bisdithiocarbamic acid are known from US Pat. No. 2,317,765, which are highly effective fungicides. The zinc salt (known under the trade name "Zineb") as well as the Manganese salts (known under the trade name "Maneb") were widely used Used to combat a wide variety of plant diseases. Nevertheless, there is a need for connections which either in lower doses the same effects or at the same doses achieve better effects than »Zineb« or »Maneb«, whereby the aim is also to that even particularly delicate leaves are not attacked. There is also a need for connections which maintain their effectiveness over longer periods of time or have a broader spectrum of activity in terms of plant diseases.

Mixing different metal salts has been proposed to achieve greater stability. A mixture of manganese dimethyldithiocarbamate and zinc dimethyldithiocarbamate is said to be a better one Have stability. For example, this can be used to produce such a mixture Precipitate the manganese salt in a mixture with the zinc salt. With the dialkyldilhiocarbamic acid you can act on this In this way only salt mixtures are produced, while the result is the result of the Äthylenbisdithiocarbamaten is completely different.

It has now been found that a new type of compound of metal-manganese mixed salts is obtained, if you use an aqueous solution of a water-soluble manganese salt in a manner known per se and a water-soluble cobalt or copper, iron, lead, nickel, zinc and mercury salt, wherein the molar ratio of the manganese salt to the other metal salt is 40:60 to 90:10, at a temperature of 10 to 5 (K'C with an equivalent amount of a water-soluble salt of Ethylenebisdithiocarbamic acid converts.

Working methods described for the formation of mixtures of a manganese salt and a zinc salt to lead. According to this United States patent, "only the dimethyldithiocarbamic acid which a monobasic acid is used. Monobasic acids, however, are only easier to form and monomeric salts and not capable of forming mixed salts.

In contrast, according to the invention of the ethylene bisdithiocarbamic acid, a dibasic Assumed acid, with mixed salts when using the above-mentioned higher-valent cations with a chain-like or lattice-like structure and a polymeric character.

The German Auslegeschrift 1 055 526 describes the precipitation of simple heavy metal salts of Äthylenbisdithiocarbamic acid by reacting a corresponding heavy metal salt with alkali or Alkaline earth dithiocarbamate in the presence of a flocculant and when maintaining a specific pH range described. As heavy metals, copper and zinc are proven by examples, while iron, mercury, and bismuth are only mentioned. From this reference it can be seen that that already the double conversion between an Alkaliäthylenbisdithiocarbamat and a certain one Heavy metal salt raises problems caused by the described in the cited German Auslegeschrift Procedure to be overcome. Therefore, this German interpretative document cannot provide any suggestion whatsoever to give to the method according to the invention.

With physical methods you can get the new

5 distinguish salts of the present invention from the equivalent physical mixtures of insoluble manganese ethylene bisdithiocarbamate with another metal ethylene bisdithiocarbamate.
The X-ray diagrams show that the products of the invention are not mixtures. Mixtures show patterns which combine the patterns of the individual salts, while the products of the present invention produce different lines therefrom or reveal other differences. The data of the X-ray diagrams reproduced below are obtained with _{radiation designated as CuK 11} with a copper electrode and a nickel filter.

For example, you can use the zinc-manganese mixed salts of Äthylenbisdithiocarbamic acid Manganese to zinc molar ratios in the range of 40:60 to 90:10 indicate the x-ray lines or peaks consider. First and foremost, it should be noted that the lines characteristic of "Manch" at 8.0 and 6.51 Å in the mixed salt are reduced in intensity, while those for "Maneb", "Zineb" and the new mixed salts characteristic lines at 6.90, 4.48 and 3.03 Å also in their relative proportions Intensity are greatly changed. Some of the lines characteristic of pure "Zineb" disappear fully. At the same time, however, the manganese-zinc mixed salt of the invention has a value of about 7.36 Å new line of medium intensity.

Another distinguishing feature of the X-ray diagram of the mixed salts of the invention lies in the broadening of lines and diffraction packs. The pure individual metal salts of ethylene bisdithiocarbamic acid result in relatively sharp lines or peaks, even in mixtures.

These points become clearer by comparing the numbers obtained, which are summarized in Table I. are for

1. Zinc-manganese mixed salt of Äthylcnbisdithiocarbamic acid, produced by reacting 70 moles of manganese sulfate, 30 moles of zinc sulfate and an equivalent amount of disodium ethylene bisdithiocarbamate (Products),

2. a mixture of »Maneb« / »Zineb« 70:30 (Ge <> o mixed Z),

3. "Maneb" alone,

4. "Zineb" alone.

The relative intensities of the peaks are identified as follows: S = strong, MS = medium, M = medium, MW = medium weak, W = weak, VW = very weak.

"Maneb" S. Table I. ( agramm (Ä Products 8.00 in the X-ray di jcmisch Z 8.00 M. M. "Zineb" 8.00 p 7.36 M. 6.90 M. 6.90 M. Peaks 6.51 6.90 p 6.51 W MS 6.90 p 6.51 S 4.48 4.82 W. 4.48 M. 4.81 M. 4.48 MS 4.48 MW 3.62 W. S. 3.50 W 3.45 VW 3.03 3.45 W 3.03 M. 3.25 W 3.03 S 3.03 MW

The mixed salts of mangano and mercury salts, such as in the molar ratio 40:60 to 90:10, keep some lines characteristic of pure "maneb", but with some variations in relative intensity. For example, the line at 8.0 Å has dropped from strong to medium, and the lines at 4.48 and 3.03 Å are also a little less intense. New lines appear at 6.07 Å (strong), 4.27 Å (strong) and 3.32 Å (medium). The latter is a bit wide.

Also the mixed salts of mangano and lead salts within the molar ratios 40:60 to 90:10 preserve some of the lines of pure "maneb", but with reduced intensity. This is the case, for example for the lines at 8.0, 4.48 and 3.03 Å, all of which are attenuated. New lines appear at 9.60 Å (strong), 5.47 Å (weak) and 4.93 Å (weak).

The mixed Äthylenbisdithiocarbamate from mangano and ferric salts with molar ratios of Metals like above keep the lines of "Maneb" at 8.0, 4.48 and 3.03 Å, but with attenuation the intensity from strong to medium. A broad peak of medium intensity appears in the range 6.5 to 7.5 Ä. The X-ray lines or maxima are also generally characterized by a width.

The mixed salts produced from mangano and ferrous salts within the specified molar ratios preserve the characteristics of the pure "maneb" with subordinate changes in intensity. For example, the lines at 4.48 Å (medium) as well as the lines at 8.0 and 3.0 Å are somewhat attenuated, while the lines at 6.9 and 6.51 Å have a slightly higher intensity. A new medium faint line appears at 7.36 Å.

The mixed salts with nickel or cobalt are by broadening the lines or maxima, which for "Maneb" are characteristic, with all lines characteristic of "Maneb" experience a weakening. For example, the lines at 8.0 and 3.03 Å are strong for pure "maneb" and only medium for the mixed salts, while the line at 4.48 Å decreases in intensity for the mixed salt.

For the manganese-copper mixed salts with molar ratios of the metals in the range from 40:60 to 90:10 are two somewhat broad maxima characteristic, which are 7.65 to 7.80 Å and about 3.86 Å. At the same time, the lines characteristic of copper-ethylene bisdithiocarbamate are of medium intensity at 7.42, 5.25, 3.49, 3.15 and 3.0 Å and the one strong line at 4.36 Å attenuated to almost extinction. The lines at 8.0, 4.48, and 3.03 Å are very faint.

"Maneb", "Zineb" and the individual other metal salts of ethylene bisdithiocarbamic acid are used characterized and identified by the following infrared absorption maxima: at least

ίο a sharp band at 3 to 3.3 α (medium), absorption in the range of 6.5 μ (strong), three usually sharp bands in the range of 7 to 6.2 μ (medium to weak) and at least one band at 9.5 µ (medium), one band in the range of 10.3 to 10.6 µ (strong), and one weak Band in the range from 12.5 to 13 μ.

"Zineb" alone or in physical mixtures shows the general characteristics given above Infrared absorption maxima of ethylene tennis dithiocarbamates and additional individual special maxima at 9.55 and 10.25 μ. The zinc-manganese mixed salts of the invention do not reveal these specific maxima of "Zineb", and consequently they cannot be physical mixtures.

In general, infrared technology can also be used to show that the others Metal-manganese mixed salts of the invention are not mixtures of the simple salts.

To provide ethylene bisdithiocarbamate ions, all water soluble salts of ethylene bisdithiocarbamic acid are used suitable, for example the salts of lithium, sodium, potassium, ammonium, quaternary Ammonium, calcium or magnesium.

Any soluble manganese salt such as acetate, sulfate, chloride is used as a source of manganese ions or nitrate applied in anhydrous or hydratisicrier form. The manganese salt does not need pure / 11 being. The other metal salts are made of some water soluble chloride, sulfate, nitrate. acetate or the like of cobalt, copper, iron. Lead. Nickel. Mercury or zinc or mixtures of several such metals supplied. Inorganic salts are generally preferred for reasons of cost. because Lead sulphate and lead chloride are insoluble, must of course in the case of lead, such a combination of salts are chosen that lead and sulfate or Chloride ions are not present at the same time. Likewise, when using Calciumäthylcnbisdithiocarbamat that sulfate ion can be excluded. In the case of the mercury salts, nitrate is preferred, because the chloride is only partially soluble in water and the sulfate is in aqueous solution known to decompose. The concentrations of the salts in their solutions can be largely of high Vary dilution to saturation. It is crucial that the salts, when used with the solution of a Äthylenbisdithiocarbamats come into reaction, at least 5% insoluble product, calculated on the weight of the reaction mixture.

f> o The mixture of manganese salt and an or several other salts will be in roughly stoichiometric equivalent amounts to the Äthylenbisdithiocarbamationen applied. The metal ions or the ethylene bisdithiocarbamate ions can optionally also be present in excess be, usually an excess in both cases of 10 mole percent not exceeded. The excess of each component can be in the product

be left or by washing or extracting be removed from it.

The molar ratio of the metal ions in the mixture of the water-soluble salts for reaction with the equivalent of soluble Äthylenbisdithiocarbamat can be varied within a certain range. Preparations with superior fungicidal effectiveness are obtained when the molar ratio of the manganese to the other metal ions between 40:60 to 90:10. preferably between 50:50 to 80:20. The optimal ratio fluctuates somewhat in Depending on the metal to be combined with manganese and the reaction conditions.

The aqueous solution of the mixture of salts of manganese and the other metal can be used as an aqueous solution Solution of Äthylenbisdithiocarbamats are added. But you can also do the reverse Work sequence, or you can the two reaction solutions at the same time in a reaction vessel let it flow. The latter method is preferable because in this way a continuous working method can result.

The reaction between the soluble salt of ethylcnbisdithiocarbamic acid and the mixture of manganese salt and the other metal salt is at temperatures between about 10 and 50 C in carried out an aqueous system. Concentrations are used, the slurries with 5 to about 10 percent by weight, preferably about 10 to 30 percent by weight of the soluble precipitate. The lower limit results from one or more Reactions in which the reaction mixtures are more dilute than indicated and which are therefore not too lead to the desired mixed salts. On the other hand, the above concentrations are only those at which mixing of the reactants can be carried out most conveniently and which resulting product slurry is best to handle.

If desired, the pH can be adjusted during the reaction by the presence of buffer substances or acids are regulated so that the reaction mixture has a pH of 2 to 11. preferably 3 to 8.

The reaction is rapid, but with dwell times 10 minutes to 2 hours are recommended. In a usable way of working, approx stoichiometrically equivalent amounts of manganese and other metal ions in solution with a solution a soluble Äthylenbisdithiocarbamats at about 40 C with stirring and mixed for 15 to 25 minutes held.

The product can for example be isolated on the filter or in the centrifuge and then underneath its decomposition temperature. But you can also let the reaction mixture settle, Separate the supernatant liquid by suction or the like and dry the remaining slurry. Finally, you can also evaporate the entire reaction mixture to dryness, of course soluble salts remain in the product.

Drying can be carried out under normal or reduced pressure, for example by spray drying. Drying in the rotating vacuum drum! or in bowls. The products of the invention must below their decomposition temperatures, and for this purpose the products are said to be so dried be that the temperature of the dry end product remains below about 90 ° C. For example it is favorable to the reaction products between 40 and 80 C under reduced pressure, for example from 5 to 30 mm Hg, to dry.

After drying, it is expedient to convert the solid substance into a fine division, for example by micropulverization, micronization. Breaking, sieving or other methods of crushing. In order to promote the accumulation of finely divided products, one can, if necessary, on one or several stages of manufacture wetting or dispersing agents, e.g. B. sodium lignosulfonal, sodium naphthalene formaldehyde sulfonate or sodium dioctyl sulfosuccinal or combinations such as alkylphenoxy polyetheroxyethanol and lignosulfonal, or condensation products of polyglyccrine or oleic acid and Use sodium naphthalene formaldehyde sulfonate. If desired, one can use the Melall manganese mixed salts Ethylcnbisdithiocarbamic acid by adding 0.5 to 4 "," Hexamethylenetetramine to the slurry or to the dry products or by adding a small amount stabilize a non-reactive desiccant.

The mixed salts can be made flame-proof by giving them at least 20% of their Weight of fuller's earth added. Also synergistic substances like calcium polysulphide. can be added.

.10 The purity of the products changes depending on the particular isolicrmcthodc and / or the presence of additives.

Tables 11A and II B show analytical values calculated in percent by weight, of proportionate

-V ^s pure metal-manganese mixed salts of ethylcnbisdithiocarbamic acid. in which the second metal (X) is zinc. Is copper, nickel, cobalt or iron and the ethylene bisdithiocarbamates are free of soluble reactants and moisture. The

4 ^U corresponding values for mixed salts of lead and mercury can be seen in tables ΠΙΑ and 1MB. The range of metal values is given for the limits of manganese to other metal with molar ratios from 40:60 to 90:10.

Table IIA

Composition of metal-manganese mixed salads of Ätlnlenbisdithiocarbamatc

Suhstilucnt

CS, j

Nitrogen [

Carbon I.

hydrogen

56.1 to 57.3

10.3 to 10.5

17.7 to 18.1

2.1 to 2.3

Table II B

Metal content! in metal-manganese mixed salts of ethylene bisdithiocarbamic acid

Melatl i

6, ■ - ■ j

Manganese p. I to I p. 5

/ inc 2.4 to 14.5

Nickel 2.2 to 13.2

continuation

metal

Cobalt.
Copper.
Iron ..

2.2 to 13.2
2.4 to 14.1
2.1 to 12.6

Table IHA

Compositions of metal-manganese mixed salts of ethylene bisdilhiocarbamic acid

Substituent

CS ₂

Nitrogen...
Carbon.
Hydrogen.

% 54.3 42.7 until 10.0 7.9 until 17.1 13.5 until 2.1 · 1.7 until

Table IHB

Content of metal in metal-manganese mixed salts
of ethylcnbisdithiocarbamic acid

Mclal!

manganese

lead

mercury

6.2 to 17.6
7.4 to 34.9
7.1 to 34.1

ED «,, - value of» Maneb «

ED ₅₀ value of the sample

represents.

For the sake of simplicity, the various metal-manganese mixed salts tested are shown in Table IV marked with abbreviations.

The test data are summarized in Table V for the following preparations.

Table IV

Abbreviations for the metal-manganese mixed salts of Ethyienbisdithiocarbamic acid

connection Metals Molar ratio
implemented A (comparison) Manganese to zinc 30:70 15th B. Manganese to zinc 40:60 C. Manganese to zinc 50:50 D. Manganese to zinc 60:40 E. Manganese to zinc 70:30 20th F. Manganese to zinc 80:20 G Manganese to zinc 90:10 H Manganese to Nickel 50:50 I. Manganese to Nickel 70:30 25th J Manganese to Cobalt 80:20 K Manganese to Cupri 50:50 L. Manganese to Cupri 60:40 M - Manganese to Ferri 70:30 30th N Nangan to Ferro 70:30 O Manganese to lead 70:30 P. Manganese to Mercuri 60:40

40

The metal-manganese mixed salts of ethylene bisdithiocarbamic acid have unusually high efficacy in comparison with the pure manganese ethyl bisdithiocarbamate. In a test, the resistance to late blight on tomato plants checked. Be there

1. Tomato plants until they run off with suspensions of the active ingredients to be tested in one Injected dose series,

2. the sprayed plants are dried,

3. the dried plants a mist of finely atomized Exposed to water for 16 hours,

4. dried the plants again,

5. the plants exposed for 4 days,

6. the plants with Phytophthora infestans in a suspension with 30 (XK) spores in cubic centimeters inoculates,

7. Place the plants at 100% relative humidity and 11 to 13 C for about 22 hours for spore incubation held,

8. the plants exposed to light for 42 hours,

9. The injuries are counted.

_{The ED 50} values are calculated from the counts of the various dosage series, ie the amount, expressed in 10 ~ ^f ~ parts, which results in a 50% kill of the pest. This test is carried out with "Maneb" and "Zineb" as standard and with various zinc-manganese mixed salt preparations. The results are given as the “Maneb” value, which corresponds to the expression. In Table V below, test values for typical preparations are given.

Table V

connection

Maneb index 0.5 2.1 2.8 3.0 3.2 2.7 2.2 1.00 0.31 Manganese zinc Molar ratio 30:70 40:60 50:50 60:40 70:30 80:20 90:10 100: 0 0: 100

A.
B.
C.
D.

E.
F.
G

"Maneb"
"Zineb"

Table VI below shows dry mixtures of various weight percentages of "Maneb" and rated "Zineb".

Table VI
Long-term effect of mixtures against late blight

Dry mixes Maneb index ⁶⁵ 20% "Maneb", 80'V ₀ "Zineb" ..
30% "Maneb", 70% "Zineb" ..
50% "Maneb", 50% "Zineb" .. 0.48
0.60
0.79

009 515/187

continuation

Dry mixes

67% »Maneb«, 33 ^b / ₀ »Zineb«
80% »Maneb«, 20% »Zineb«

"Maneb"

"Zineb"

Maneb index

0.98
0.93
1.00
0.29

Tables V and VI prove that the zinc-manganese mixed salts of Äthylenbisdithiocarbamic acid with zinc-manganese molar ratios of 60:40 to 90:10 compared to Phytophthora infestans Tomatoes are much more effective than "Maneb" alone, "Zineb" alone, or dry mixtures of both Fabrics.

Table VII shows other test results the same pest.

Various ethylene bisdithiocarbamates have been used against Pseudoperonospora on cucumber plants grown in the field cubensis with a 7-day spray, starting when the plants have three leaves, applied. Spray irrigation was used from above. The application amounts were 0.5 kg / 380 1. 3 weeks after the start of the experiment, the injuries that were most severe on the ten were counted infected leaves were recognizable. The averages of the enumeration are given in Table VIII compiled.

is also confirmed against Cercospora Apii on celery plants. Here, a 4-day spray treatment with 0.5 kg / 380 l was carried out 15 days after the seedlings had been transplanted. Spray irrigation was applied. The damage was counted 6 weeks after the first spraying. The injuries to randomly chosen seedlings were counted and the average number of injuries to 25 sets of leaves was calculated. The results are given in Table IX. ^^ , _χ

Control of Cercospora Apii on Sellcrie plants

Injuries
25 sheet seats each

Applied amount 15th Product C 50:50 Mn / Zn - Product F - 80: ·> () ²⁰ Mn / Zn Product H 50:50 Mn / Ni "Maneb".

table ; VII 50 »Manetx <-
index Injuries
on ten sheets each connection metal 30th 1.2 H Mn / Ni 20th I. Mn / Ni Molecular Ratio 50 J Mn / Co 50 40 K Mn / Cu 70 30th L. Mn / Cu 80 30th M. Mn / Fe ⁺³ 50 30th , 2 N Mn / Fe ⁺² 60 40 , 3 O Mn / Pb 70 , 2 P. Mn / Hg 70 , 2 "Maneb" 70 , 9 "Zineb" 60 3.3 table 2.6 1.5 VIII 1.0 0.25 ! 2 of Pseudoperonospora cubensis 8th on cucumber plants crowd 18th 46 50 .. 20th 50 Combat Applied Products C Mn / Zn - 50 Products F Mn / Zn - 80: Products H Mn / Ni - 50: "Maneb" ...

The same high effectiveness of the typical mixed salts of the invention representing products C, F, H 78
66

62
107

Favorable results were obtained with the metal-manganese mixed salts of the invention against Stemphylium solani achieved on tomatoes. You start the treatment with 0.5 kg / 3801 of tomato plants with three real leaves and carries out a 4-day treatment Application of spray irrigation from above. 6 weeks after the first spray are five Plants in each bed selected 20 sets of leaves and counted the average number of injuries on them. With product C, 73 injuries were determined, with »Maneb« 93 injuries.

Also favorable results were obtained against Alternaria solani on tomatoes and potatoes, against Septoria apii on celery, against Collatotrichum lindemuthianum and Uromycea phaseoli on beans.

The metal-manganese mixed salts of the invention can be used in almost pure form or as unpurified products, namely in the Ways in which "maneb" and "zineb" are currently substituted. Application can be made using by hydraulic spraying or by dusting. The respective dilution and the Application method depend on the equipment used, the application method and that used

pest to be controlled. ^{In general, 225 to 2250 g / 4.05 × 1000 m 2} are used in aqueous spray solutions which are used in amounts of 19 to 662 liters. In order to improve the coverage of the plants by the spray, it is often advisable to add surface-active substances. A typical spray formulation consists of 0.9 kg of iron-manganese mixed salt deräthylenbisdithiocarbaminsüurc, made from metal salts in a molar ratio of 80:20, 113 g of a condensate of polyglycerol, oleic acid and phthalic anhydride, and 38 liters of water. Mix thoroughly with stirring and dilute with water to a volume of about 380 liters to make an effective spray. Instead of the specified condensate, a commercial product can be used which is referred to as glycerol mannitane laurate. Furthermore, condensation products of sorbitol esters with ethylene oxide can be used.

The metal-manganese mixed salts according to the invention are processed into dust by adding them Extenders such as natural clay, kieselguhr, pyrophyllite, tallow, calcium silicate, magnesium carbonate, Sulfur or the like, admits. For example, 90 parts of calcium carbonate are mixed with 10 parts of a Zinc manganese mixed salt, which contains 7.3% manganese and 12.9% zinc.

If desired, this recipe can also contain an addition of 0.5 to 2% of a dispersing agent, such as lignin sulfonate or sodium formaldehyde naphthalene sulfonate. Will be wettable powders prepared from the metal-manganese mixed salts according to the invention by being with one or several wetting agents and optionally with a dispersing agent and for some purposes mixed with a minced solid carrier. For example, a copper-manganese mixed salt is mixed in a weight ratio of 50: 5: 45, which is made from salts in a molar ratio of 1: 1, with a commercial product made from 60% magnesium carbonate and 40% cetylphenoxypolyoxyalhanol with about ten ether groups, as well as with Fuller earth.

The metal-manganese mixed salts according to the invention are applicable alone or in conjunction with other known fungicides, e.g. B. with dinifro- (l-methylheptyl) -phenylcrotonate, fixed copper or sulfur, with insecticides or miticides, such as 1,1,1-trichloro-2,2-bis- (p-chlorophenyl) -ethane, l, l-bis (p-chlorophenyl) -2,2,2-trichloroethanol, 2- (p-tert-butylphenoxy) -isopropyl-2-chloroethyl sulfite, or organic phosphorus compounds such as "parathion" or "malathion", or combinations thereof.

The following examples illustrate embodiments of the invention. The parts are parts by weight, unless otherwise stated.

example 1

• 40

_{A solution of 1584 parts of manganese chloride.4H 2} O and 1637 parts of zinc chloride in 4000 parts of water is allowed to flow over the course of 4 hours with stirring to a solution of 22,260 parts of a 23% strength aqueous solution of disodium ethylene bisdithiocarbamate, while the temperature of the reaction mixture is increased to 35 holds up to 42 C. The mixture is stirred for a further 2 hours at the same temperature. The resulting slurry is suctioned off on the filter, the filter cake is washed with 1000 parts of water, then reslurried with 6500 parts of water and spray-dried in an atomizer at 40,000 rpm at an air inlet temperature of 285 ° C. and an average outlet temperature of 130 ° C. It is crushed the dried product has an average particle size of 2.1 μ and contains 4630 parts of a yellowish white powder which, according to analysis, contains 49.6% CS ₂ , 7.3% manganese, <*> 12.9% zinc and 1.5% water According to the CS ₂ value, the product contains 89% pure ethylene bisdithiocarbamate. It shows the typical infrared lines of the ethylene bisdithiocarbamates, but not those that are characteristic of "Zineb". It is a zinc-manganese mixed salt of ethylene bisdithiocarbamic acid and shows in the X-ray diagram the characteristic maximum at 7.36 Å.

Example 2

A solution of 143.5 parts of manganese nitrate · 6 H ₂ O and 149 parts of zinc nitrate · 6 H ₂ O in 800 parts of water is added with stirring over the course of 90 minutes at a temperature of the liquid of 40 to 44 ° C. with a solution of 256 parts of disodium ethylene bisdithiocarbamate in 894 parts of water and stirred for a further 90 minutes at the same temperature. The resulting slurry is suctioned off on the filter, the filter cake is washed with 1500 parts of water and filtered again. The filter cake is dried for 18 hours at room temperature in the dish and then for 6 hours at 10 to 18 mm with a jacket temperature of approximately 75 ° C. in the vacuum drum. 252 parts of zinc-manganese-ethylene bisdithiocarbamate with a particle size of 1.8 α and a purity of 89% (CS, analysis) are obtained. The product contains 50.3 "" CS "9.2% Mn, 11.7% Zn and less than 0.2""H ₂ O. In the X-ray diagram, the characteristic maximum occurs at 7.36 Å.

Example 3

_{A solution containing 936 parts of manganese sulfate · 2H 2} 0.1436 parts of a 47.5 is added to 5430 parts of a 45% strength aqueous solution of diammonium ethylene bisdithiocarbamate over the course of 3 hours at a temperature of 26 to 29 ° C. with stirring % aqueous solution of zinc chloride and 5000 parts of water was prepared. The mixture is stirred for a further 2 hours while maintaining the same temperature, the product is filtered off, washed with about 20 (X) parts of water, the filter cake is dried in the dish for 20 hours at room temperature and then at up to 80 ° C./10 mm in a rotary vacuum dryer . 2451 parts of a zinc-manganese mixed salt of ethylene bisdithiocarbamic acid purity 79% are obtained, which, according to analysis, contains 44.1% CS ₂ . Contains 8.7% Mn and 10.8% Zn. The characteristic maximum occurs at 7.36 A in the X-ray diagram.

Example 4

1000 parts by volume of an aqueous solution containing 48.4 parts of zinc sulfate and 88.1 parts of manganese chloride are placed in a reaction vessel and 1000 parts by volume of an aqueous solution containing 256 parts of disodium ethylene bisdithiocarbamate are added at constant speed and with stirring over a period of 2 hours. The temperature is kept at 23 to 28 ° C. and the mixture is stirred for a further hour. The insoluble precipitate is separated off by filtration, washed thoroughly with water to remove all soluble substances, dried overnight in air and then for 6 hours at 2 mm pressure and a temperature of up to 28 ° C. in a rotary vacuum dryer. 250 parts of a yellowish-white substance are obtained as zinc-manganese mixed salt. According to analysis, it contains 55.6% CS ₂ , 14.3% Mn, 7.2% Zn, 17.5% C, 2.2% H and 10.1% N. The characteristic maximum appears in the X-ray diagram at 7.36 Å.

Example 5

800 parts of water are placed in a reaction vessel equipped with a stirrer, two feed lines and a thermometer. A solution of 1259 parts of disodium ethylene bisdithiocarbamate 6H ₂ O in 2740 is fed through one supply line

Divide water and through the other supply line introduced a solution of 141.7 parts of zinc chloride and 365.6 parts of manganese sulfate in 35 (K) parts of water. After the water in the reactor has been heated to 38 ° C., it is left with over the course of 1 hour uniform speeds both solutions flow into the reactor at the same time with stirring, while the temperature of the reaction mixture is kept at 38 to 42.degree. A solid substance falls and the resulting slurry is stirred for an additional 2 hours. Then you filter that Product off, washed with 4 (K) parts of water, dried for 12 hours in a vacuum tray dryer, whereby 75 to 80 ° C circulating water and 5 to 15 mm of pressure are used.

953 parts of a solid substance (purity 88%) are obtained which, according to analysis, contain 49.6% CS ₂ , 12.6% Mn, 6.5% Zn and 5.1% H ₂ O. In the X-ray diagram, the characteristic maximum occurs at 7.36 Å. The zinc-manganese mixed salt is comminuted to an average particle size of about 2 u.

Example 6

An apparatus suitable for continuous operation is used, consisting of two with a stirrer provided, jacketed reactors of the same content and a continuous rotary filter. At first Two feed systems and pumps are provided to transfer slurry from the first to the reactor second and from the second reactor to the filter. The two feed systems are with filled with the solutions to be used, the first of which is an aqueous solution of 256 g of disodium ethylene bisdithiocarbamate per liter and the second is an aqueous solution of 121 g of manganese sulfate and 32.3 g of zinc sulfate per liter.

These two stock solutions are allowed to flow into the first reactor at uniform rates. During operation, the pump speeds are adjusted so that the average residence time in each reactor is 60 minutes. Cooling water is allowed to flow through the jackets of the reactors in order to maintain the temperature in the range of 20 to 24 "C. The slurry from the second reactor is continuously filtered and washed once during the filtration step. Prepared 5% aqueous slurry and fed to a spray dryer, which is operated with an atomizer speed of 40,000 rpm, an average inlet temperature of 290 ° C. and an average outlet temperature of 125 ° C. The product obtained as powder is atomized again. Finally, the zinc-manganese is contained -Mixed salt 49.8% CS ₂ , 14.5% Mn, 4.4% Zn and I,! ⁰ ,, H ₂ O, with an average particle size of 2.2 μ. In the X-ray diagram, the characteristic maximum occurs at 7, 36 A on.

60 Example 7

To a solution of 2190 parts of manganese _{sulfate.2H 2} O, 373 parts of 47.5% strength aqueous zinc chloride solution and 9000 parts of water in a reactor, 14,600 parts of an aqueous Nabam solution are allowed to flow with stirring at a temperature of 21 to 24 ° C. Contains 7% disodium ethyl bisdithiocarbamate. The resulting slurry is stirred for an additional 2 hours, then filtered on a rotary continuous filter with spray washing during the filtration cycle. The filter cake is dried for 24 hours in a vacuum pan dryer at 10 mm and a jacket temperature of 75 C. Using a 0.5 mm sieve with six hammers and a corrugated dome at 6950 rpm, the dried material is micropulverized and 3465 parts of one are obtained zinc-manganese mixed salt contains (90% per pure CS ₂ -Analysc healing), which 51,2'V ₀ CS _2, 17.1% Mn and 2.2% Zn the Äthylenbisdithiocarbaminsäure. In the X-ray diagram, the characteristic maximum occurs at 7.36 Å.

Example 8

5570 parts of an aqueous solution containing 1280 parts of disodium ethylene bisdithiocarbamate are placed in a reactor equipped with a stirrer, thermometer and two supply systems. A solution of 468 parts of manganese sulfate · 2H ₂ O in 2000 parts of water is fed through one feed system, while a solution of 594 parts of nickel chloride · 6H ₂ O in 2000 parts of water is fed in through another. In the course of 3 hours, the two stock solutions are allowed to flow into the reactor at a temperature of 25 to 34 ° C. while stirring at approximately the same rates. The mixture is stirred for a further 2 hours, the resulting slurry is filtered under full vacuum, washed with 20 (K) parts of water and the filter cake is dried at 70 ° C., 5 to 15 mm on a rotary vacuum dryer. The dark brownish-green solid material is sieved through a sieve with a mesh size of 0.8 mm and 1360 parts of a nickel-manganese mixed salt with an average particle size of 2 μ are obtained with a purity of 85%. The product contains 48.6% CS ₂ , 9.1% Mn, 9.7 "ο Ni. The X-ray diagram of this product and of the product prepared according to Example 9 is similar to that of" Maneb ". It is distinguished by the broadening of the lines or peaks characteristic of "Mancb" where the intensity is reduced.

Example 9

Into a reactor with KK) parts of water and can be at substantially equal speeds flow, simultaneously with stirring two separate solutions of which one of 149,7Teilen manganese sulfate · 2 H ₂ O, 49.7 parts Kobaltacctat -4H ₂ O and 1000 parts Water and the other of 1200 parts by weight of an aqueous solution of 364 parts of disodium ethylene bisdithiocarbamate · 6H ₂ O consists. The feed takes place at a temperature of 27 to 33 C and lasts 60 minutes. The mixture is stirred for a further 2 hours, filtered through a suction filter, the filter cake is washed with 200 parts of water and allowed to air dry. The air-dried filter cake is dried in a chamber kept at 50 to 60 ° C. at 20 to 30 mm pressure for 6 hours with stirring in vacuo. 285 parts of a brownish green cobalt-manganese mixed salt of ethylcnbisdithiocarbamic acid are obtained in 85% purity, which according to analysis contains 48.4 "" CS _2. 14.3% Mn and 3.8 "" Co.

Example 10

A solution of 46.8 parts of manganese _{sulfate.2H 2} O, 39.9 parts of cupric sulfate and 400 parts of water is added to a solution of 124.5 parts of dipotassium ethylene bisdithiocarbamate in 425 parts of water at 34 to 41 ° C. over a period of 2 hours with stirring . A small amount of a filter aid is added to the resulting slurry and filtered on the suction filter. The filter cake is washed with 200 parts of water and the solid substance is dried with stirring at 70 ° C./5 to 10 mm in vacuo. The dried product is sieved through a sieve with a mesh size of 0.8 mm and 156 parts of a copper are obtained Manganese mixed salt (purity 78% according to CS ₂ analysis) in a brownish-gray color with a particle size of 0.8 μ. The product contains 44.1% CS ₂ , 8.5% Mn and 9.7% Cu this product has two broad peaks at 7.65 to 7.80 Å and at 3.86 Å.

Example 11

_{A solution of 131 parts of manganese sulfate · 2 H 2} O and 48.6 parts of ferric chloride in 885 parts of water and a solution of 131 parts of manganese sulfate · 2 H 2 O and 48.6 parts of ferric chloride in 885 parts of water are added to 100 parts of water with stirring and at a temperature of 26 to 33 ° C. for one hour simultaneously and at practically the same rates those of 364 parts of disodium ethylene bisdithiocarbamate ■ 6H ₂ O and 836 parts of water are poured in, the resulting slurry is stirred for a further 2 hours, then suctioned off, the filter cake is washed with 200 parts of water, dried in air for 18 hours and then in a vessel for 6 hours, which is in a water bath at 50 to 60 C, with stirring at 10 to 15 mm pressure in a vacuum. 265 parts of a dark brown colored iron-manganese mixed salt are obtained which _{contain 49.1% CS 2} , 12.6% Mn and 5.5% Fe. The X-ray diagram of this product shows a broad peak with an average intensity between 6.5 and 7.5 Å.

If, in the above formulation, the first-mentioned solution is replaced by a solution of 131 parts of manganese sulphate · 2 H ₂ O and 83.4 parts of ferrous _{sulphate · 7 H 2} O in 865 parts of water, 298 parts of a brownish-green colored iron-manganese mixed salt are obtained. containing 45.2% CS ₂ , 12.6% Mn and 5.3% Fc. The X-ray diagram of this product shows strong lines at 6.90 and 6.51 Å and a medium faint line at 7.36 Å.

Example 12

In one with a stirrer, thermometer and feed funnel equipped reactor brings 140 parts of water. The one feed funnel is filled with KKX) space parts of an aqueous solution of 99.4 Tci-

len lead nitrate and 250 parts of 50% manganese nitrate solution, while the second funnel is filled _{with 1200 parts of an aqueous solution of 364 parts of disodium ethylene bisdithiocarbamate · 6H 2 O.} Both solutions are allowed to flow into the water within one hour while stirring at a temperature of 31 to 36 ° C., stirring is continued for 2 hours, suction filtered, the filter cake is washed with 200 parts of water, the brownish yellow substance is allowed to air dry at room temperature, then dries in vacuo at 50 to 60 ° C. and receives 336 parts of a lead-manganese mixed salt (purity 86% according to CS ₂ analysis) which contains 42% CS ₂ , 10.8% Mn and 17.4% Pb. The characteristic X-ray diagram of this product shows a strong line at 9.60 Å and weak lines at 5.47 and 4.93 Å.

Example 13

A reactor is charged with 170 parts of water and, at the same time, a solution of 147 parts of manganese acetal 4H ₂ O and 127.5 parts of mercury acetate in 725 parts of water and at a temperature of 24 to 33 ° C. within 1 hour is left at practically the same rate pour a solution of 265 parts of Nabam in 750 parts of water. The mixture is stirred for a further 2 hours, filtered off with suction, the filter cake is washed with 200 parts of water, air-dried for 18 hours and then in a reaction vessel placed on a water bath at 50 to 60 ° C. for 6 hours with stirring at 30 ° C mm pressure in vacuo and receives 334 parts of a gray mercury-manganese mixed salt containing 41.7% CS ₂ , 10.9% Mn and 17.2% Hg. The X-ray diagram of this product shows strong lines at 6.07 and 4.27 Å and a medium-broad peak at 3.32 Å.

Claims (2)

Patent claims: 1. Mixed salts of ethylene bisdithiocarbamic acid with manganese and insoluble in water with cobalt or copper, iron, lead, mercury, nickel and zinc, the molar ratio of Manganese to metal is between 40:60 and 90:10. 2. A process for the preparation of water-insoluble metal-manganese mixed salts deräthylenbisdithiocarbamic acid according to claim 1, characterized in that an aqueous solution of a water-soluble manganese salt and a water-soluble cobalt or copper, iron, lead, , reacted nickel, zinc and mercury salt, wherein the molar ratio of the manganese salt is to the other metal salt of 40:60 to 90:10 at a temperature of 10 to 5O ^'J C with an equivalent amount of a water-soluble salt of Äthylenbisdithiocarbaminsäure. 009 515/187