CS261052B1 - Method of ethylenbisdithiocarbomidic acid's manganate salt complex production with zincate salt - Google Patents
Method of ethylenbisdithiocarbomidic acid's manganate salt complex production with zincate salt Download PDFInfo
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Abstract
Riešenie sa týká sposobu výroby komplexu manganatej soli kyseliny etylénbisditiokarbamidovej so zinočnatou soíou s teplotou rozkladu minimálně 190 °C. Spósob výroby je možné využit v chemickom priemysle.The solution relates to the method of manufacturing the complex manganese salt of ethylenebisdithiocarbamic acid zinc with temperature decomposition of at least 190 ° C. The method of production can be used in the chemical industry.
Description
Vynález sa týká sposobu výroby komplexu manganate] soli kyseliny etylénbisditiokarbamidovej so zinočnatou solOu.The present invention relates to a process for the preparation of a zinc salt of a manganate salt of ethylene bis-dithiocarbamic acid.
Komplex manebu so zinočnatou sofou je látka polymérna s fungicídnymi vlastnosťami obsahujúca min. 85 % účlnnej látky stanovenej ako sírouhlík, min. 20 % mangánu a 2,5 % zinku z nájdeného obsahu účinnej látky, známa pod všeobecným názvom mancozeb. Ako bod vzplanutia pre mancozeb je udaná teplota 137 až 138 °C. (FAO 34/1/5/8 z 5. 6. 1979, Pesticide manual, 6. vydanie, str. 324, 1979).The zinc salt maneb complex is a polymeric substance with fungicidal properties containing min. 85% of active substance determined as carbon disulphide, min. 20% manganese and 2.5% zinc from the active ingredient content found, known under the generic name mancozeb. The flash point for mancozeb is given a temperature of 137-138 ° C. (FAO 34/1/5/8 of 5 June 1979, Pesticide manual, 6th edition, p. 324, 1979).
Tieto látky nemajú presne definovanú štruktúru ani presne stanovené fyzikálno-chemické konstanty, ktoré by ich mohli charakterizovat ako chemické individuum. Súvisi to s ich polymérnym charakterem.These substances do not have a well-defined structure or precise physicochemical constants that could characterize them as a chemical individual. This is related to their polymeric character.
Nemajú bod topenia, ale zahrievaním sa vznietia a rozložia.They do not have a melting point, but ignite and decompose by heating.
Z patentovej literatúru sú známe visceré sposoby přípravy maneozebu, ktoré v podstatě vychádzajú:The patent literature discloses visceral processes for the preparation of maneozeb, which are essentially based on:
— z postupu, kde sa manganatá sol' kyseliny etylénbisditiokarbamidovej (maneb) připraví z ekvimolárnych množstiev soli kyseliny etylénbisditiokarbamidověj a manganate j soli, alebo sa použije maneb hotový vo formě vodnej suspenzie, přidá sa vodný roztok zinočnatej soli a zmes sa ďalej suší a upravuje na finálny produkt. Pri tomto sposobe sa pracuje v rozmedzí teplot 10 až 50 °C (US pat. 3 379 610, FR pat. č. 1 326 689), — z postupu, pri ktorom sa na jeden mól soli kyseliny etylénbisditiokarbamidovej použije zmesný roztok soli mangánu a zinku v sumárnom množstve jeden mól a zráža sa v rozmedzí teplot 10 až 50 °G a následuje filtrácia, sušenie a finálna úprava produktu (US pat. 3 210 394, GB pat. 1000 137), — z postupu, kde k vodnému roztoku soli kyseliny etylénbisditiokarbamidovej sa přidá podstechiometrické množstvo vodného roztoku soli mangánu a k vzniknutej suspenzii manebu, ktorá obsahuje ešte nezreagované množstvo soli kyseliny etylénbisditiokarbamidovej, sa přidá v stechiometrickom nadbytku vodný roztok zinočnatej soli. Produkt sa ďalej známým spůsobom spracuje. Reakčné teploty sú v rozmedzí 10 až 25 °C (US pat. 3 869 486), — z postupu, kde reakcia zrážania amónnej soli kyseliny etylénbisditiokarbamidovej s manganatými a zinočnatými sofami prebieha pri teplotách 20 až 50 °C, za postupného zmiešavania jednotlivých reakčných komponentov v časovom intervale prevyšujúcom 30 minút a vzniknutý produkt, ktorého viac ako 50 % hmoty tvoria částice vSčšie ako 0,040 mm sa filtruje, rozplaví a podrobí mokrému mletiu na vefkosť častíc do 0,032 mm v najmenej 60 %-tách hmoty produktu (CS AO 218 084).- from a process wherein the manganese salt of ethylene-bis-dithiocarbamic acid (maneb) is prepared from equimolar amounts of the salt of ethylene-bis-dithiocarbamic acid and manganese salt, or using maneb prepared as an aqueous suspension, an aqueous solution of zinc salt is added and further dried final product. The process is carried out at a temperature range of 10 to 50 ° C (US Pat. No. 3,379,610, FR Pat. No. 1 326 689). zinc in a total amount of one mole and precipitates in the temperature range of 10 to 50 ° C, followed by filtration, drying and finishing of the product (US Pat. 3 210 394, GB Pat. 1000 137), A substoichiometric amount of an aqueous manganese salt solution is added to the ethylenebisdithiocarbamic acid, and an aqueous zinc salt solution is added in a stoichiometric excess of the maneb slurry containing an unreacted amount of the ethylenebisdithiocarbamic acid salt. The product is further processed in a manner known per se. The reaction temperatures are in the range of 10 to 25 ° C (US Pat. 3,869,486), - a process wherein the reaction of the precipitation of the ammonium salt of ethylenebisdithiocarbamic acid with manganese and zinc salts takes place at temperatures of 20 to 50 ° C, gradually mixing the individual reaction components at a time interval of more than 30 minutes and the resulting product having more than 50% by mass of the particles greater than 0.040 mm is filtered, washed and subjected to wet grinding to a particle size of up to 0.032 mm in at least 60% of the product mass (CS AO 218 084) .
Ani jeden zo známých postupov přípravy nie je zameraný na teplotu rozkladu produktov ani sa uvedenou problematikou nezaoberá. Táto fyzikálno-chemická veličina je důležitá z výrobnobezpečnostného hradiska přípravy kovových solí kyseliny etylénbisditiokarbamidovej, pretože sú známe případy zahorenia produktov hlavně pri ich sušení.None of the known methods of preparation is focused on the decomposition temperature of the products, nor is it addressed. This physicochemical quantity is important from the production safety point of view of the preparation of the metal salts of ethylenebisdithiocarbamic acid, since there are known cases of heating of the products mainly during their drying.
Bolo zistené, že podukty.s vyššou teplotou rozkladu sú odolnejšie voči různým vonkajším vplyvom, hlavně pri skladovaní.Higher decomposition sub-products have been found to be more resistant to various external influences, especially when stored.
Vo všetkých, doteraz v patentovej liiteratúre popísaných spůsoboch přípravy maneozebu sa robí zrážanie soli kyseliny etylénbisditiokarbamidovej sofami mangánu, připadne i zinku v rozmedzí teplůt 10 až 50 CC, kedy sa získavajú produkty s teplotou rozkladu od 157 do 177 °C.In all the prior art processes described for the preparation of maneozeb, the precipitation of the ethylenebisdithiocarbamic acid salt with a manganese salt, optionally zinc, in the temperature range of 10 to 50 ° C, yields products with a decomposition temperature of 157 to 177 ° C.
Teraz bol vyrobený komplex manganatej soli kyseliny etylénbisditiokarbamidovej so zinočnatou solou s teplotou rozkladu minimálně 190 °C reakciou vodorozpustnej soli kyseliny etylénbisditiokarbamidovej s vodorozpustnou sofou mangánu a zinku spůsobom podfa vynálezu.A manganese salt of ethylene-bis-dithiocarbamic acid with a zinc salt having a decomposition temperature of at least 190 ° C has now been prepared by reacting a water-soluble salt of ethylene-bis-dithiocarbamic acid with a water-soluble salt of manganese and zinc according to the invention.
Podstata vynálezu spočívá v tom, že najprv sa nechá zreagovať vodorozpustné sol' kyseliny etylénbisditiokarbamidovej s vodorozpustnou sofou mangánu prl teplote 50 až 100 °C a potom vzniknutá manganatá sol' kyseliny etylénbisditiokarbamidovej reaguje s vodorozpustnou sofou zinku.SUMMARY OF THE INVENTION The invention is based on the first step of reacting a water-soluble salt of ethylenebisdithiocarbamic acid with a water-soluble manganese salt at a temperature of 50 to 100 ° C, and then reacting the manganate salt of ethylene-bisdithiocarbamic acid with water-soluble zinc salt.
Výhoda spůsobu výroby podfa vynálezu spočívá hlavně v tom, že zvýšením teploty pri príprave manebu, resp. maneozebu z teplotného rozmedzia 10 až 50 °C na 50 až 100 °C sa zvyšuje hodnota tepelného rozkladu získaného produktu, ktorá je rovná alebo vyššia ako 190 CC. čím sa zvýši stabilita produktu najma počas skladovania ale aj počas technológie spracovania.The advantage of the process according to the invention is mainly that by increasing the temperature during the preparation of the maneb, respectively. Maneozeb from a temperature range of 10 to 50 ° C to 50 to 100 ° C increases the thermal decomposition value of the product obtained, which is equal to or greater than 190 ° C, thereby increasing the stability of the product not only during storage but also during processing technology.
Ďalšia výhoda spočívá v tom, že pri sušení produktov s vyššou teplotou rozkladu sa umožní práca pri vyšších teplotách, čím je možné zvýšit výkon sušiaceho zariadenia.A further advantage is that when drying products with a higher decomposition temperature, it is possible to work at higher temperatures, thereby increasing the performance of the drying device.
Teplota rozkladu sa posudzovala zo získaných meraní tepelnej stability, ktoré sa robili na kalorimetri Perkin—-Elmer DSC 1 B v spojení so zapisovačom Speedomax W, v otvorených hliníkových vzorkových miskách, v prúde dusíka, pri rýchlosti vyhrievania vzorkovej misky 8 °C/min metodou diferenčně snímájúcej kalorimetrie (DSC).The decomposition temperature was judged from the obtained thermal stability measurements made on a Perkin-Elmer DSC 1 B calorimeter in conjunction with a Speedomax W recorder, in open aluminum sample dishes, under a stream of nitrogen, at a sample plate heating rate of 8 ° C / min. differential scanning calorimetry (DSC).
Uvedené příklady ilustrujú, ale neobmedzujú predmet vynálezu.These examples illustrate but do not limit the scope of the invention.
Příklad 1Example 1
Do kadičky opatrenej miešadlom sa navážilo 87,3 g 23,37 %-ného vodného roztoku síranu manganatého a 100 g vody. Roztok sa vyhrial na 85 °C a za miešania sa k němu přidalo 83,4 g 39,76 %-ného vodného roztoku amónnej soli etylénbisditiokarbamidovej kyseliny. Po 5 min. miešania sa vzniknutá suspenzia ochladila na 25 °C. Produkt sa na frite odfiltroval a premyl vodou, od6 filtroval sa, premyl a rozsuspendoval v roztoku 1 g heptahydrátu síranu zinočnaíého v 100 ml vody. Vzniknutá suspenzia sa mlela na laboratórnom mlýne tak, aby 80 % hmot. častíc bolo menších ako 20 mikrometrov. Potom sa přidalo 3,6 g heptahydrátu síranu zinočnatého rozpuštěné v 10 ml vody. Získaný produkt po vysušení mal teplotu rozkladu 194 °C merané metódou DSC a obsahoval 89,7 % účinnej látky (stanovené ako sírouhlík).87.3 g of a 23.37% aqueous manganese sulfate solution and 100 g of water were weighed into a beaker equipped with a stirrer. The solution was heated to 85 ° C and 83.4 g of a 39.76% aqueous solution of ethylenebisdithiocarbamic acid ammonium salt was added with stirring. After 5 min. with stirring, the resulting suspension was cooled to 25 ° C. The product on the frit was filtered and washed with water, filtered, washed and suspended in a solution of 1 g of zinc sulfate heptahydrate in 100 ml of water. The resulting suspension was ground in a laboratory mill to 80% by weight. the particles were smaller than 20 microns. Then, 3.6 g of zinc sulfate heptahydrate dissolved in 10 ml of water was added. The product obtained after drying had a decomposition temperature of 194 ° C as measured by DSC and contained 89.7% of active ingredient (determined as carbon disulphide).
P r í k 1 a d 2Example 1 a d 2
Do kadičky opatrenej miešadlom sa navážilo 87,3 g 23,37 %-ného vodného roztoku síranu manganatého a pridaio 100 ml vody. Roztok sa vyhrial na 85 nC a za miešania sa k němu přidalo 83,4 g 39,76 %-ného vodného roztoku amónnej soli kyseliny etylénbisditiokarbamidovGj. K suspenzi! sa přidal 1 g heptahydrátu síranu zinečnatého v 10 ml vody a po 3 min. miešania sa produkt odfiltroval, premyí a znovu rezsuspen-doval vo vodě. Suspenzia as mk-ila ηε iahoratórnom mlýne tak. aby 80 % hmot. častíc bolo menších ako 29 mikrometrov. K suspenzii sa přidal ešte roztok 3,3 g heptahydrátu síranu zinočnatého. Po zamiešaní sa suspenzia sušila na rotačnom vákuovom odparováku při 50 °C a 3,0 kPa a produkt sa ešte vákuovo dosušil pri 70 °C a 0,15 kPa. Suchý produkt obsahoval 90,7 °/o účinnej látky (stanovenej ako sírouhlík), 19,2 % mangánu a 2,5 % zinku.A beaker equipped with a stirrer was weighed with 87.3 g of a 23.37% aqueous manganese sulfate solution and added with 100 ml of water. Solution, heated at 85 C and n stirring to it was added 83.4 g 39.76% aqueous solution of ammonium salt of etylénbisditiokarbamidovGj. To the suspension! 1 g of zinc sulfate heptahydrate in 10 ml of water was added and after 3 min. with stirring, the product was filtered off, washed and resuspended in water. The suspension with mk-ila ηε iahoratone mill so. to 80 wt. the particles were smaller than 29 microns. A solution of 3.3 g of zinc sulfate heptahydrate was added to the suspension. After stirring, the slurry was dried on a rotary evaporator at 50 ° C and 3.0 kPa and the product was further dried at 70 ° C and 0.15 kPa. The dry product contained 90.7% active ingredient (determined as carbon disulphide), 19.2% manganese and 2.5% zinc.
Příklad 3Example 3
Do kadičky opatrenej miešadlom sa navážilo 99,9 g 21,1 %-ného vodného roztoku síranu manganatého a 80 g vody. Roztok sa vyhrial na 95 °C, za miešania sa k němu přidalo 83,4 g 39,76 %-ného vodného roztoku amónnej soli kyseliny etylénbisditiokarbamidovej a potom ešte 0,8 g heptahydrátu síranu zinočnatého ZnSCU. 7 HaO rozpuštěné v 10 ml vody. Po 2 min. miešania sa suspenzia ochladila na 30 °C. Produkt sa odfiltroval, premyl vodou a znovu rozsuspendoval do 100 ml vody, kde sa ešte přidalo 3,8 g heptahydrátu síranu zinočnatého ZnSOá. 7 H2O. Suspenzia sa mlela na laboratórnom mlýne tak, aby 80 % hmot. častíc bolo menších ako 20 mikrometrov. Po zhomogenizovaní sa suspenzia sušila na vákuovom rotačnom odparováku pri 50 °C a 2,5 kPa. Vlhký produkt sa ešte dosvšil vo vakuové) sušiarni pri 70 °C a 0,15 kPa. Produkt obsahoval 87,4 % účinnej látky (stanovené ako sírouhlík) 19,8 % mangánu a 2,51 % zinku. Teplota rozkladu 194 ;C stanovené metódou DSC.99.9 g of a 21.1% aqueous manganese sulphate solution and 80 g of water were weighed into a beaker equipped with a stirrer. The solution was heated to 95 ° C and 83.4 g of a 39.76% aqueous ammonium salt of ethylenebisdithiocarbamic acid ammonium salt was added thereto with stirring, followed by 0.8 g of zinc sulfate heptahydrate ZnSCU. 7 HaO dissolved in 10 ml of water. After 2 min. with stirring, the suspension was cooled to 30 ° C. The product was filtered off, washed with water and resuspended in 100 ml of water, where 3.8 g of ZnSO4 heptahydrate was added. 7 H2O. The suspension was ground in a laboratory mill to 80% by weight. the particles were smaller than 20 microns. After homogenization, the suspension was dried on a vacuum rotary evaporator at 50 ° C and 2.5 kPa. The wet product was even further dried in a vacuum oven at 70 ° C and 0.15 kPa. The product contained 87.4% active ingredient (determined as carbon disulphide) 19.8% manganese and 2.51% zinc. Decomposition temperature 194 ; C determined by DSC.
Příklad 4Example 4
Do kadičky opatrenej miešadlom sa navá0! 2 žilo 89,1 g 23,3 %-ného vodného roztoku síranu manganatého. Roztok sa zohrial na 60 °C a potom za miešania sa k němu přidalo 83,4 g 39,76 %-ného vodného roztoku amónnej soli kyseliny etylénbisditiokarbamidovej, 0,6 g heptahydrátu síranu zinočnatého' v 10 ml vody. Po 5 min. sa vyzrážaný produkt odfiltroval, premyl a znovu rozsuspendoval v 100 g roztoku pozostávajúceho zo 4,8 g heptahydrátu síranu zinočnatého ZnSO-ί. 7 HrO a 95.4 g vody. Suspenzia sa mlela na laboratórnom mlýne tak, aby 80 % hmot. častíc bolo menších ako 20 mikrometrov. Nakoniec sa suspenzia vysušila v tenkej vrstvě pri 80 'C. Suchý produkt obsahoval 89,6 % účinnej látky (stanovenej ako sírouhlík), 19,5 % mangánu a 2,4 % zinku.Place in a beaker fitted with a stirrer. 2 had 89.1 g of a 23.3% aqueous manganese sulfate solution. The solution was heated to 60 ° C and then, with stirring, 83.4 g of a 39.76% aqueous solution of ethylenebisdithiocarbamic acid ammonium salt, 0.6 g of zinc sulfate heptahydrate in 10 ml of water were added. After 5 min. the precipitated product was filtered off, washed and resuspended in 100 g of a solution consisting of 4.8 g of zinc sulfate heptahydrate ZnSO4. 7 H 2 O and 95.4 g water. The suspension was ground in a laboratory mill to 80% by weight. the particles were less than 20 microns. Finally, the slurry was dried in a thin layer at 80 ° C. The dry product contained 89.6% active ingredient (determined as carbon disulphide), 19.5% manganese and 2.4% zinc.
Teplota rozkladu produktu bola 192 CC stanovená metódou DSC.Decomposition temperature of the product was 192 C C DSC onset.
Příklad 5Example 5
Do kadičky opatrenej miešadlom sa navážilo 87,3 g 23,37 %-ného vodného roztoku síranu manganatého a přidalo 100 ml vody. Roztok sa vyhrial na 70 C a za miešania sa k němu přidalo 83,4 g 39,76 %-ného vodného roztoku amónnej soli kyseliny etylénbisditiokarbamidovej. K vzniknutej suspenzi! manebu sa přidal 1 g heptahydrátu síranu zinočnatého v 10 ml vody a po 3 minútach miešania sa 2krát zdekantoval 100 ml vody, znovu rozsuspendoval vo vodě. Suspenzia sa mlela na laboratórnom mlýne tak, aby 80 % hmot. častíc bolo menších ako 20 mikrometrov. K suspenzii sa přidal ešte roztok 3,6 g heptahydrátu síranu zinočnatého v 10 ml vody. Po premiešaní sa suspenzia sušila na rotačnom vákuovom odparováku pri 50 CC a 3,0 k?a a produkt sa ešte dosušil za vákua 0,15 kPa a 70 °C. Suchý produkt obsahoval 88,1 % účinnej látky, 19,0 % mangánu, 2,4 % zinku a mal teplotu rozkladu 194 °C stanovené metódou DSC.87.3 g of a 23.37% aqueous manganese sulphate solution were weighed into a beaker equipped with a stirrer and 100 ml of water were added. The solution was heated to 70 ° C and 83.4 g of a 39.76% aqueous ammonium salt of ethylenebisdithiocarbamic acid was added with stirring. To the resulting suspension! 1 g of zinc sulfate heptahydrate in 10 ml of water was added and after stirring for 3 minutes, 100 ml of water were decanted twice, then resuspended in water. The suspension was ground in a laboratory mill to 80% by weight. the particles were smaller than 20 microns. A solution of 3.6 g of zinc sulfate heptahydrate in 10 ml of water was added to the suspension. After stirring, the suspension was dried on a rotary evaporator at 50 ° C and 3.0 kPa and the product was dried under vacuum at 0.15 kPa and 70 ° C. The dry product contained 88.1% active ingredient, 19.0% manganese, 2.4% zinc and had a decomposition temperature of 194 ° C as determined by DSC.
Příklad 6Example 6
Do kotli opatřeného miešadlom a teplomerora sa navážilo 29,1 kg 23,37 %-ného vodného roztoku síranu manganatého, 30 kg vody a vyhrialo sa na 75 °C. Potom sa postupné za miešania přidalo 27,8 kg 39,76 %-ného vodného roztoku amónnej soli etylébisditiokarbamidovej.A stirrer and thermometer were weighed into 29.1 kg of a 23.37% aqueous manganese sulfate solution, 30 kg of water, and heated to 75 ° C. Then, 27.8 kg of a 39.76% aqueous solution of ammonium ethylisodithiocarbamide ammonium salt was added successively with stirring.
Obsah kotlá sa schladil na 30 CC. Po odstavení miešadla sa vyzrážaný produkt nechal usadit, vrchná vodná vrstva sa stiahla. K produktu sa přidalo 90 kg vody, suspenzia sa zamiešala a nechala usadit. Vrchná vrstva sa znovu stiahla. K vysedimentovanému produktu sa přidalo 50 kg vody, 1,53 kg heptahydrátu síranu zinočnatého a 0,5 kg urotropínu.The contents of the boiler were cooled to 30 ° C. After the stirrer was stopped, the precipitated product was allowed to settle, the upper aqueous layer was stripped off. 90 kg of water was added to the product, the suspension was stirred and allowed to settle. The top layer was withdrawn again. 50 kg of water, 1.53 kg of zinc sulfate heptahydrate and 0.5 kg of urotropin were added to the sedimented product.
Suspenzia sa premlela na perlovom mly7 ne a sušila na rozprašovacej sušiarni pri teplote vstupu 285 °C a výstupu 105 °C.The suspension was ground in a pearl mill and spray dried at an inlet temperature of 285 ° C and an outlet temperature of 105 ° C.
Suchý produkt obsahoval 88,5 % účinnej látky (stanovenej ako sírouhlík), 19,2 % mangánu a 2,5 % zinku. Teplota rozkladu bola 192 °C stanovená metódou DSC.The dry product contained 88.5% active ingredient (determined as carbon disulphide), 19.2% manganese and 2.5% zinc. The decomposition temperature was 192 ° C by DSC.
Příklad 7Example 7
Do kadičky opatrenej miešadlom sa navážilo 79,3 g 21,8 %-ného vodného roztoku chloridu manganatého. Roztok sa zohrial na 60 °C a potom za miešania sa k němu přidalo 83,4 g 39,76 %-ného vodného roztoku amónnej soli kyseliny etylénbisditiokarbamidovej a 0,3 g chloridu zinočnatého v 10 ml vody. Po 5 mlnútach sa vyzrážaný produkt odfiltroval, premyl a znova rozsuspendoval v 100 g roztoku pozostávajúceho z 2,2 g chloridu zinočnatého a 97.8 g vody. Suspenzia sa mlela na laboratórnom mlýne tak, aby 80 % hmot. častíc bolo menších ako 20 mikrometrov, Nakoniec sa suspenzia vysušila v tenkej vrstvě pri 80 °C. Suchý produkt obsahoval 89,6 °/o účinnej látky (stanovenej ako sírouhlík) 19,5 % mangánu a 2,4 % zinku. Teplota rozkladu produktu bola 192 °C stanovené metódou DSC.79.3 g of a 21.8% aqueous manganese chloride solution were weighed into a beaker equipped with a stirrer. The solution was heated to 60 ° C and then 83.4 g of a 39.76% aqueous solution of ethylenebisdithiocarbamic acid ammonium salt and 0.3 g of zinc chloride in 10 ml of water were added with stirring. After 5 minutes the precipitated product was filtered off, washed and resuspended in 100 g of a solution consisting of 2.2 g of zinc chloride and 97.8 g of water. The suspension was ground in a laboratory mill to 80% by weight. the particles were less than 20 microns. Finally, the slurry was dried in a thin layer at 80 ° C. The dry product contained 89.6% active ingredient (determined as carbon disulphide) of 19.5% manganese and 2.4% zinc. The decomposition temperature of the product was 192 ° C as determined by DSC.
Příklad 8Example 8
Do kadičky opatrenej miešadlom sa navážilo 87,3 g 23,37 %-ného vodného roztoku síranu manganatého a přidalo 100 ml vody. Roztok sa vyhrial na 70 °C a za miešania sa k němu přidalo 87,6 g 39,5 %-ného vodného roztoku disodnej soli kyseliny etylénbisditiokarbamidovej. Vzniknutá suspenzia manebu sa 2krát zdekantovala 100 ml vody, maneb sa znovu rozsuspendoval vo vodě a přidalo sa 4,6 g heptahydrátu síranu zinočnatého v 10 ml vody. Suspenzia sa mlela na laboratórnom mlýne tak, aby 80 % hmot. častíc bolo menších ako 20 mikrometrov. Získaná suspenzia sa sušila na rotačnom vákuovom odparováku pri 50 CC a tlaku 3,0 kPa a produkt sa dosušil za vákua 0,15 kPa a 70 °C. Suchý produkt obsahoval 88,7 % účinnej látky, 19,1 % mangánu, 2,52 % zinku a mal teplotu rozkladu 193 °C stanovené metódou DSC.87.3 g of a 23.37% aqueous manganese sulphate solution were weighed into a beaker equipped with a stirrer and 100 ml of water were added. The solution was heated to 70 ° C and 87.6 g of a 39.5% aqueous solution of ethylenebisdithiocarbamic acid disodium salt was added with stirring. The resulting maneb suspension was decanted twice with 100 ml of water, the maneb was resuspended in water and 4.6 g of zinc sulfate heptahydrate in 10 ml of water was added. The suspension was ground in a laboratory mill to 80% by weight. the particles were smaller than 20 microns. The resulting slurry was dried on a rotary evaporator at 50 ° C and 30 mbar and the product was dried under vacuum at 0.15 mbar and 70 ° C. The dry product contained 88.7% active ingredient, 19.1% manganese, 2.52% zinc, and had a DSC decomposition temperature of 193 ° C.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS851786A CS261052B1 (en) | 1983-09-16 | 1985-02-22 | Method of ethylenbisdithiocarbomidic acid's manganate salt complex production with zincate salt |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS675483A CS261051B1 (en) | 1983-09-16 | 1983-09-16 | Method of ethylenbisdithiocarbomidic acid's manganate salt production |
| CS851786A CS261052B1 (en) | 1983-09-16 | 1985-02-22 | Method of ethylenbisdithiocarbomidic acid's manganate salt complex production with zincate salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS261052B1 true CS261052B1 (en) | 1989-01-12 |
Family
ID=5415277
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS675483A CS261051B1 (en) | 1983-09-16 | 1983-09-16 | Method of ethylenbisdithiocarbomidic acid's manganate salt production |
| CS851786A CS261052B1 (en) | 1983-09-16 | 1985-02-22 | Method of ethylenbisdithiocarbomidic acid's manganate salt complex production with zincate salt |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS675483A CS261051B1 (en) | 1983-09-16 | 1983-09-16 | Method of ethylenbisdithiocarbomidic acid's manganate salt production |
Country Status (1)
| Country | Link |
|---|---|
| CS (2) | CS261051B1 (en) |
-
1983
- 1983-09-16 CS CS675483A patent/CS261051B1/en unknown
-
1985
- 1985-02-22 CS CS851786A patent/CS261052B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS261051B1 (en) | 1989-01-12 |
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