CS261051B1 - Method of ethylenbisdithiocarbomidic acid's manganate salt production - Google Patents
Method of ethylenbisdithiocarbomidic acid's manganate salt production Download PDFInfo
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Abstract
Riešenie sa týká spósobu výroby manganatej soli kyseliny etylénbisditiokarbamidovej s teplotou rozkladu minimálně 178 °C. Spósob je možné využiť v chemickom priemysle.The solution relates to a process for the production of manganese salts of ethylenebisdithiocarbamic acid with a decomposition temperature of at least 178 ° C. The method can be used in the chemical industry.
Description
Vynález sa týká sposobu výroby manganatej soli kyseliny etylénbisditiokarbamidovej s teplotou rozkladu minimálně 177 °C.The invention relates to a process for the production of a manganese salt of ethylenebisdithiocarbamic acid with a decomposition temperature of at least 177 ° C.
Manganatá so! kyseliny etylénbisditiokarbamidovej je látka polymérneho charakteru vyznačujúca sa fungicídnymi vlastnosťami a známa pod všeobecným názvom MANEB. Látka nemá presne definovaná štruktúru ani presne stanovené fyzikálno-chemické parametre — chemické konstanty, ktoré by ju mohli charakterizovať ako chemické individuum. Súvisí to s jej polymérnym charakterom. Nemá teplotu topenia, ale zahrievaním sa rozloží.Manganates so! ethylenebisdithiocarbamic acid is a polymeric substance with fungicidal properties and known under the common name MANEB. The substance does not have a well-defined structure or precise physico-chemical parameters - chemical constants that could characterize it as a chemical individual. It is related to its polymer character. It has no melting point but decomposes by heating.
Z patentovej literatury sú známe sposoby přípravy MANEB-u, ktoré v podstatě vychádza jú — zo zrážania vodorozpustnej soli kyseliny etylénbisditiokarbamidovej s vodorozpustnou sofou mangánu v ekvimolárnom pomere. Získaný produkt sa filtruje, suší a upravuje na finálny produkt. Teplota přípravy nie je uvádzaná (US pat. 2 504 404);Methods for preparing MANEB are known from the patent literature, essentially starting from the precipitation of a water-soluble salt of ethylenebisdithiocarbamic acid with a water-soluble manganese salt in an equimolar ratio. The product obtained is filtered, dried and treated to give the final product. The preparation temperature is not shown (US Pat. 2,504,404);
— z postupu, kde sa MANEB připraví z ekvimolárnych množstiev soli kyseliny etylénbisditiokarbamidovej a manganatej soli v rožmedží teplót 10 až 50 °C (US pat. č. 3 379 610; FR pat. 1 326 689).A process wherein MANEB is prepared from equimolar amounts of ethylenebisdithiocarbamic acid salt and manganese salt at temperatures between 10 ° C and 50 ° C (US Pat. No. 3,379,610; FR Pat. 1 326 689).
Ani jeden zo známých postupov přípravy nie je zameraný na teplotu rozkladu produktov a ani sa uvedenou problematikou nezaoberá. Táto fyzikálnochemická veličina je dóležitá z výrobnobezpečnostného hladiska přípravy kovových solí kyseliny etylénbisditiokarbamidovej, pretože sú známe případy zahorenia produktov, hlavně pri ich sušení. Bolo zistené, že produkty s vyššou teplotou rozkladu sú odolnejšle voči róznym vonkajším vplyvom, hlavně pri skladovaní, ale aj počas technologického spracovania.None of the known methods of preparation is focused on the decomposition temperature of the products, nor does it address this issue. This physico-chemical quantity is important from the manufacturing and safety point of view of the preparation of the metal salts of ethylenebisdithiocarbamic acid, since cases of heating of the products are known, especially during their drying. It has been found that products with a higher decomposition temperature are more resistant to various external influences, especially during storage but also during technological processing.
Vo všetkých doteraz v patentovej literatúre popísaných spósohoch přípravy a stabilizácie manebu sa uskutočňuje zrážanie soli kyseliny etylénbisditiokarbamidovej sofami mangánu v rozmedzí teplót 10 až 500 Celsia, kedy sa získavajú produkty s teplotou rozkladu od 157 do 177 °C.In all the maneb preparation and stabilization processes described in the patent literature, the precipitation of the ethylenebisdithiocarbamic acid salt of manganese is carried out in the temperature range of 10 to 50 ° C, whereby products with a decomposition temperature of 157 to 177 ° C are obtained.
Teraz bol zistený spósob výroby manganatej soli kyseliny etylénbisditiokarbamidovej s teplotou rozkladu minimálně 178 °C reakciou vodorozpustnej soli kyseliny etylénbisditiokarbamidovej s vodorozpustnou sofou mangánu podfa vynálezu. Podstata vynálezu spočívá v tom, že vodorozpustná sof kyseliny etylénbisditiokarbamidovej reaguje s vodorozpustnou sofou mangánu pri teplote 50 až 100 °C.We have now found a process for producing a manganese salt of ethylenebisdithiocarbamic acid having a decomposition temperature of at least 178 ° C by reacting a water-soluble salt of ethylenebisdithiocarbamic acid with a water-soluble manganese salt according to the invention. The essence of the invention is that the water-soluble salt of ethylenebisdithiocarbamic acid reacts with the water-soluble salt of manganese at a temperature of 50 to 100 ° C.
Získanú suspenziu manebu po izolácii niektorou z běžných izolačných metód, ako je napr. filtrácia. dekantácia, odstredenie a pod. je možné sušiť spravidla po rozplavení v tenkej vrstvě alebo v rozprašovacej sušiarni a/alebo vo vákuovej sušiarni.The obtained maneb suspension after isolation by any of the conventional isolation methods, e.g. filtration. decantation, centrifugation and the like. As a rule, it is possible to dry after thinning in a thin layer or in a spray drier and / or in a vacuum drier.
Výhoda spósobu výroby podfa vynálezu spočívá hlavně v tom, že zvýšením teploty pri přípravě manebu z teplotného rozmedzia 10 až 50 °C na 50 až 100 °C sa zvyšuje hodnota tepelného rozkladu získaného produktu, ktorá je vyššia ako 178 °C, pričom získaný maneb nestráca na čistotě.An advantage of the process according to the invention is mainly that by increasing the temperature in the preparation of maneb from a temperature range of 10 to 50 ° C to 50 to 100 ° C, the thermal decomposition value of the product obtained is higher than 178 ° C, purity.
Tento výsledok je prekvapujúci a nebolo ho možné předpokládat, pretože autoři uvedených patentov a v literatúre všeobecne sa uvádza, že pri vyšších teplotách vznikajú pri príprave manebu rózne splodiny rozkladu, ktoré znižujú čistotu získaného produktu. Pri tejto příležitosti ako vznikajúca nečistota sa uvádza najčastejšie etyléntiomočovina (ETU).This result is surprising and could not be assumed, as the authors of these patents and literature generally state that at higher temperatures, during the preparation of maneb, various decomposition products are formed which reduce the purity of the product obtained. On this occasion, ethylene thiourea (ETU) is the most commonly reported impurity.
Ďalšia výhoda spočívá v tom, že pri sušení produktov s vyššou teplotou rozkladu sa umožní práca pri vyšších teplotách, čím je možné zvýšiť výkon sušiaceho zariadenia. 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 snímá júcej kalorimetrie (DSC).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. 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 pan heating rate of 8 ° C / min. 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 banky opatrenej teplomerom, miešadlom a dávkovacím lievikom sa navážilo 87,3 g 23,37 %-ného vodného roztoku síranu manganatého a 100 g vody. Roztok sa vyhnal na 80 °C a za miešania sa k němu přidalo 83,4 g 39,76 %-ného vodného roztoku amónnej soli kyseliny etylénbisditiokarbamidovej. Obsah banky sa 5 minút miešal a potom ochladil. Vyzrážaný maneb sa dekantoval a premyí 3 x 100 ml vody. Z tohto produktu sa 1 g vysušil a stanovila sa teplota rozkladu metodou DSC, ktorá bola 186° Celsia.A flask equipped with a thermometer, stirrer and addition funnel was weighed with 87.3 g of a 23.37% aqueous manganese sulfate solution and 100 g of water. The solution was driven to 80 ° C and 83.4 g of a 39.76% aqueous ammonium salt of ethylenebisdithiocarbamic acid was added with stirring. The contents of the flask were stirred for 5 minutes and then cooled. The precipitated maneb was decanted and washed with 3 x 100 ml water. From this product, 1 g was dried and the decomposition temperature was determined by DSC, which was 186 ° C.
Příklad 2Example 2
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. P 5 min. miešania sa vzniknutá suspenzia ochladila na 25 °C. Produkt sa na frite odfiltroval a premyl vodou. 1 g produktu sa odsušil. Teplota rozkladu produktu bola 187 °C.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. P 5 min. with stirring, the resulting suspension was cooled to 25 ° C. The product was filtered on a frit and washed with water. 1 g of product was dried. The decomposition temperature of the product was 187 ° C.
P r í k 1 a d 3EXAMPLE 1 a d 3
Do kadičky opatrenej miešadlom sa navážilo 87,3 g 23,37 %-ného vodného roztoku síranu manganatého a přidalo 100 ml vody.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.
Roztok sa vyhrial na 65 °C a za miešania sa k němu přidalo 83,4 g 39,76 %-ného vodného roztoku amonné] soli kyseliny etylénbisditiokarbamidovej. Po 1,5 min. sa zo suspenzie odobralo 5 ml. Produkt po odfiltrovaní, premytí a vysušení mal teplotu rozkladu 187 °C stanovené metódou DSC.The solution was heated to 65 ° C and 83.4 g of a 39.76% aqueous ammonium salt of ethylenebisdithiocarbamic acid was added with stirring. After 1.5 min. 5 ml was withdrawn from the suspension. After filtration, washing and drying, the product had a decomposition temperature of 187 ° C as determined by DSC.
Příklad 4Example 4
Do banky opatrenej teplomerom, miešadlom a dávkovacím lievikom sa navážilo 78 g 21,8 %-ného vodného roztoku chloridu manganatého a 100 g vody. Roztok sa vyhrial na 80 °C a za miešania sa k němu přidalo 83,4 g 39,76 %-ného vodného roztoku amónnej soli kyseliny etylénbisditiokarbamidovej. Obsah banky sa 5 min. miešal a potom ochladil. Vyzrážaný maneb sa dekantoval a premyl 3 x 100 ml vody. Z tohto produktu sa 1 g vysušil a stanovila sa teplota rozkladu metódou DSC. ktorá bola 186 °C.78 g of a 21.8% aqueous manganese chloride solution and 100 g of water were weighed into a flask equipped with a thermometer, stirrer and addition funnel. The solution was heated to 80 ° C and 83.4 g of a 39.76% aqueous ammonium salt of ethylenebisdithiocarbamic acid was added with stirring. The contents of the bank took 5 min. stirred and then cooled. The precipitated maneb was decanted and washed with 3 x 100 ml water. From this product, 1 g was dried and the decomposition temperature was determined by DSC. which was 186 ° C.
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 65 °C a za miešania sa k němu přidalo 91,5 g 37,5 %-ného vodného roztoku disodnej soli kyseliny etylénbisditiokarbamidovej. Po 1,5 min. sa zo suspenzie odobralo 5 ml. Produkt sa odfiltroval a po premytí a vysušení mal teplotu rozkladu 187 °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 65 ° C and 91.5 g of a 37.5% aqueous solution of ethylenebisdithiocarbamic acid disodium salt was added with stirring. After 1.5 min. 5 ml was withdrawn from the suspension. The product was filtered off and after washing and drying had a decomposition temperature of 187 ° C as determined by DSC.
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Application Number | Priority Date | Filing Date | Title |
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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 |
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CS675483A CS261051B1 (en) | 1983-09-16 | 1983-09-16 | Method of ethylenbisdithiocarbomidic acid's manganate salt production |
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CS261051B1 true CS261051B1 (en) | 1989-01-12 |
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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 |
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CS851786A CS261052B1 (en) | 1983-09-16 | 1985-02-22 | Method of ethylenbisdithiocarbomidic acid's manganate salt complex production with zincate salt |
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1983
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1985
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