DE1468805A1 - Process for the production of new complexing agents - Google Patents

Description

FATHY ADVOCATE

8000 MUNICH 22

WIO £ i <IMAYCRSTR. B. ^{A 20 O65} April 30, 1965

BM / Ab / tf.

Mr Andre FOLOAR, 18, rue Tißserant, Boulogne Sur Seine France Process for the production of new complexing agents

The invention relates to new complexing agents, especially those made from urea, formaldehyde and an alkali salt of hydrogen cyanide produced in an alkaline medium its derivative compounds act which are capable of acting on the nitrogen atoms derived from urea Graft alkylenecarboxyl groups in such a way that you get molecules obtained, which at the same time contain acid groups and nitrogen atoms, which are capable of coordinating bonds with metals to result in *.

A process for the production of complexing agents based on aminocarboxylic acids is already known, which therein consists of having cyanide and formaldehyde on ethylenediamine let it act. In this way, ethylenediaminetetraacetic acid is obtained (EDTA), the classic complexing agent

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According to the invention, a complexing agent is produced by the action of formaldehyde and alkali metal anide or one Alkali shark acetates based on urea, in one as in the other Case in medium with low alkali. The alkali salt used (oyanide or halogen acetate) is practically a salt of sodium or potassium. The advantage of this complexing agent is that it is very cheap and that it mixes with soap can be to a cheap, biodegradable detergent au surrender. In fact, complexing agents based on urea are considerably cheaper than ethylenediaminetetraeac acid.

You can proceed in the following way, for example: Example 1

To 15Θ kg of urea, 21 kg of sodium cyanide, dissolved in 85 1 of water, and 15 kg of caustic soda, dissolved in 50 1 of water. added. Under a vacuum (50 cm, Hg) the ^{mixture is heated to 60 °} C. and 32 kg of 40% formaldehyde are slowly added <,

The reaction starts with the development of heat and the release of ammonia; once the latter is finished, it will add another 21 kg of sodium cyanide in 85 1 water released, and again slowly 32 kg 40 # weight formaldehyde to · It should be noted that the temperature wirdο not überβohritten of 60 ⁰ C

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Han Betet nooh 5 times 21 kg sodium cyanide, each in 85 1 Dissolved water, and 32 kg of 40% formaldehyde added 16 kg of formaldehyde are added to the last addition in order to neutralize any trace of cyanide

This gives in total 147 kg of sodium cyanide in 595 liters of water dissolved, and 224 kg of formaldehyde.

Then the vacuum is released in order to come to normal pressure and ^{heated to 105 °} C. for two hours. At the end of this process, you have 750 to 800 liters of a solution which complexes 10.5 mg calcium carbonate per g solution. Acidification gives a precipitate which gives a crystalline powder which, when dissolved in an alkaline medium, possesses a corresponding complex binding capacity.

Example 2

In a bowl brings to 120 g Natriumchloraoetat and 170 oor water and heated for dissolving at 55 ⁰ O · In a Beoherglas brings one 42 g of caustic soda dissolved in 165 onr water, and added 66 g of urea to · will shell warmed slightly and wherein the temperature is maintained for one hour under stirring at 65 ⁰ C slowly poured into the contents of the Beoherglases Sohale, ·

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It is allowed to cool and a clear, good solution is obtained

complex-forming properties

Contamination has also been found to fester through some modifications of the production term described above Ahrens "possible" complexing agent is also available "which gans are particularly effective and are part of the economic picture.

It was found in particular that the best yields of Koaplexblldnern are obtained if one adheres to a very specific production process, which concerns the addition of the reactants and the reaction temperatures the alkali metal cyanides susufUgen very slowly, optionally with cooling, so that the fseperator not exceed 30 ⁰ C _β

When it comes to the proportions of urea, alkali metal cyanide and formaldehyde to be used, 1 mol of urea can be used swisohen 2 and 4 moles of the alkali metal cyanide and between 2 and Allow 4 MbI formaldehyde to act, in any case Note that per mole of alkali metal cyanide, at least 1 mole of formaldehyde is used.

ϊβ Would it be found that the complex bond »

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ability of the products obtained according to the invention noticeably is increased if after the condensation of the urea, the alkali metal cyanide and the formaldehyde in an alkaline medium then an excess of formaldehyde - if necessary after one has passed an acidic medium, allows to act, this reaction with a Poraaldehyd-Ubereohuse (at least 1/2 MbI per mole of urea) either directly on the liquid reaction mass after completion of the alkaline hydrolysis can be carried out or on the addition of acid to the liquid reaction masae after completion of the alkaline. Hydrolysis precipitated product can be carried out

The other examples explain the invention without it restrict; specified parts are weight parts.

Example 3

60 parts of urea »100 parts of NaCN, dissolved in 200 parts of water, and 15 parts of HaOH dissolved in 20 parts of water are mixed. Dropwise is added within 4 to 5 hours parts 3Oxigen formaldehydes, while cooling so that the temperature never exceeds 30 ⁰ C. You let the Genieoh rest for a few hours until the Aanonlakentwloklung begins and reflux for 3 hours or let the Gemisoh infaoh Behrer stand for days »Then add» to 5 parts of soda, see below

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and heated again for an hour. You get 00 350 ropes a solution of which 1 cm * 75 ag of CaCO * complex binds.

Duron acidification with HCl _1, subsequent filtration and drying of the precipitate formed, a crystalline powder is obtained, which, dissolved in dilute soda or potash, binds complexes per g ΥΘ1 ng of CaCO.

Bilnlil ♦

Mao aieoht 60 parts · Harnetoff, 100 parts NaCH, dissolved in 150 parts fatfter and 15 parts ITaOH, dissolved in 20 parts! «•« er. Is added dropwise over 4 to 5 hours 200 parts 30jfigen to fontaldehyd, wherein one cools to 30 ⁰ C nioht tu ftbersohreiten.

are reads a few hours until the liquid is colored and see ammonia begins to develop and heated under reflux for 5 Btunden · Kan leaves at 50 ⁰ C to cool and Fogt 50 parts formaldehyde to 3Obigen; it is heated under Rüokfluas for 1 hour. After cooling, it is acidified with HOl and a crystalline powder is obtained, which separates out, and the sian is filtered and dried.

This powder »dissolved in a dilute soda solution, binds every g

JM ; - *; rr <o J ' ^KÜ ORIGINAL BATHROOM *

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325 ag OaOO. complex.

Nan misohts 60 parts of Harnetoff, 200 parts of IeCV, dissolved in 300 parts of water and 15 _{parts of HaOH 9} dissolved in 20 parts of water. Men fttgt dropwise 400 parts 30jligen Formaldehyde su _f wherein Mpn cools, not in au 30 ⁰ O Ubereohrelten.

Let stand a few hours and get 3 hours under Rüokfloee. Sann fttgt stan 15 parts caustic soda su and he hit Et noohmal 2 hours. After cooling down is the liquid diok and binds each g 97.5 ng OaCO ^ complex.

You drop old BDI, filter and dry the leather sole *. An acidic powder is obtained which complexes binds 200 ag per g.

Example 6

25 feile dee powder-shaped products, which one sews Example 3 has been obtained, one lusts in 25 parts of formaldehyde. 100 parts of water are added and the mixture is heated for 1 1/2 hours under Htlokfluae. A crystalline separates as it cools down Solid from. Haoh filtering and drying you get an eauree, Powder, which, dissolved in dilute soda solution, per g

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331.2 ag OaCO, complex binds.

Example 7

25 ropes of the powdery, acidic product obtained according to Example 5 are dissolved in 25 ropes of formaldehyde. Add 100 ropes of water and reflux for 1 1/2 hours; After cooling, the crystals are filtered off with suction and an acidic powder is obtained, which, when dissolved in dilute sodium carbonate solution, binds _{375 mg of CaOO 5 complex per g.}

Example 8

60 ropes of urea are mixed with 100 parts of HaOH, dissolved in 200 ropes of barrel and 15 ropes of HaOH, dissolved in 40 ropes of water. 200 ropes of 3Obigen formaldehyde SU _{9 are} added dropwise, with cooling so as not to exceed ^{30 0 O.} The mixture is left to stand for 24 hours. 50 ropes of formaldehyde and the required amount of hydrochloric acid are added to bring the pH to 1 su, and it is refluxed for an hour. It is allowed to cool, 40 ropes of soda and 200 ropes of water are added to bring the pH to 13. Bann is heated under a river for 1 1/2 hours. 960 cm * of a solution is obtained, of which 10 om '140 mg of CaCO 2 coaplex bind.

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These complexing agents produce stable qhelates with metals.

Some of the chelating properties of the product according to Example 1 are listed below:

Weight of the complexing agent per mole bound as Cheiat Metal: 156 ^.

Desired of the complexing agent per g bound as a carbonate Calcium 3 "9 g"

It is difficult, the inventive complexing agents or Characterize chelating agents according to their constitution

The products obtained can be found in all branches of industry Use »where it is necessary, metals» such as the alkaline earth metals or sohr metals, such as Elsen »zinc» manganese » Bind cobalt us «» »complex au.

The invention relates to the same mass of soaps »which the ·· Complexing agents contain "and which are biodegradable detergents" can be found in calcareous waters like synthetic detergents.

These soaps are obtained by, for example, 2/5 usually · » Belf «and 1/5 complexing agent wmleoht. ~ *

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The applications extend beyond the production of biodegradable detergents, as mentioned above, for example on the pharmaceutical, cosmetic, metallurgical and photographic industries, on agriculture, in particular on fertilizers (water-soluble metal chelates, especially of trace elements, for the treatment of plants through the root or through the leaves), the paper industry, the textile industry, the food industry, the sugar industry etc., thanks to their chelating ability not only for OaIoium, but also for iron, zinc, magnesium, manganese, copper

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Claims (6)

U68805 AA A 20 065 claims 1. Process for the production of a complexing agent ι dadaroh known that urea is in alkaline medium with formaldehyde and an alkali anide or with an alkali halogen acetate react. 2. The method according to Anapruoh 1, characterized in that the formaldehyde is added very slowly to the aqueous alkaline solution, the urea and the alkali metal cyanide, while cooling to the extent that the temperature does not exceed ^{30 0.} 3. The method according to claims 1 or 2, thereby germinating worthwhile, that to 1 mole of urea 2 to 4 moles of alkali metal anide and 2 to 4 moles of formaldehyde can act, at least en β 1 mole of formaldehyde is used per mole of alkali anide » 4 «Procedure naoh one or more of claims 1 to 3» ^! daduroh kenneelehnet that one naoh Abeohluee the TJm-, eetsung of the urate β with the alkali anide and the formaldehyde an excess of formaldehyde in an alkaline medium, miödeetens 1/2 mole of formaldehyde per mole of urea, directly to the flueelge reactioneaaeee, possibly im ■ ■■■ f ·· - - ti -., 809813/1353 ^{BATHROOM 0WGINAL} A 20 065 acidic medium to act » 5 «Method according to one or more of Claims 1 to 3» characterized »that after completing the occupation of the urea with the alkali metal cyanide and the formaldehyde In the alkaline medium the Eomplezbildner precipitates by adding an acid to the liquid reaction, the precipitate is separated off and dried and an excess of formaldehyde, at least 1/2 mole of formaldehyde per mole of urea, optionally on the dry precipitate in acidic medium, leaves to act * 6. Biodegradable detergents consisting of mixtures of ordinary soap and complexing agents based on urea according to claims 1 to 5 · - 12 r 80981 3/1353 BATH ORIGINAL