NO813385L - PROCEDURE FOR THE PREPARATION OF METAL OXYLYCYLATES - Google Patents

Description

li li i Zinc oxyacetate (zinc hexakis (acetato) oxotetral) with j I the empirical formula<c>i2H18^13<Z>n40<^ the structural formula | ! i Zn^O(CH^CC^)g is described in the literature, for example in the jBulletin of the Chemical Society of Japan, March 1954, in

Volume 27, No. 2, pages 112-114. According to this ; in 27, No. 2, pages 112-114. according to this article as well as others, the compound is prepared by slow distillation of powdered anhydrous zinc acetate under high vacuum. Zinc oxyacetate gradually sublimes and collects as a crystalline crust in the cool part of the container. This procedure is time-consuming and expensive. j

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j il: It is a purpose of the present invention to provide | in bringing an efficient and economical method for the production of zinc and other metal oxyalkylates. It is a further object of the invention to provide a metal compound which is an effective carrier for supplying metal

i i ;to plants, animals and people. in

The above-mentioned and other purposes will be apparent to a person and are achieved according to the present invention by providing a method for the production of metal oxyalkylates by reacting a metal, acetic acid and hydrogen peroxide in an aqueous reaction medium, precipitate the metal oxylate and separate the precipitated metal oxylate. Preferred metals include beryllium, magnesium, chromium, manganese, iron, cobalt, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium and mercury. Mixtures or alloys of metals such as manganese and zinc can be used. Preferred carboxylic acids include aliphatic carboxylic acids containing up to 8 carbon atoms, such as formic acid, acetic acid, propionic acid and butyric acid.

<!><!>iFurthermore, according to the invention, the metal, oxyalkylates represent an effective carrier for supplying the metal to plants, animals and humans. The metal oxyalkylate can be added | the soil for assimilation by plants and is supplied with fertilizer for animals and humans as a supplement in fertilizer mixtures. j|

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i I The metal used as a reactant is free metal and' i<1>]: is preferably in finely divided form, such as shot or powder I to facilitate the reaction. The carboxylic acid is used in any suitable concentration, but relatively high concentrations are preferred because it is preferred that the third reactant, namely hydrogen peroxide, be added in a dilute aqueous solution and because it is preferred to minimize ;the total amount of water in the reaction mixture. When the acid is j acetic acid, then glacial acetic acid, which is easily available by hand, can be used. The amount of acid used is preferably no more than the stouchometric amount. As it is relatively easy to remove similarly reacted metal, which remains undissolved, it is preferred ;å| use the metal in an amount that exceeds the staucome-1 ■ itric in relation to the acid. A profit of 1.0 - 3 times j

1 idea; n stouchometric quantity is preferred. I i |i : 'i ! ■ Hydrogen peroxide is preferably used in an excess in relation to the stouchometric quantity. A weight ratio of 0.1- ; |0.5 parts by weight per metal by weight is preferred. j ; The hydrogen peroxide is preferably used in a diluted form!

in 1 ; solution of up to 10% H~0_. A 3% o.p solution is preferred! et iI ;i,certain situations, for example when glacial acetic acid is used in jbecause the total amount of water in the aqueous reaction mixture I is appropriate when the hydrogen peroxide is introduced in this way. The amount of water in the system can vary within wide limits and is preferably at least sufficient to prevent boiling without further cooling. It is preferred that the quantity

i of water is sufficient to prevent the temperature of the reaction mixture from rising to approx. 90°C without further i

: ' i;refrigeration. j\

The reaction is preferably carried out at atmospheric pressure for economic reasons and at a temperature below the boiling point of the reaction mixture. In general, a temperature from room temperature and up to 130°C will be preferred. ;

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'When the reaction is complete, the excess of metal in 'f' is preferably removed by filtering or decanting the liquid phase.IJ j Precipitation is preferably achieved by adding acetone and[cooling, but can also be achieved by careful evaporationj of ! ; the aqueous reaction mixture. The amount of acetone is preferably 1-5 volumes per volume of aqueous phase and the aqueous phase is preferably cooled or allowed to cool at least to i<1>i

1 room temperature before adding acetone to minimize evaporation of this. The solution is then preferably ' cooled and then to a temperature below 10°C to precipitate u,t !

in j;metaloxyalkylate. Although the reaction mixture can be cooled ! in addition, it is generally not necessary to precipitate essentially all of the metal oxyalkylate, and to cool below -1°C.

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in ;; The precipitated metal oxyalkylates are recovered by filtration or clay

.similar and dried. ,

<!><;>Although the structure for zinc oxyalkylate is determined to be Zn40(R-CO2) and that for manganese to be Mn^O (R-CO,,)^, in which; R' is hydrogen or alkyl, the structure for the reaction products of all the other metals and acids has not yet been determined. Meanwhile, the following general information can be given in j

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;wherein M is a metal, x is an integer in the range 2-8 and; R 1 is hydrogen or alkyl. JJ! I I .The examples shall be illustrated by the following examples. : i I!!I : M l i ; I j I

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I 1 EXAMPLES 1 'iI

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1 Example 1 Preparation of zinc oxyacetate

!Into a 600 ml beaker, 50 g (0.765 gram atoms) of zinc-j metal shot are introduced. Then 45 ml (0.767 mol) of glacial acetic acid was added. To the mixture was added 400 ml of 3% hydrogen peroxide and the mixture was stirred at room temperature for 1 h.

i 1 i: The reaction mixture was decanted to remove unreacted zinc precipitate. Then 1200 ml of acetone was added to the decanted liquid and the solution cooled to 4°C. After 1 hour, the precipitate was filtered off to give 50 g of the white precipitated final product (heleakis (acetato)oxotetrazinc). j

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j Example II Preparation of zinc oxyacetate

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Into a 2000 ml beaker was introduced 100 g (1.53 g-atom) of zinc metal shot. Then 90 ml (1.57 mol) of glacial acetic acid was added and to the resulting mixture was added 800 ml of 3% hydrogen peroxide. The mixture was heated to 94°C for 30 min. while stirring. Unreacted zinc was removed and the solution cooled overnight in a large container and after the addition of 2400 ml of acetone gave 115 g of white product (hexakis (acetato) oxotetra;

.zinc).

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As mentioned above, the metal oxyalkylate can be added to the soil as such or in a mixture with a suitable carrier such as a fertilizer mixture containing other plant nutrients. components such as nitrogen, phosphorus or potassium. Forbindel-i i 'sen is also suitable for supplying metals to animals or humans and can be supplied in tablet or other suitable form | in mixture with a suitable carrier such as water, soluble wax<1> or other solid excipient. The compounds can also be mixed! with food products for human or animal consumption<1>, such as breakfast cereals, animal feed and the like. j

li! Mi engde of connections managed will of course vi;s\1 ! i i be dependent on the amount of metal that it is desired to j j add to the plant or for absorption in animals or humans j For agricultural purposes, the amount of metal used can be determined based on the amount that the soil is assumed to contain {

I in the arm with regard to a particular metal or with an amount in which the plant is believed to be lacking. In the same way for animal or human application, the metal dose can be determined based on the lack of metal in the diet or lack of the relevant metal in the blood plasma, in the body tissue or the like. The dose can vary widely I for the different metals, especially for agricultural purposes, in 'For zinc the dose will generally be as follows:

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l in Examples III - XVI \

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i 'Example I is repeated except that the zinc metal shot

i i i was replaced with 50 g of the following finely divided metals:j I III - beryllium; IV - magnesium; V - chrome; ! VII - iron; VIII - cobalt; IX - nickel; X - palladium; XI -;

platinum; XII - smallpox; XIII - silver; XIV - gold; XV - cadium,;

XVI - mercury. The obtained metal oxyacetate reaction products are useful in the same way as indicated for the zinc oxyacetate reaction product for supplying metal to plants, animals and humans. The amount of metal added will naturally depend on the metal and desirable amounts of metal to be added will be well known for particular applications. IN

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Examples XVII - XX ! j

Example 1 was followed except that glacial acetic acid was replaced by an equivalent amount of the following acids: !• ■!<1>. I XVII - formic acid; XVIII - propionic acid; XIX - n-butyric acid and ' !XX - isobutyric acid. The zinc oxyalkylate products obtained are in !ny1 ttige as indicated above.<i>]

Example XXI i

!to feed! |hrba idndeen l■ sføen lgeinfdøe lge streukksetmupreel llVe I fobrlme ealn: alysed and found ; j I<I>j|

il II i ! ! i i I Mn40(CH3-C02)6.|

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Claims (1)

j i liI <.> Process for the production of a metal |i Ioxyalkylate, characterized by reacting I j e.t metal, a carboxylic acid and hydrogen peroxide in an aqueous i ]reaction mixture, precipitating the metal oxyalkylate and recovering j this. j 2'. Method according to claim 1, grade i-j is! e r t in that the metal consists of zinc. j M i : I in 3. Method according to claim 1, character i-I ; especially in that a metal such as beryllium is used, 1 manganese, iron, cobalt, nickel, I imagnesium, chromium, manganese, iron, cobalt, nickel, palladium^, pla-jtina, copper, silver, gold, cadmium and mercury. in ! :4 <!.> Method according to claim 1, character i-] s|e r t in that the carboxylic acid used is an aliphatic! carboxylic acid containing 1-8 carbon atoms. in I i i u i I 5. Method according to claim 4, character i-; . sure that the acid used is formic acid, acetic acid, propionic acid or butyric acid. I ■ 6. Method according to claim 1, character i-'s]e r t in that the acid consists of acetic acid. \ \ i i .7. Method according to claim 1, character i-i in that the metal oxyalkylate is precipitated by the addition of acetone to the reaction mixture. j <:><1><1><1> i8. Method according to claim 1, character i-i ■ i . i sle r t in that hydrogen D eroxide is used in an amount i of 0.1 - 0.5 parts by weight per parts by weight per weight part metal, ' ' li <1> : i <!> ! <!> in ; 9 in . Metal oxyalkylates are characterized by the formula : IMxO (R -C02 )6 in j! li! in which M is a metal cation, x is an integer in the range 2 - 8 i i 1 i i ; and R is hydrogen or alkyl. ! j