CA1243331A - Diphosphonic derivate applications to cation exchange, novel diphosphonic derivatives, and their manufacture - Google Patents

Abstract

Summary of The Disclosure Application to the exchange of cations of diphosphonic derivatives, the acid form of which is represented by the following general formula G: <IMG> where R is chosen from the group consisting of alkyl radicals containing 1 to 12 carbon atoms and at most 2 branches on the main chain and with hydrogen, or A is a divalent organic radical chosen from the group of mono, di or tri-substituted ethylenes and mono or di-substituted ethylenes.

Description

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The subject of the present invention is the application diphosphonic drifts in the exchange of cations, new diphosphonic derivatives and their process Manufacturing.
In recent years ~ recovery metal ions and the purification of aqueous solutions have increasingly used ion exchangers under resin form or sub-form of liquid extracting agents quide-liquid.
There are already dlores and already on the market of name-brous extracting compositions. However, these compounds some metal cations cannot be exchanged when these are dissolved in solutions very acidic and / or highly complexing aqueous ions.
One of the most difficult issues to deal with is recovery of actinides and certain rare earths contained in phosphoric acid solutions and more particularly the recovery of uranium contained in solutions of crude phosphoric acid, the content of which P205 ranges from 10 to 50% by weight.
This is why one of the aims of this vention is to provide a co ~ position extractor suscep-tible to extract certain metallic cations present in certain complexing or very acidic media.
Another aim is to provide a composition of the previous type likely to extract uranium from ~ phosphoric acid with a P20 content ~ varying from 10 to : ~ ~ 0%.
~: ~ Another aim finally is to provide a method of : 30 uranium recovery by exchange of cations in the : phosphoric medium above by using said compositions, the temperature possibly varying from the temperature ambient temperature at 70-80C.
:: These goals are achieved by means of the application :: 35 for the exchange of ciphosphonic derivatives including the H ~: ~: acid form is represented by the general formula G
: next :
.: O ~ O
RO - P - A - ~ - O - R x o ~ ~ OH

`- ~ 2 ~ 333 ~

- 2 -where R is chosen from the group consisting of the remains alkyls having 1 to 12 carbon atoms and at most 2 ramifications on the main chain and by hydrogen, or A is a divalent organic radical chosen from the 5 group of mono, di or tri-substituted ethylenes and mono or di-substituted methylenes.
Among the active diphosphonic groups, it should point out a group which has the merit of having excellent extractrlces capacities while being easy 10 access. It is the hydroxy-methylene group diphosphonic.
Another group that is also easily accessible is the amino-methylene diphosphonic group.
However, although it is more difficult to syn-15 thetiser, the methylene diphosphonic group seems to be the one with the best chemical stability with excellent extraction characteristics.
The derivatives according to the present invention can be liquid-liquid extracting agents whose 20 total number of carbons is between 7 and 50, which are optionally diluted in a hydrocarbon thinner chosen from the group of saturated hydrocarbons and aliphatic and aromatic unsaturated and mixtures thereof.
The total number of carbon atoms in these 25 derivatives is preferably between 15 and ~ 0, the domain the more satisfactory being between 18 and 30.
As can be seen from the examples, the properties extractors of these derivatives can vary significantly according to the characteristics of the hydrocarbon chains A
30 or R. Thus a highly branched chain and / or comprising cyclanic or bicyclic compounds gives the poses resulting from the synthesis a very weak lipophilicity lower than that given by the linear chains having the same number of carbons. However we will not depart from 35 the invention considering that when there is a cyclane in a chain, the chain is equivalent to a chain ; ~ linear or cyclane is counted for half of carbons it contains.
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We can compare the hydroxy-diphosphones obtained by the action, described below, of phosphorus trichloride on naphthenic acid having in principle 23 carbon atoms and very branched on the one hand, 5 and on products from known stationery residue under the name of Scandinavian origin "Tallol" and which is a mixture of oleic and linoleic acids, acids whose linear chains have 1 ~ carbon atoms and which have one and two unsaturations respectively 10 on the other hand. In the first case, the solubility of the derivative diphosphonic in water is very high, which makes its very expensive job. In the second case the solubility in the aqueous phase is extremely weak, less than 1 / 3000th. Symmetrical diesterification, or 1 ~ asymmetrical, plays a very important dual role; she considerably reduces the water solubility of acids thus obtained and it leads to an increase very important to the selectivity of the extraction of uranium versus iron in backgrounds 20 phosphorics.
In view of the above and the data we can give a definition of a product of inexpensive synthesis and presenting excellent qualities extraction. Such a product is derived from a fatty acid to 25 linear chain and having undergone diphosphonation using phosphorus trichloride and having undergone a diesterification cation. The product thus obtained must have a radical A having at least 8 carbon atoms and preferably between-be 15 and 25 and have at most two ramifications and 30 preferably none, the radical R having from 1 to 15 atoms carbon, preferably from 8 to 1 ~, and presenting at most two ramifications.
These products have the remarkable advantage than any other extraction product 35 of the uranium in the oxidation state IV contained in the acid phosphoric, to be insoluble in basic medium, which allows re-extraction using carbonate solutions alkaline or ammonium and an oxidant allowing the passage of uranium from valence IV to valence VI.
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The compounds according to the invention can also be ion exchange resins whose groupings active ingredients meet formula G.
The present invention also aims to provide new diphosphonic derivatives of formula G ' characterized by the fact that they meet the formula general G or A corresponds to the formula:
AT' I

A = -G-I
z where R is chosen from the group consisting of the atom of hydrogen and hydrocarbon residues of 1 to 15 atoms carbon, where A 'is selected from the group consisting of hydrocarbon radicals having from 1 to 30 atoms of carbon and at most two ramifications by chains side of a resin with other chains lateral carrying groups of type G 'and having a rate phosphorus of at least 5 ~ where Z is chosen from the group is formed by hydrocarbon radicals having from 1 to 30 carbon atoms and at most two ramifications, by the amino groups (NH2 non, mono- or di-substituted), by alcohol groups (non-substituted or substituted OH) and by the hydrogen atom.
The radical R of formula G preferably having from 8 to 12 carbon atoms and having at most two ramifications.
The total number of carbon atoms being advantageously between 10 and 50, preferably between 15 and 40, the most satisfactory area being between 18 and 30.
Compared to known phosphorus derivatives . ~
likely to extract uranium, such as OPPA, derivatives according to the invention have the originality of seeing their lipophilic nature is linked to the length of a chain directly attaches to phosphorus through bonds carbon-phosphorus and located between the two atoms of ~ 333 ~ L

phosphorus. This is why the constraints at the level of ~ group A are the strictest, i.e.
advantageously must have at least 8 carbon atoms and preferably between 15 and 25. These derivatives also have advantage of having great stability with respect to acid reagents, in particular hydrofluoric acid.
Finally, it should be noted that when Z is hydrophilic, i.e. when it is amino or hydroxyl and when this is not offset by a loss hydrophilicity by partial esterification of phosphonic acid groups, to obtain a satisfactory lipophilicity it is necessary that the group A 'has at least 14 carbon atoms.
With regard to the new derivatives that constitute the ion exchange resins according to the invention, they are preferably characterized by the the resin is chosen from the group by acrylic resins and cross-linked polystyrenes.
Preferably the phosphorus content by weight of the resin is between 10 and 25%.
An additional object of the invention is to him provide a process for the synthesis of new derivatives ~ elon the invention.
The invention provides a method for synthesizing diphosphonic derivatives of formula G 'characterized in that the phosphorus content by weight of the resin is understood between 10 and 25%, and characterized in that it includes the following steps:
(1) a resin carrying acid groups is acidified carboxylic ~ using a mineral acid;
(2) the acidified resin is rinsed in order to remove the traces of mineral acid;

(3) we bring the r ~ sine ~ at least a degree of dryness equal ~ that obtained by azeotropi training ~ eu at benzene;

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- 5a ~ 333 ~

(4) it is made to inflate the dried sine using a inert solvent preferably comprising at least one ether bridge and capable of dissolving at least 3% of its volume of water and at least 8% of its volume of ~ xichloride phosphorus;

(5) we add ~ ute to the r ~ sine inflated between 5 and 50 ~ sound volume of Pau and phosphorus trichloride, at a rate 1 ~ 2.5 mole of water per mole of trichloride phosphorus;
lQ (6) the temperature is brought to between 90 and 140 ~ C for 0.5 to 10 hours;
(7) repeating the ~ operations (5) and (6) at least one times and preferably at least twice, lowering ~ possibly the temperature between 20 and 80 C before each new introduction;
(8) rinsing with water and drying the resin;
(9) the resin is completely esterified so that known in itself.
Synthesis of the above derivatives of formula G
which are fat soluble and therefore can be qualified of micro-molecules, can be carried out using well-known homogeneous single phase reactions of the specialist in phosphorus chemistry. These reactions are exposed below by the following equations where the radicals R, R 'and R "~ have different from cPux which are ~ ~ exposed in formula G and where X has the meaning of a ; halogen atom:

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~ ~) 7 '' :. '''' -,:
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~ 2 R - COOH + PC13 - ~ R - C tOH) (P03H2) 2 R - CN + PC13 ~ R - C (N ~ 2) (P03H2) 2 1) Na CH2 - (PO) OR ') 2 - ~ ~ R - CH - (P03H2) 2 2) R - X
2) HCl at 60C
R - CHX - C ~ R '+ NaP03R "~
R - CH (P03HR ") - CEI (P03HR" ~ - R '+ NaX
The stoichiometry of these reactions is not respected.
Regarding the esterification of solvents diphosphonated, it can be effected by the action of the corresponding acyl orthoformate according to a mode identical operating procedure ~ that followed for esterification carboxylic acids.
All fat-soluble derivatives according to the present invention were made using the techniques described above.
When the diphosphonic derivatives are resins, the preferred method of synthesis is to graft diphosp ~ onic groups on a resin carrier of carboxylic acid functions, known per se.
Another method is to prepare diphosphosnic monomers, to polymers and crosslink the polymer obtained to transform it into a - resin.
When using the grafting method, we can either use the reactions indicated above simply transposed to the case of resins, or : ~
implements a process specially designed to prepare resins according to the invention. In the first case, we generally obtains weakly charged resins ~, ~ 3 ~ 3 ~

phosphorus in the second case, resins are obtained, the phosphorus content by weight is considerable, generally cost between 10 and 25%, which leads to particularly efficient disphosphonic derivatives S vis-à-vis the cation exchange.
The invention therefore also relates to a method for the synthesis of phosphorus-containing diphosphonic resins by weight between 10 and 25% by weight.
This procedure has three essential aspects. The first concerns the degree of dryness of the resin departure. In this respect, it is essential to dry the resin in depth: an azeotropic training of benzene humidity is a sufficient method. Vne even more efficient method or treatment ~
additional desiccation are beneficial although not essential. The second important aspect of the process is the nature of the solvent used. The solvent must be inert, will allow a later reaction in medium homogeneous and preferably have ether bridges. The polarity of the solvent is not a crucial point.
However, the use of a solvent whose dielectric constant is between 2 and 10 to 25C
~ is advantageous. Likewise, solvents are preferred, the boiling point is higher than the temperature of 25 reaction between 90 and 140C ~ Point solvents of lower boiling point are nevertheless usable, even if it means operating the reaction under pressure. Finally, the third important aspect of the process is the temperature used: we operate preferably between 90 and 120C, without exceed about 140C. It has been found, in fact, that despite the thermal brittleness of type resins carboxylic terminations, the use of these temperatures is a very favorable parameter not only from the point of kinetics, but also from the point of view of the rate of su ~ stitution. The capacity of resins to undergo several - 8 - ~ 333 ~

cycles under the above conditions also appears as astonishing and is attributed to the selection of precise conditions performed.
It is thus possible to modify any resin comprising carboxylic groups such as resins acrylic or resins with imino-diacetic groups crosslinked polystyrene derivatives.
Another object of the present invention is to supply new positions likely to allow the extraction by solvents of different cations metallic.
~ n effect, the fat-soluble derivatives according to the invention are difficult to dissolve in diluents hydrocarbons conventionally used in industry and especially those who per ~ ettent use up 60-80C and does not dissolve although in some aromatic carbides, such as toluene, the toxicity of which is important and / or in relatively polar diluents flammable like ether and various esters carboxylic.
This is the reason why, during the study that led to this research, we sought to develop diluents capable of dissolving these compounds whose main constituent is a non-aromatic hydrocarbon.
This is how it could be shown that the addition in proportions varying from 1 to 20% of a compound polar water-immiscible lipophile allowed dissolve the compounds satisfactorily according to the present invention.
These lipophilic and immiscible poI compounds with water can in particular be alcohols, ketones, phosphoric acid triesters ~ sulfones, sul ~ oxides, halogenated derivatives, oxides of trialcoyl ~ phosphine. They can also be acids ~ g ~ Z ~ 333 ~ l long chain carboxylic acids such as those hydroxydiphosphonation to obtain one of the derivatives according to the invention.
However, it is more practical to use primary, secondary or tertiary alcohols, the number of carbons is between 5 and 12 and preferably between 6 and 10.
Octanol-2, more often called ~ alcohol caprylic, and dodecanol are ideal in proportions between 2 and 20%, from preference between 3 and 10%.
It should be noted here that these compounds water-immiscible lipophilic fleeces do not have without influence ~ ur behavior of derivatives ~ elon ~
the invention and their pui ~ extractor ance tends to decrease when the concentration of said polar compound increases, the respective selectivity between the various cations also varies. In the case of the extraction of Uranium by solvent, said compounds cause also an extraction of phosphori acid ~ ue especially l ~ rsque the latter is very concentrated.
This is the reason why the compositions ~ According to the present invention are constituted by s ~ lution from 0.01 M to 0.2 M of derivative ~ n corresponding to the formula G di ~ s ~ us in a diluent h ~ drocarbon, preferably non-aromatic, and in a polar compound water-immiscible lipophilic chosen from the group consisting of leg ~ liquors, ketones, triesters of phosphoric acid, ~ ~ ulfones, ~ sulfoxides, halogenated derivatives, the trialkyl phosphine oxides and carboxylic acids ~ long chain (7 to 30 atoms of carbon, preferably 15 to 25).
You can choose the diluent ~ hydrocarbon from those sold industrially by societeR
oil. Mention may in particular be made of the product sold by the ~ ESSO company under the no ~ "EXSOL D lOO" or ESC ~ ID 120.

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Regarding the recovery process the uranium present in phosphoric acid, in the case use of solvents, just use the techniques of contacting developed in the well known case octyl-pyrophosphoric acid, better known by its acronym of OPPA, the elution then being carried out by contact with hydrofluoric acid.
However the extraction techniques are much easier in the case of the use of extractants according to the present invention and in particular in the case of the diesterified compounds according to the invention.
We observe indeed, even in the presence of fairly strong ferric iron concentrations, very few emulsions. In in addition, these compounds are capable of extracting uranium even at very high concentrations of P2O5 such than that marketed as 50% by weight With regard to re-extraction, it is possible to re-extract using sulfuric solutions iron sulfate. However the kinetics of these re-extractions is slow. In the case of compounds diesterified it is ~ however possible to re-extract uranium using sodium carbonate solutions and / or ammonium and an oxidant capable of oxidizing uranium IV in the solvent e ~ uranium VI. Said oxidant maybe hydrogen peroxide. Carbonate concentration of sodiu ~ can vary between 0.5 and the limit of olubility of this carbonate. For other alkali carbonates or the same limits apply.
With regard to re-extraction techniques basics and solutions likely to re-extract uranium content, we can use techniques described and / or cited in patent applications French posted by MINEMET RECHERCHE under the numbers 77/25889, 78/25815, 79/04760 and 79/04761, respectively 35 published under No. 2,423,545; 2,435,444; 2,449,728; and .

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2,449,652, November 16, 1979, April 4, 1980, 19 September 1 ~ 80, and September 19, 1980.
In the case of the use of resins, contact the resin with uranium phosphoric acid, chemically reduced or not, pui ~ eluted in an oxidizing medium using solutions of alkali carbonate or ammonium, from 10 to 200 grams per liter.
However such reextraction, ~ years doubt cause of the presence of oxygenated water, has a ~ endance to alter the resin and reduce the quantity of groupings active in this resin. This is the reason which ~ 1 ~ is better to use other techniques which also have the advantage of not having neutralize the acidity of the acid phosphoric ~ So we could show ~ ue we could elute the re ~ ines using 6ulfate solutions ~ errique concentrated in the presence of a little sulfuric acid (O, 1 N a 1 ~) to avoid the precipitation of this ~ elO
Products ~ according to the invention, resins or solvent ~ have excellent extracting qualities for many ~ vices and p ~ ur which little extractant6 é have known6 in ~ acid place. Among the ~ cation6 easily extracted we can cite all ~ vices presenting a 60us-neck ~ he f ain6i ~ ue the yttrium and by consequently the lanthanides and the actinides. They have relatively high capacity for alkaline earth and for different elements of Tri- or tetravalent transmissionb In particular the lead is selectively extracted by comparison with ~ inc and copper, these two ~ last elements being extracted them also but at lower acidities.
The derivatives according to the invention are also treated uranium or ~ has form VI, although the coefficients of sharing be, for ~ olvants in ~ out case, less lower than uranium IV. However, as far as ~~
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- 12 - ~ Z ~ 333 ~

relates to the resins according to the invention, the fixing of uranium VI is excellent since it is possible to fix non-negligible quantities of uranium VI in presence of a very strong excess of ferric iron. This phenomenon could be due to the ~ that the ions metallic in the resin can only be liganded times, in the extreme, twice, while in phase liquid the cations can be as liganded as necessary.
As a purely indicative uraniu ~ IV seems linked in the extraction phenomena involving the diesterified liposoluble product according to the invention to two molecules of extractant. In other words it can be considered diliganded while iron III would form a complex involving two ions ferric and three molecules of extractant.
The following examples which do not show no limiting nature are intended to put the specialists able to easily determine the conditions which should be used in each case particular ~
Example 1 Preparation of Alkyl Methylene Diphos Acid phonic I - Preparation of the sodium derivative of the ester (the ~
We operate on equimolecular quantities ester and sodium.

~ a + H2C CP (0) (0C ~ (CH3) 2) 2] 2 t Na CH [P (0) (OCH (CH3) 2) 2] 2 In a balloon, fitted with a thermometer, a metallic stirrer driven by an electric motor, of a dropping funnel and a coolant, 1.6 are dispersed g of ~ a in 15 ml of anhydrous toluene heated to reflux, under vigorous agitation. Then cooled to 20C and 24.3 g of isopropyl methylene disphosphonate, la, maintaining ~ 2 ~ 333 ~

the reaction mixture between 20 and 30 by means of a bath of acetone-dry ice until the sodiumO disappears completely II - Alkylation of the sodium derivative. Preparation of benzyl-me-isopropyl thylene disphophonate, lb On ~ joust, in ~ itu, to the soda derivative in solution in toluene, heated to 100, 11 ml of bromide benzyl. We continue to heat at 60 for one hour.
The toluene SOU9 is then evaporated off the vacuum of the tube at water. 50 ml of technical hexane and 50 ml of water are added.
This mixture is transferred to a separatory funnel. We separates the organic phase in hexane from the phase aqueus ~ with 50 ml portions of hexane. The sentence hexanic is ens ~ ite washed with water until disappearance of traces of brominated derivatives in washing water (test at N03Ag). The organic phase is dried over anhydrous sodium. Then evaporate the empty SOU5 solvent.
The distillation of the raw product allows collect 14.6 g of expected lb ester. The content residue in the flask (3.4 g) is composed of a mixture of acids benzyl-methylene-diphosphonic (diacids and triacids).
Yield of alkylation of 1 ester lb = 60%. The formation of ben7yl-disphosphonic acids can can be explained by the hydrolysis of the ester lb during the organic phase extractions and washes.
III - Hydrolysis of the ester lb. Acid preparation benæyl-methylene-diphosphonic, 2b CH - ~ P (0) (OCH (CH3) 2) 2] 2 ~ IH - [P (0) (OH) 2 ~ 2 ~ 6H5 ~ 6H5 1.5 g of lb ester and 11 ml of hydrochloric acid concentrate are heated at reflux for 3 hours. We the acid and water are then evaporated under vacuum and added to the pasty mass 15 ml of isopropyl alcohol and distills under vacuum to entrain acidic water.
The operation is repeated 3 times O We end up drying the "i :.
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crystals in a vacuum desiccator. The yield in acid is quantitative.
The method developed for the synthesis of ester 1b, the sodium derivative of ester la and acid 2b has been successfully applied for the synthesis of esters heptyl, dodecyl, hexadecyl, methylene-diphosphonic as well as corresponding acids.
Regarding the dialkyl ester l7Hl5 I [P (0) (OCH - (CH3) 2) 2] 2, we got it easily C 7.15 am from the goded derivative of the monoheptyl ester. The dialcoylation is obtained with a yield of 27%.
Hydrolysis of isopropyl esters of acids diphosphonic acid corresponding is done with good yields and easily; that's the reason which we have chosen.
The analytical method used to follow these syntheses was ~ NMR spectrography of the proton. The routine spectra were recorded on a device Varian EM 360 V, ~ from solutions in the carbon tetrachloride with TMS as reference internal.
Characteristic signals for esters are:

CH - [p (O) (OC ~ - (c ~ 3) 2) 2 ~ 2 CH2 ~ 2.1 ppm (triplet) CH - (CH3) 2 - 4.7 ppm (7 open lines) CH3 - CH - 1.2 ppm ~ doublet J = 8 Hz) CH - ~ P (0) (OCH - (CH3) 2) ~] 2 C6H5 - 7.2 ppm C ~ - tCh3) 2 - 4.7 ppm (7 split lines) CH3 - 1.3 ppm ~ 333 ~

CH - [P (O) toCH - (CEI3) 2) 2] 2 (CE ~ 2) 6 CH3 - (CH2) 6 - 0.9 ppm CH - (CH3) 2 - 4.65 ppm (7 split lines (CH3) - CH - 1.3 ppm (doublet J = 6 EIz) C ~ - [p (O) (OCH - (CH3) 2) 2] 2 I (CH2) 11 CH3 and C ~ - ~ p (O) (OCH ~ (CH3) 2) 2] 2 (CH2) 15 CH3 CH3 (CH2) n - O, 85 ppm CH - (CH3) 2 - 4.7 ppm (7 open lines (CH3) - CH - 1.3 ppm (doubet J = 8 Hz) (CH2) 6 CH3 C - tP ~ O) (OCH - (C ~ 3) 232 I

(CH2) 6 - CH3 CH3 (CH2) 6, pp CH - (CH3) 2 - 4 ~ 75 ppm (multiplet) (CH3) 2 ~ CH - 1.3 ppm (doùblet) ~ `Regarding methylene disphos acids-phonic, we see in RM ~ the disappearance of the protons isopropyl at 1.3 ppm methyl doublet and 4.7 ppm massive ~ u CH - CH and the appearance of signals ~ low fields : due to acid protons - which helps control partial or total hydrolysis.

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Example 3: ~ ydroxy-phosphonization of the acid sold by SHELL under the name naphthenic acid Seven molecules of naphthenic acid for two phosphorus chloride (PC13) molecules are put in reaction according to the techniques described in the patent Belgian 619,600. The reaction product is then diluted to 30% in kerosene then the mixture thus obtained is put in contact with a 30% phosphoric acid solution P205 containing 100 mg / liter of uranium. The biggest part of the uranium is extracted so that the solution is reduced or not.
Example 4 Diphosphonation test of the product known as the name "Tallol"
We proceed as in the previous example.
Example 5: Diesterification of the products obtained according to examples 3 and 4 These products are mixed with a very wide excess (2 times the stoichiometric amount) ethyl or methyl orthoformate depending on the ester we want to do. During this opera ~ ion two functions of hydroxy diphosphonic acids and the acid function of tall oil or naphthenic acid are esterified. We proceed according to classical techniques in organic chemistry for esterification using alkyl orthoformate. Once the reaction has been made, we evaporates solvents using a device commonly called "rotavapor", pUi8 by drawing under vacuum using a puck pump. Like resonance studies nuclear magnetic show, the base is made of diesterified hydroxy-diphosphonic products practically pure.
The methyl derivative of the acid was thus prepared naphthenic and ethylated from the product from Tallol.
Example 6: ~ Hydroxy-diphosphonization of the resin sold under the trade name C 464 DIAPROSIM *.
* ~ arque de co ~ merce -``? ~
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- 17 ~ 333 ~

We tried to get rid of excess water c ~ ntenue in the resin either by pre-treating it with anhydrous dioxane, either by using a large excess of PC13.
Procedure.
- Resin: 5 ml - Anhydrous dioxane: 50 ml Heating 30 minutes to 100C.
- Filtration on sintered, hot O Drying by holding aspira ~ ion for 5 minutes.
- Transfer of the dry product in ~ be to essa1. Addition of:
Dioxane: 2 ml P ~ 13: 0.9 ml - Heating in a hot water bath for 2 hours.
Resumption by H2O, filtration, washing, drying.
Several resin samples were processed in this way and the resins obtained were put in contact with 30 ~ phosphoric acid solutions containing 100 mg of uranium in reduced form (90% iron in Fe form). Reduced to a concentration per kilo resin of one mole of hydro group ~ ym ethylene disphosphonic, the resin has a partition coefficient between the resin phase and the phase aqueous of about 80 and the saturation capacity of around 70 g / kg of resin.
Furthermore, all of the compounds described in examples 1 and 2 were tested on the same solution and all exhibited uranium mining activity very high.

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Other tests have shown the possibility to extract, in addition to uranium, other divalent metals, especially in the group ~ ent actinides and lanthanides.
Example 7: Extraction with the derivative obtained in Example 3 of elements other than uranium.
Com ~ osition of the aqueous phases and form under the elements have been introduced.
The selected elements are divided into two solution at pH 1, Sl, and S2 containing approximately 100 mg / l of each of them.

~ l S2 ¦ Pb - p ~ C12 ¦ V - V2 ~ 5 Zn - ZnCl 2 ¦ Mo MoO3 Cu _ CuCl 2 ¦ In _ InCl 3 Ni ~ _. NiC12 ¦ Bi - BiC13 20. I Co _ CoCl 2 ~ Sn _ SnCl 2 Cr _ CrCl 3 ¦ Tl Tl C03 Sb _. SbC13 ¦ Ca - CaC12 Ga _ GaCl 3 ¦ Cd _ CdC03 - 19 ~ 333 ~

¦ initial ¦ contact ¦ initial ¦ contact I Cu 1100 ~ 75 1 100 100 ¦ Fe ¦ND ND
¦ Ga ¦100 ¦ ND
¦ Zn ¦100 ¦ 100 I Co I100 1 50 1 ll ¦ Ni 100 ¦ 75 ll ¦
¦ ~ r 100 ¦ 100 ¦100 ~ ND
¦ The 100 ~ ND
IVI ~ I100 ~ 50 ¦ Cd ¦ l l100 ~ 80 - 90 ¦ In ¦ ¦ ¦100 ¦ ND
¦ MB ~ I100 ¦ ND
¦ Tl ¦ ¦100 ¦ 50 Hg I ¦100 1 lO0 ¦ Sn l lND ¦ ND
¦ Bi l lTP ~ ND
2 ~ ¦ Th ¦ l lTP ¦ ND
l Ca l ¦ ¦100 ~ 90 - 100 ~.
:: TP = possible traces ND - n ~ n detected.

omission of ~ organic hase 0.1 M diphosphonic derivative in Exsol D100 octanol 5% by volume Conditions ~ e ~ test procedure ~: Contacts organic phase and aqueous phase ~ 1 are carried out in ampoules ~ decant with:
/ A = 1/15 ~: - Contact time: 10 min ~: ~ 35 - Ambient temperature.
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Results The elements are dosed semi-quantitatively.
by X-ray fluorescence, in the aqueous phases before and after contact with the organic phase.
The table above expresses the quantity of element present as a percentage compared to the initial solutions (100% basis).
Note: the virgin organic phase would contain traces of copper and iron (probably mg / l).
Exe ~ le 8: Uranium extraction test in the environment phosphoric using hydroxy-diphosphonic compounds from the reaction of phosphorus trichloride on Tallol Organic phases containing 0.1 mole per liter of reagent dissolved in the solvent sold by ESSo 80US the trade name ESCAID * 120, (* brand of trade) added with 5 ~ of Octanol, are put in contact with uranium and dissolved iron solutions in phosphoric acid containing 30% P2O5. The iron is introduced ~ in the form of Mohr salt and uranium under form of uranium IV dissolved in a 1 N solution of acid sulfuric.
The duration of the contact, chosen 30 minutes, is very much higher than that necessary for reach equilibrium ~ 5 minutes).
In these experiments, we vary the uranium concentration in the starting aqueous phase dP.
The first table corresponds to the product from ~ allol years modified and additionally containing Tallol residual (approximately the same amount expressed in moles as that of the hydroxy-diphosphonated reagent) (see example 4). The second table corresponds to the reagent obtained; from Tallol and having undergone an esterification reaction, which leads to a diethyl ester of acid hydroxy-diphogphonic. This product contains only a few or no residual Tallol. (see example 5).

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~ 21 -Table 1 ¦ Phase ~ queuse ¦ Organic phase¦ ¦
- ~ Kd ~ FeII / Fe tot.¦U introduced¦U equil ~ - ¦ R IU equilibrium¦ î
(mg / l ~ brebre ~ g ~ (mg / l) 100 - I 20 1 ~ 10 IL8 1200 ~> 20 ~ 5 ~ 0 1 ~ 10 1 "I5000 1> ~
1 ~ 11,000 1,260 1 '17,400 l 2 Table 2 ~ T--Aqueous phase ~ Organic phase¦ l Kd ¦
FeII / Fe tot. U intro ~ uit U equili- RU balance (X) (mg / l) bre (mg / l ~ I ~ g / l) ., -,. , 1100 - ~ 20 ~ <10 1'9 1 ~ 1 ~ 20 500 1 ~ 10. I "I5000 17 ~
750 1 75 ~ 6860 1 9I
1000 1180 1 u 1823 ~ l 4 ~ 2000 11470 1 u 18440 1 6 1 ~ 0 ~ I 100 1 30 1 u 1700 1 23 Example 9 - Study of the Influence of Octanol and the Rate .

reduction in the extraction of uranium by the compound 30 diesterized hydroxy diphosphonates from Tallol.
The phosphoric acid used is the same as the one described in the previous example. However, iron was introduced as Mohr salt and sulfate ferric so that the amount of total iron 35 dis & ous remains con ~ tante and of ~ ani to obtain the rate of reduction ~ specified in ~ the following tables ~.

~ 2 ~ 33 ~ L

The first table corresponds to the use of a solvent containing 0.1 M of the diphonic component diesterified. The second table corresponds to a 0.05 M concentration of the same compound.
The Octanol content of the phase was varied organic.
T ~ bl water FeII ¦Octanol I Phase I Organic phase Fe tot. IS euseaqueuse ~ KdU¦SU / Fe¦
XI ¦ UA 3 uo ¦ F ~ o ¦ pl ~ l (mg / l ~ I (mg / l) I (mgtl 1 I (g / l) 3 ~ 65I 653 ~ I 680 I 7.19 24.6I 5 ~
IS I 325I 5890 I 930 I 6, g ~ 18.1I ~ 8 100 _ 15 2056900 ~ 50 ~, 84 33, 7 I
9û 15 2806250 500 6 "84 ¦ 22 D 3 ¦ 67 3155800 660 6 ~ 84 l lB ~ 4 l 84 ~ _ Water table 2 = ~ ~ rr ~
~ Fe tot.¦ X ¦aqueuse ¦ KdUls U / Fe¦
: ~ ¦ X l ¦ UA ~ U0 ~ Feo ¦ P ¦
~ mg / l) ¦ ~ mg / l) ¦ (mg / l) ¦ (~

~ 0 I 5 I 160 I 2980 1 350 I 3.21I1896I 80 ~ I 190 2680 I 4 ~ 0 I 3.21 I 14.1 100- 1 ~ 1 12 ~ 3390 1 ~ 3.49127 ~ 30 9O 1 ~. I 165 3040 I ~ 90 3.46I1 ~, 4I 9 . ~ ~ ~ 80 15 I 18 ~ ~ 740 1 3 ~ 1 3.51I15.2I 120 ~, :: 35 ~. , ~ 333 ~

dU UO / UA partition coefficient SU / Fe = coeffectiveness of ~ electivity ~ of uranium by compared to iron:
UA / Fe.a, OU / FeO

Example 10: Eg ~ ai of golubility of ~ olvants from Tallol.
The phases ~ organi ~ ues containing 0.1 M of the derivatives Tallol iS8US, diethyl ~ s or not, modified in contact with ~ phaæes aquPuses constituted.by de pho ~ phoric acid at 30%, the ratio of the two phases being equal to 1.
The results for the two solvan $ ~ show a loss less than I / 3000th.
E ~ sai re-extraction of uranium content in the organic phases ~ using hydrofluoric acid ~ eu.
An organic phase containing 0.05 M dP compound diphosphonique i ~ su du Tallol and die & terrified loaded ~
~; 4.2 gram 8 per liter of uranium is brought into contact with AYec ~ varying amounts of hydrofluoric acid ~ 50%. With - ~: an O / A of 40, 80% of the uranium is already precipitated 80U8 ; ~ ~ form of its tetrafluoride ~ With a 0 / A of 3.99 ~
: ~; 25: the uranium is ~ recovered ~.
This ~ results should be improved 8i before to do the rextraction we washed the organi ~ ue phase for get rid of dissolved phosphoric acid ~ for example with concentrated sulfuric acid.
The pha ~ 6th: organic thus regenerated has been brought to ; : new in contact ~ with an aqueous phase containing 30%
pho ~ phoric acid, 15 srams per liter of iron totally: reduced ~ The charge obtained after a contact makes it possible to reach saturation and to note that the diphosphQné product, despite ~ a rain contact of a ~ i ~

333: L

day at ~ ec hydrofluoric acid at 50 ~, did not see 6th altered extraction characteristics.
Example 12: Comparative Es of Verified Products and not esterified.
Phosphoric acid solutions at 30 ~
P205 are mi ~ es in contact with an organic phase containing naphthenic acid after hydroxy-diphosph ~ nation and the product from e ~ téri ~ ication of the first product. The ~ ~ eneurs ~ have indicated in the following table as well as the results of the extraction.

.... ,, _ ~, 15 Derived non esterif ~ e esterified ¦U 911 ¦Fe g / l ¦P 9/1 ¦U 9/1 ¦Fe 9 / l ~ P 9/1 ¦

¦ Water phase ¦0.15 ¦ 14.2 ¦ - ¦0.15 ¦ 14.2 ¦ - ¦
~ 'ni t ~ al e ~ Organ phase ~ which ¦ 13.67 1 ~ 12.70 vle rg e - ~ ~
¦Phase nrgan ~ que¦l, 30 ~ 1,01¦3,38 11 "3 1 0,55¦2,7D ¦
load ~ ~~
¦ Aqueous phase ¦ ~ 50 ~ 14.2 ¦ ¦ ~ 0 ¦ 14.5 ¦ ~ ¦
30 ~
:

~ '-~ 2 ~ 333 ~ L

Example 13: Uranium fixation test by percolation on a resin bed A resin prepared as described in the example 6 container after shaping cycles acid-base 9 ~ phosphorus by weight is placed in a column and a 30% phosphoric acid solution of P205 having the following composition Fe total 2 q / l, reduction rate of Fe 50 ~ uranium content ~ (at 124 mg / l is percolated at a speed of 6 bv (volume of the resin bed per hour). Then the resin is rinsed against the current and finally is eluted co-current by an olution of 100 g / l ferric sulfate at a rate of one bv per hour.
All these operations are carried out at one temperature of 60 degrees Celsius.
During the first 20 bv, there is no trace of uranium detectable on analysis. Then the content uranium from the phosphoric solution after percolation increases slowly.
Once the initial concentration is reached (120 bv approximately), we calculate the total amount of uraniu ~ fixed which is approximately 10 g / l.
Following percolation, elution allows recover 95% of the fixed uranium.
However, the content of the eluate does not exceed 0.7 g / l, probably due to the slowness of the exchange between the resin and the solution and the slowness of oxidation of uranium IV to uranium Vl.
EXAMPLE 14: Different types of uranium fixation P205 contents and at different oxidization rates.
These tests were carried out on the resin produced as described in Example 15.
2 ml swollen resin that has undergone cycles acid-base activation and shaping, are put in ~ scales in contact with 40 ml of solution phofiphoric containing uranium and iron in a state oxidation ~ specified in the table ~ next.

\ ~

. ~ _ __. , .. ~
t of cations Fe UU mg / l Fe g / l SO4 g / l P205 g / l IF FeII UIV 410 SF FeII uIV 100 SI FeII UIV 505 24.1 77.8 632 SF FeII uIV 190 23.3 78.5 635 5.I. FeIII UVI 405 SF FeIII uVI 240 SI FeIII u ~ I 495 26.7 99.0 694 SF FeIII UYI 380 26.7 101 713 l _, Example 15 ~ Synthesis example We pass 50 g of DUOLITE ES 466 resin, marketed by "DIAPROSIM", placed in a column, 80U ~ acid form by percolation using 2 liters of hydrochloric acid l N. Rinse thoroughly resin by a ~ eotropic training with benzene. We have swells 250 ~ 1 of DIOXA ~ E, 30 g of dry resin. We then poured over the swollen resin with stirring, 11.2 ml of water (i.e. 0.63 mole) and slowly 34 ml PCL3 (i.e. 0.4 mole). We brought the temperature ~ 95C and we maintained the medium under these conditions for 3 hours.
After this time, the mixture was allowed to cool to about 60C and again added 11.2 ml of water and 34 ml of PCL3, then it was heated for 3 hours at 95C. We have taken a sample of the resin obtained, which was washed with demined water ~ ali ~ ée and expired by distillation azeotropic to ben ~ ene. This resin already had a phosphorus level of 10 ~ by weight. On the rest of the mixture we repeated the previous cycle twice, after which we obtained, after rinsing and drying as indicated previous ~, 42 g of resin showing a phosphorus level 16.5% by weight, 60U ~ form of sites hydroxydiphosphonic.

.

~ 333 ~

The starting resin is a resin of the type poly ~ tyrene carrying imino-diacetic groups, crosslinked using divinylbenzene.
Example 16: Trial of Extraction of Various Elements by hydroxydiphosphon resin ~ e and sol ~ ant after hydroxy-diphosphonation and di-esterification of Tallol.

El ~ t Element Re ~ d ~ t of extraction Sol AE ~: 0, 3e3 Sol B / H ~ 2N P ~ sine L8, lM Lg 0, lM

V (IV) 1 ~ 0% 100% 100%
MnII 50% 100% 100%
Co (II) ~ 0 ~ 50% ~ 50%
Ni (II) ~ 0 ~ 0 ~ 0 CU (II) 50% 75% 75%
Zn (II) 10 to 15% 40% 60%
Ga (III) 100% 100% 100%
Ge (II ~ 85% 100% 100%
Cd (II) 50% ~ 80% 50%
In (III) 100% 100% 100%
Mo (VI) 100% 100%
H ~ (II) 90% * 30%
Pb (II) 100% 100%
. Bi (III), ._ 100% 1 100%

* doubtful Resin = resin of example ~ 5 after diphosphonation L8 = hydroxydiphosphonic acid derived from Tallol Lg = diethyl ester of L8 L8 and Ls are dissolved in ESCAID 120 containing 5%
octanol , ~
.

Claims (28)

The embodiments of the invention, concerning the-what an exclusive property right or lien is claimed, are defined as follows: 1. Composition of metal cation exchange characterized by the fact that it comprises as a grouping active a diphosphonic drift whose acid form is represented by the following general formula G:

G

where R is chosen from the group consisting of the remains alkyls having 1 to 12 carbon atoms and at most 2 ramifications on the main chain and by hydrogen, where A is a divalent organic radical chosen from the group of mono, di or tri-substituted ethylenes and mono or di-substituted methylenes. 2. Composition according to claim 1, characterized by the fact that A is a hydroxy-methylene radical. 3. Composition according to claim 1, characterized by the fact that A is an amino-methylene radical. 4. Composition according to claims 1 to 3 taken separately, characterized in that R = H. 5. Composition according to claims 1 to 3 taken separately, characterized in that the total number of carbon atoms is between 7 and 50. 6. Composition according to claims 1 to 3 taken separately characterized by the fact that the total number of carbon atoms is between 15 and 40. 7, Composition according to claims 1 to 3 taken separately characterized by the fact that the total number of carbon atoms is between 18 and 30. 8. Composition according to claims 1 to 3 taken separately, characterized in that the total number carbon atoms of group A is between 15 and 25. 9. Composition according to claims 1 to 3 taken separately, characterized in that the number of carbon atoms of group R is between 1 and 15. 10. Composition according to claims 1 to 3 taken separately, characterized in that the derivative is a resin whose active group corresponds to the general formula rale G. 11. Diphosphonic derivatives of formula G ', characterized by the fact that they correspond to the general formula G according to claim 1, where A has the formula:

where R is chosen from the group consisting of the atom of hy-drogen and hydrocarbon residues of 1 to 15 atoms of carbon, where A 'is chosen from the group consisting of hydrocarbon radicals having from 1 to 30 carbon atoms and from zero to two ramifications, by the side chains a resin comprising other supporting side chains group type G 'and having a phosphorus level at least 5% where Z is chosen from the group made up by hydrocarbon radicals having from 1 to 30 atoms of carbon and at most two ramifications, by the groups-amine elements (NH2 non, mono- or di-substituted), by alcohol groups (OH not or substituted) and by the hydrogen atom. 12. Diphosphonic derivatives according to claim 11, characterized in that A is chosen from the group consisting of linear hydrocarbon radicals having from 1 to 30 carbon atoms and the total number of carbon of said derivatives is between 10 and 50. 13. Diphosphonic derivatives according to claim 11, characterized in that A is chosen from the group consisting of linear hydrocarbon radicals having from 1 to 30 carbon atoms and the total number of carbon of said derivatives is between 15 and 40. 14. Diphosphonic derivatives according to claim 11, characterized in that A is chosen from the group consisting of linear hydrocarbon radicals having from 1 to 30 carbon atoms and the total number of carbon of said derivatives is between 18 and 30. 15. Diphosphonic derivatives according to claims 11 with 13 sockets separately, characterized in that the group Pement A has at least 8 carbon atoms. 16. Diphosphonic derivatives according to claims 11 to 13 sockets separately, characterized in that the grouping A has between 15 and 25 carbon atoms. 17. Diphosphonic derivatives according to claims 11 with 13 sockets separately, characterized in that Z is chosen in the group of amino and hydroxyl functions and in that the group A 'has at least 14 atoms of carbon. 18. Diphosphonic derivatives according to claims 11 to 13 taken separately, characterized in that the radical R of formula G is an alkyl radical. 19. Diphosphonic derivatives according to claims 11 to 13 taken separately, characterized in that the radical R has 8 to 12 carbon atoms. 20. Diphosphonic derivatives according to claim 11, characterized in that the resin is chosen from the group made up of acrylic resins and polystyrenes crosslinked. 21. Diphosphonic derivatives according to any one of claims 11 and 20, characterized in that the rate of phosphorus by weight of the resin is between 10 and 25%. 22. Process for the synthesis of diphosphonic derivatives according to claim 11, characterized in that the rate of phosphorus by weight of the resin is between 10 and 25%, and characterized in that it comprises the stages following:
(1) acidifying a resin bearing acid groups carboxylic using a mineral acid;
(2) the acidified resin is rinsed in order to remove the traces of mineral acid;
(3) the resin is brought to at least a dryness degree equal to that obtained by azeotropic training at benzene;
(4) the dried resin is swollen using a inert solvent preferably comprising at least one ether bridge and capable of dissolving at least 3% of its volume of water and at least 8% of its volume of trichloride phosphorus;
(5) between 5 and 50% of its bran is added to the swollen resin volume of water and phosphorus trichloride, at a rate 1 to 2.5 moles of water per mole of trichloride phosphorus;
(6) the temperature is raised to between 90 and 140 ° C for 0.5 to 10 hours;
(7) repeating operations (5) and (6) at least one times and preferably at least twice, lowering possibly the temperature between 20 and 80 ° C before each new introduction;
(8) rinsing with water and drying the resin;
(9) the resin is optionally esterified, so known in itself. 23. Method according to claim 22, characterized in that that the solvent in state (4) is chosen from the group consisting of dioxane and tetrahydrofuran. 24. Metallic cation exchange composition, characterized by the fact that it is constituted by a derivative corresponding to formula G according to claim 1, dissolved in a hydrocarbon diluent chosen from the group saturated and unsaturated hydrocarbons and their mixtures. 25. Composition according to claim 24, characterized by the fact that it also comprises a polar compound lipophilic immiscible with water in a proportion included between 1 and 20%. 26. Composition according to claim 25, characterized by the fact that the polar lipophilic compounds not miscible with water are chosen from the group of alcohols, ketones, phosphoric acid triesters, sulfones, sulfoxides, halogenated derivatives and trialkyl phosphine oxides. 27. Composition according to claim 26, characterized by the fact that the non-lipophilic polar compound miscible with water is a primary, secondary or tertiary with 4 to 12 carbon atoms. 28. Composition according to claim 27, characterized by the fact that the non-lipophilic polar compound miscible with water is a primary, secondary or tertiary with 6 to 12 carbon atoms.