AU607586B2 - Macro-porous ion-selective exchange resins - Google Patents

Description

UUK KtE: S&F CODE: 55370 1. 4 02 2 070 75 ACCEPTED AND AMENDMENT 5845/2

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St 1.

L n r- ;r i Ir 607586 S F Ref: 78775 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: This document contains the amendments mad, undr Section 49nd is correct for printing Class Int Class Complete Spec ification Lodged: Accepted: Published: Priority: Related Art: f t t Name and Address of Applicant: Address for Service: Henkel Kommanditgesellschaft auf Aktien Henkelstrasse 67 4000 Dusseldorf FEDERAL REPUBLIC OF GERMANY Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia r Complete Specification for the invention entitled: Macro-Porous Ion-Selective Exchange Resins The following statement is a full description of this best method of performing it known to me/us invention, including the 5845/3 Abstract Macro-porous ion-selective exchange resins The invention relates to macro-porous ion-selective exchange resins, their preparation and their use.

In well-defined me~tal cxmplexes, which can be polyme~rized, obtained by cross-linking co-plyterization in a reagent, which contain ligands, which can be polymerized, and possibly further ligands, which cannot *be polymnerized, as well as anions, which cannot be polyfferized, the mretal ions are present in the same co-ordination sphere, typical of the n etal as in the initial cxxplexes. By eluting with a suitable eluant spaces reirain behind in the macro-porous ion-selective exchange resins, which contain donor atoms as capture positions in metal-specific 0 arrangemnent.

00 0 -1A- Macro-Porous Ion-Selective Exchange Resins The present invention relates to macro-porous ion-selective exchange resins, which are obtained by cross-linking polymerization of well-defined metal complexes, which can be polymerized; a process for their production and the use of this type of exchange resins.

It is known that polymerization in the presence of metal ions can lead to a certain ion-selectivity of the ion-exchange resins produced by this Nishide and E. Tsuchida, Makromol. Chem. 177 (1976), 2295). It is assumed and made probable, that through this then metal complexes with Smonomers or oligomers are formed in situ, without it being possible to describe theses as homogeneous and, with regard to their co-ordination li sphere, as well-defined.

Furthermore it is known, that starting with metal ions, polycondensates with a certain ion selectivity are obtained Bernard and F. Grass, "Mouatshette der Chemie" 98, (1967), 1050 and 1464). oo o Go 0 Ion-Selective exchange resins are known from U. Braun and W. Kuchen, "Chemikerzeituug", 108th volume (1984), No. 7/8, Pages 225, which are obtained in the following way: Well-defined metal complexes, which can be polymerized, of characteristic co-ordinate geometry are cross-linked G/136P BJG/136P i i

M

,ft> -2o a 0 0 O 0 0 60 00o t oo a 0 0 0 00 0 090 00 0 0 00 o 0 0 00 0 0 00 00 0 00 o o0 0 o co-polymerized with suitable ronomers of the type, that after eluting the metal ions, so to say "tailored-to-fit" spaces remain behind in the polymer matrix, in which by renewed loading of the resin the ion type of the original complex is preferentially stored.

Vinylised di-thio-phosphinato-complexes of transition metals are used as model substances. These resins have a very distinct behaviour with regard to their ion exchange ability.

It is known from C. Tiby, Bundesministerium far Forschung und Technologie, Forschungsbericht T84/163 (Federal Ministry for Research and Technology, Research Report T84/163), August 1984 from Sci. Tech.

Aerosp. Rep. 1985, 23 how to produce honogeneous organic menbranes with various copper complexes by condensation. A polymerization, however, did not succeed. The copper-ion specific transport properties of this membrane were examined. The membranes produced based on 8hydroxy-quinoline-copper-complexes (N20 2 -complexes) showed no copperion specific transport properties. The experiments carried out simply showed, that the Cu 2 -ions are so strongly bound by the ligands, that they cannot be extracted from the omplex even with the application of an electrical field.

With membranes, which are characterised by oxygen-binding ligands (ionotrope membrane, Cu-salicylic-aldehyde-membrane and Cu-maleic-acidanhydride-mmnbrane) it can be shown that the electrical field can be used as a driving force to extract Cu 2 +-ions from the complex and to transport them through the membrane. In ccnparison to the unselective NafionR-cation exchange membrane a preference of the Cu 2 +-ion transport as opposed to the Na-ion transport by up to 38 can be observed. The :i

Z

c h

I

II

it

):I

rri Ci

I

t

"I

I i 3 Cu-maleic-acid-anhydride-complexes mentioned were, however, not produced by cross-linking polymerization of well-defined metal complexes, but by condensation.

The object of the present invention is to make available macro-porous ion-selective exchange resins, which are obtained by the cross-linking polymerization of well-defined metal complexes, which can be polymerized, with cross-linking agents, whereby preferably simple, commercially obtainable molecules should be used as ligands. The object of the present invention is furthermore to produce a process which makes available the production of macro-porous ion-selective exchange resins, which makes possible a practical use of these types of products for ion-exchange purposes.

In a first embodiment of the present invention there is provided a S macro-porous ion-selective exchange resin, obtained by the cross-linking polymerization of metal complexes, of the general formula 00 o 0 0 0 o 0 o0 0 00 0 0 9 0 0 t 00o 0 0 o e 0 0 0000 ooo 2 00 4 9 0 0 0 t o i MaLbBcX d wherein: M is a main group metal and/or sub group metal; L is a ligand, which can be polymerized; B is a ligand, which cannot be polymerized; X is an anion, which cannot be polymerized; a is a whole number in the range from 1 to 6; b is a whole number in the range from 1 to 8; c is a whole number in the range from 0 to 4; and d is a whole number in the range from 0 to 6 with at least two polymerizable carbon-carbon- multiple-bonds.

-'p 1Vr O~k W:1471R 1 a '9 .L. 11b a whole number in the range from 1 to 8, c a whole number in the range from 0 to 4, d a whole number in the range from 0 to 6, 0 0 t o ot o as 00o 0 0 o 0 0 0 00 0 00 0 00 0 0 00 In the sense of the invention metal complexes of the general formula (I) are preferred, in which the indices a to d have the following meanings.

a a whole number in the range from 1 to 4, b a whole number in the range from 1 to 6, c a whole number in the range from 0 to 2, d a whole number in the range from 0 to 2.

A preferred embodiment of the present invention relates to metal complexes of the following general formula, in which for M, L, B and X the meanings given above apply:

ML

2

ML

3

M

2

L

6

M

2

L

4 8 2

M

4

L

6 B, ML 2 X, ML 4

X

2

ML

6

X

2 Details of the metal complexes of the general formula as well as the preferred metal complexes just given are as follows: in principle all main or sub group metals can be used as the central atom M in the metal complex, provided they have sufficient complex stability. A preferred embodiment of the present invention relates to such metal complexes, in which the main or sub group metal M is chosen from: zinc, cadmium, lead, nickel, cobalt, copper, silver as well as the usual precious metals. The index "a" a 000 o o a 0€ 0r 0 0 C0 t t

I

I

BJG/136P _I -r i; L indicates the number of metal atoms per complex unit.

As ligands L, which can be polymerized, all such compounds, which can be polymerized and which are capable of complex formation with the central atom M, can be considered. In the sense of the Invention, for example, the following ligands L, which can be polymerized, can be used: vinyl derivatives, such as vinyl pyridine, vinyl imidazole or vinyl acetyl acetonate, and styrene derivatives such as 4-amino styrene or 4-carboxylic acid styrene, in unsaturated carboxylic acids of the general formula (II):

I

-rr 0 a r oo r o a f 0 C o 00 0 00 0000 o 0 00t 0 0 4 C 0000 0s 0 0 0 00 C C C (II) where stands stands stands stands H, CH 3 or C 6

H

5 H or for CH 3 H or CH 3 and COOH, CH 2 COOH or CO-NH-CH 2

COOH;

for example acrylic acid, methacrylic acid, glycinato-N-methacrylic acid, cinnamic acid or crotonic acid.

These types of complex ligands have olefinic double bonds, which under the action of, for example, actinic radiation or the action of radical C I oc LS m

U

XW:1471R r -I of"n o o o. o; P lll IUi~Vi -6- 00 a 0 00 0 00 00 0 o 0 o 0 0 o0 0 oo oo o0 0 00 0 00 0 no 0 0000 0 00 00 0 o 00 0 0 0 0 00 00 0 0 0o 0o 0000 0 o starters can be subjected to a cross-linking polymerization.

A preferred embodiment of the present invention relates to such metal cmplexes, in which the ligand L, which can be polymerized, is chosen from the group: acrylic acid, methacrylic acid, N-methacryloyl-glycine, 4-vinyl pyridine and 1-vinyl imidazole.

It is generally true that the metal complexes according to the invention as ligands L, which can be polyrerized, can contain one of the preceding named compound types alone but also two or more of these.

Thus, for example, in addition to methacrylic acid, 4-vinyl pyridine can also be present as ligand L.

The index relating to the ligand L is dependent on the number "a" of metal atoms per complex unit, on the co-ordination number of the central atom M as well as on the number of possible ligand B, which cannot be polymerized, present in the complex.

As ligands B, which cannot be polymerized, compounds or atcns can be considered which, in the sense of the invention, are at the same time capable of complex formation with the central atom M. Examples of these can be: water, pyridine, quinoline and oxygen. These ligands B, which cannot be polymerized possibly present in the metal complexes -serve to saturate possible open co-ordination positions of the central atom M. This means then that the metal complexes can always contain further Ligands B, if all the co-ordination positions of the central atom or atoms M are not already occupied by ligands L, which can be polymerized. The index relating to the ligand B is therefore at the same time dependent on the index and on the co-ordination number of

A

I:

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-7the central atom M as well as on the number of the ligands L, Which can be polymerized, present in the ccrrplex.

Preferred as ligands B, which cannot be polymerized, according to the invention, are: oxygen, water and pyridine.

Finally the acid radicals of the usual inorganic or organic acids can be onsidered as anions X, which cannot be polyme~rized, acco~rding to the invention. For exarrle and in the sense of the invention the o0 folloing are named as preferred anions X, which cannot be polymerized: o o;oN 3 Cl-, CH 3 OO and SO 4 2 The metal ccTplexes then alasce this type of anion X, if this is necessary for the neutralisation of o the central atcxn or atoms. The numnber of these anions X per conplex unit is dependent on the index on the valency of the central atomn 0 M and the of respective anions X as well as on the number of the o 0 ooligands L.

O 00 The following is an exemplary surruaiy of the polymerizable metal onlexes acording to the ineto.

S'

LI- 1- ~6, Type Example 0t 0 o a 00o o0 0 0 00 0 0o 0000 000 0 0 a 0o o0 oo Ic t 1

C

ML

2 ZnL 2 CdL 2 PbL 2 with L Methacrylate, CuL 2 with L N-methacryloyl glycine,

ML

3 AgLL' 2 with L methacrylate, L' vinyl pyridine

M

2

L

6 Cu 2

L

4

L'

2 Zn 2

L

4

L'

2 with L methacrylate, L' vinyl pyridine

M

2

L

4

B

2 Cu 2

L

4

(H

2 0)2, Cu 2

L

4 (Pyridine) 2 with L methacrylate

M

4

L

6 B: Pb 4 L 0, Zn 4

L

6 0 with L methacrylate ML2X: [AgL2]+N0 3 with L vinyl pyridine

ML

4

X

2 [NiL 4 3 2 with L vinyl imidazole

ML

6

X

2 [CoL6]++(NO 3 2 with L vinyl imidazole According to the invention, for the production of the ion-exchange resins, a solution as concentrated as possible of the complexes serving as matrices is produced in a mixture of cross-linking agents and suitable inert means, which then, after addition of a radical-starter is submitted to a cross-linking polymerization in a reagent. The ion-exchange obtained are generally ground in order to obtain the desired grain size. If these ion exchange resins are treated with a suitable eluant, then the metal ions and if present also the complex ligands which cannot be polymerized, are removed therefrom, so that the donor atoms remain behind in the resin, retained as holding positions in co-ordinate geometry specific to the metal. As mentioned, in these spaces, those types of metal ions are taken up with preference, which were present in the original complex. Resulting from this matrix effect there are thus empty positions in the ion exchange resin as if "tailored-to-fit" for the respective metal ions.

It must be stressed that these resins, even after multiple charging and s

*I

I

i 31

I

I; j BJG/136P -9regeneration, show no change in capacity and with that also no tendency towards "bleeding".

In the sense of the present invention ethylene glycol di-methacrylate and di-vinyl benzene are preferably used as cross-linking agents.

The cross-linking polymerization is preferably started by a known radical-starter, which is chosen in particular from diacyl peroxide, cumene hydroperoxide, t-butylperoxide and organic diazo cmpounds, such Q. O o S° as nitrile azoisobutyric acid.

0 0 0 oo So The concentration of the radical-starter or the wave-length and 00 o intensity of the radiation to be used, which leads to polymerization is 0 0 known to the average expert working in the field of polymerization of S no honarers.

0 0 0 0 ao 0 Ion-selective exchange resins according to the invention have macro- 00 So porosity, by which the access to the most possible active exchange centres within the resin particles is ensured.

0a0 For practical implementation, the technique of suspension polymerization offers itself. This has the advantage as opposed to polymerization in a reagent, that the resin particles are obtained directly in the desired pearl form, which means the possible problems connected with grinding and sieving due to electrostatic charging no longer apply.

In the co-polymerization of metal complexes containing ligands L, which can be polyimerized, in the presence of a diluting agent inert to t

__~~~IIIIIC-X_

10 polymeri ,ation, polymers result depending on the test conditions with homogeneous, swelling-porous or permanently porous networks. The formation of permanently porous networks is favoured within certain limits by an increasing content of cross-linking agent (for example, divinyl monaner) in the reaction mixture, as well as through increasing quantities of diluting agent (inert material). Swelling-porous networks are distinguished from permanently porous networks in that their pores collapse under shrinkage. A permanent, interconnected pore system ensures at the outset the easy transport of material into the inside of 00 1 o the resin particle and is very easily demonstrated by the high internal surfaces of the dried polymer.

0 0 Q 00 0 0000 0 0 S: As inert agents in the sense of the present invention, in particular 0 agents such as benzene, toluene, acetic acid ester, methanol or mixtures of these, preferably benzene-methanol mixtures in the ratio of 0 0 0 1 1 are used, which can then be removed without difficulties under the polymerization conditions according to the present invention, 0 0 o o either by eluting or drying the resin in a vacuum at a raised Stemperature. Equally usable ion-exchange resins are obtained by the use °o*o of methanol itself as an inert agent.

0o00 0 a 0 0 The ion-exchange resins according to the invention can be produced by suspension polymerization. Hereby the polymerizate is obtained directly in a ready-to-use form and distribution. With the process described as suspension- or pearl-polymerization, the monomer is emulsified to droplets in a suspension medium which is not miscible with the monomer by stirring, and polymerized by the addition of an initiator, which is soluble in the monomer. By the addition of a suitable dispersing agent the melting of the monomer droplets can be stopped, until the 11 polymerization exchange is so advanced that the danger of coalescence no longer exists for the polymer obtained.

The obtainable size of the particles can be controlled, for example, in the range from 0.01 to 5 mn diameter by the following parameters: 1. Geometric factors: Shape and diameter of the stirrer in relation to the measurements of the reactor, if necessary, current disturbing installation.

2. Operational magnitudes: Rotational speed of the stirrer, relation of phases, height of filling, S temperature.

3. Material data: I Viscosity and density of the monomer phase and the inert middle phase, the boundary surfaces tension and the type and amount of the dispersing agent.

C, Either macro-nolecules (so-called "protective colloids"), such as C ;partially saponified polyvinyl acetate, polyvinyl alcohol or mithyl cellulose soluble in the suspension medium, or insoluble inorganic powders (so-called "Pickering-emulsifiers"), such as finely divided barium sulphate, talcum or aluminium hydroxide serve as dispersing i agents.

According to the preferred embodiment of the present invention the polymerization is, however, carried out in a reagent. For the production of macro porous ion-selective exchange resins a solution, Ii 00 f o 00 O, 00 00 o 0 o I oar 0I 0 O C 0 12 of the highest possible concentration of the complex serving as matrix, is produced in a mixture of a cross-linking agent and a suitable inert agent, which after the addition of a radical starter is then subjected to a polymerization in the reagent. The resins obtained are ground to obtain the desired particle size, and show a distinct selectivity with regard to the ion type of the matrix complex used after eluting with a suitable eluant.

The polymerization in the reagent of a solution, in particular of a the most highly concentrated solution of the matrix complex has the advantage that an extremely homogeneous distribution of the complex is achieved in the polymerizate.

A further feature of the present invention is the grinding of the polymerizate to the desired size before treatment with the eluant, as the enclosed metal ions are most eluable only after the the resin has been ground, however, not from the primarily resulting, relatively compact substance.

If the ground macro-porous ion-selective exchange resin is treated with a suitable eluant, such as for example 1-molar solution of NH 3

/NH

4 C1solution, the metal ions and, if present, the non-polymerizable complex ligands pyridine- or oxygen ions) are removed from the polymerizate, such that hollow spaces remain behind in a metal-specific arrangement in the resin. By subsequent renewed charging with metalsalt solutions the eluted metal equivalents are taken up again, whereby even after this process has been repeated several times no "bleeding" of the resin is observed.

o 0 0 ao c e o v 0 0c r4 0 4 t t fill r ii 5845/3 13 The -macro porous ion-selective exchange resins according to the invention can be used wherever, in contrast to the prior art, a higher separation factor is desired. The macro porous ion-selective exchange resins of the present invention can, for example, be used for wastewater purification, for the concentration of trace metals in metallurgic preparation processes or in recycling processes, such as the production of platinum by the recovery of Cu 2 froa etching solutions. As a result of the extremely high separation factor and the ability to recondition of the exchange resins these can in particular be used for the removal of heavy metal traces from aqueous waste solutions.

In some cases, e.g. with the use of the complexes Cu 2

L

4

B

2 or Cu 2

L

4

L'

2 as matrix complexes the relative separation factor alpha' of the ion exchange resins in the system Cu2+/M 2 (M Zn, Cd and Pb) conditioned C by the matrix effect, lies in the range from 20 to 250, and therefore in an order of magnitude which was not to be observed up till now in the template-formed ion exchange resins.

Thereby the relative separation factor alpha' is described as follows: alpha alpha' alpha 0 Where according to the invention and alpha 0 means the separation factor of a resin of the same adherin alpha 0 reans the separation factor of a resin of the same adhering 4

L.-

i, ri 14 group content, which was analogously produced, however without the characteristic co-ordination geometry of the matrix.

Production examples The preparation of matrix complexes, a few of which are mentioned in the patent literature their use as co-polymers in synthetic materials with special properties), for which nowever, not in all cases explicit instructions, or characteristic data are given, is carried out in the following way: MATRIX CdPLEXES 0 00 08 o a 0 00 0 0 0 0 o o 0 00 0 oo 0 Soo8 o o Q 00 0 0 00 0 0 0 00 0 O 0 0 08 06 Examples 1 to 6 Preparation of methacrylate-matrix complex a f 0 8 g of the metal oxide or basic copper carbonate is slowly mixed in a solvent cooled with ice with a solution of methacrylic acid in the same solvent (2 The mixture is stirred under the given conditions of temperature and time, the reaction mixture is worked up as given in Table 1 and the ccmplex is crystallised from the solution after cooling to -20 OC.

Examples 7 and 8 Preparation of pyridine- or 4-vinyl pyridine adducts of copper- (II)methacrylate i:F fl. r 10.0 g of Cu 2

L

4 2 H 2 0 is mixed in 200 ml of methanol with 4.0 g of pyridine, or 5.2 g of 4-vinyl pyridine. The crude product crystallising out at -200C is re-crystallised from benzene.

Example 9 Preparation of Cu(II)-complex from N-methacryloyl glycine g of N-methacryloyl glycine is dissolved in 20 ml of hot methanol, and mixed with 1.96 g of KOH in 10 ml of methanol and 4.4 g of CuSO 4 5H 2 0 dissolved in the least possible amount of hot water. After the K 2

SO

4 2 4 S obtained has been filtered off the filtrate is concentrated in a rotatory evaporator, mixed with a little diethyl ether and brought to crystallisation at -200C. For cleaning it is re-crystallised from methanol-diethyl ether.

eo BG t36P A090 0 a a a lfl A 0 0 0 0 0 aa e0 Table 1: Preparation of the metal methacrylate it Example Reagent Initial Solutions Methacrylic Conditions Treatment Re-crystallised Compounds (ml) Mixture acid of Reaction from: T tU I ZnL 2 ZnO 100 MeOH 21.2 25 3 filter, concentrated Methanol0 to 50 Ml; 2 CdL 2 CdO 200 MeOH 13.1 25 48 filter, concentrate, Aceton/ dissolve residue in ligroun T 100 ml aceton, mix with 0 100 ml Ligroun (30-500); t 3 PbL 2 PbO 50 MeOH 7.7 25 3 boil for a short methanol while, filter; 4 Z11 4

OL

6 ZnO 250 CH 2 Cl 2 5.0 G 0.25 filter, after adding ben2ene 300 ml Ligroun (50-800) oj concentrate to a volume d of lS0ml; Pb 4 0L 6 PbO 100 CH 2 Cl 2 5.8 0 0.5 boil, filler con- benzene centrate to 50m1 6 Cu 2

L

4 2H 2 0 Cu(OH) 2 CuC0 3 50 MeGH 16.0 25 24 add lS0ml MeOH Methanol 0 i+ fil ter; (D Then to reflux L methacrylate I -41 li i 0 0 0 0 600 0 0 0 6 0 a0 0 0 0 0 0 0 0a 0 0 0 0 0 00 3 0 0 a 0 a 0 D0 0 0 0 0 0 0 6 0a Q 0 0 0 0 0 0 0 0 Table 2 Characterisation of tile matrix complexes: Example Reagent Point of Molar mass II-IMR IR (3 MS UV u Ignition Calculated Found YC=C YC=O -vc0 (OC) (ppni) [cnf 1 [cm- 1 [cm- 1 [cnf 1 [8.11.1 ZnL2 CdL2 PbL2 Zn40L6 Pb40L6 CU21-421-120 CU21-42PY Cu2L42VPY CuL'2 235.5 291.6 377.4 788 1355.3 503.4 625.6 677.7 347.8 244(l 290(l 377(l 775(2 1375(2 614(3 689(3 6.18;5.60;2.08(l 6.08;5.52;2.10(l 6. 17;5.48;2.07( 1 6. 23;:5.53;2 .07(2 5.93;5.40; 1.83(2 1655 1640 1640 1640 1645 1640 1645 1645 1640 1525 1555 1500 1575 1530 1575 1600 1600 1610 1425 Zn 4

OL

6 1415 M+ 1405 M+- 1425 Mi- 1385 1415 Mi- 1415 M+ 1415 1390 51200( H 2 0) 5 10500H 2 0) 49800(H 2 0) 13850;27450(R) 13200;26050(R) 13400 ;25900(R) 13300;30650(R) 1.35 1.39 1.45 1.48 L methacrylate--Anlon; PY pyridin; L' N-methacryloylgycin-Anlon; VPY vinyl pyridin The values FOUnd in the elementary analysis correspond well with tile caculai-ed values in all cases 1) in methanol 2) in chloroform 3) in benzene 4) in KBr 18 General instructions for polymerization The matrix complex, dissolved in the inert medium, is mixed with a cross-linking agent and a starter. The reaction mixture, in ampoules (Volume approximately 120 ml, diameter 30 nm) is left under nitrogen, then for 8 hours in a water-bath at 60 OC and finally a further 3 days in a drying chamber at the same temperature. Finally, the polymer obtained is ground.

There was practically a quantitative resin yield. All the resins had specific surfaces of approximately 400 m 2 Their exchange capacity, referred to polymerized metal ions, amounts to approximately 40 to 60 t It o i 0 0 I o a t 0 0 G C0 0 00 0 0 00 O OS G0 00 0 G8 4 6C Example Using 3.0 rnol of the matrix complex from example 6, 20 g of methanol, g benzene, 40 g of ethylene glycol dimethacrylate and 0.2 g of azoisobutryronitrile following the general instructions a macro-porous ion-selective exchange resin is produced.

Example 11 Using 3.0 nmml of the matrix complex from example 8, 40 g of benzene, g of ethylene glycol dimethacrylate and 0.2 g azoisobutyronitrile following the general instructions, a macro-porous ion-selective exchange resin is produced.

Example 12

(I

1749 Using 10 mmtl of the matrix ccnlex f rom exiple 3, 20 g of meachanol, g of benzene, 40 g of ethylene glycol dimaithacrylate and 0.2 g of azoisobutyronitrile a macro-porous ion-selective exchange resin is produced.

Exainple 13 Using 10 irrin of the matrix cmplex from examrple 1, 20 g of methanol, 20 g of benzene, 40 g of ethylene glycol dimethacrylate and 0.2 g of azoisobutyronitrile a racro-porous ion-selective exchange resin is :4 0 o ~:Using 2.5 Tmml of the matrix complex from examrple 4, 40 g of benzene, g of divinyl benzene and 0. 2 g of azoisobutyronitrile a rracro-porous 44 ion-selective exchange resin is produced.

o 4 Fxamole Using 4.5 rrrrl of the matrix am-lex fromn example 9, 20 g of methanol, g of benzene, 40 g of ethylene glycol dinfethacrylate and 0.2 g of azoisobutyronitrile, a macro-porous ion-selective exchange resin is J pr-oduced.

20 Determination of the maximum working capacity ('Batch-process") 10.0 g of the dried resin is suspended in methanol for 1 hour for swelling and then transferred to a chromatography column (inner diameter 1.4 ancm). After eluting the column, first with 250 ml of methanol, then with 250 ml water the metal ions are oluted with 200 ml of a solution, comprising respectively 1 mole of NH1 3

NH

4 C1 and 0.3 mole of KNa-tartrate. The column is finally washed with water to neutrality, whereby the first 150 ml of the washing water is united with the eluate. The metal content of the solution obtained in this way 'is then complexometrically determined (0.1 m EDTA L-ethylene diamine- N,N,N' ,N'-tetraacetic acid 7).

.9 0 So The resin now present in the NH+4-form is transferred to a 500 ml Erlenmeyer flask and after the addition of 20 ml of a 0.1 m metal salt solution, together, if necessary with a buffer, is mixed with o sufficient water for the total volume to amount to 500 ml. Finally the contents of the flask are shaken for 2 hours ("Batch-process") and the resin is again put in the chramatography column. After washing with approximately 100 ml water, this is eluted with a solution of 04

NH

3

/NH

4 C1/KNa-tartrate (concentration as above) and the metal ion concentration in the eluate is inverse voltametrically evaluated.

After repeating this charging/eluting experiment several times the spread of individual values lay at approximately 3 whereby in a few cases a distinct dependency of the exchange capacity on the type of metal ion offered could be established.

Determination of the separation factors alpha and alpha'

I

B-7 -a1 -21- To 10.0 g of the dried, formed resin (NH 4 +-form) were added equimolar amounts of two metal salt solutions, of which the cations can be taken from Table 3 (each being 10 ml of a 0.1 molar solution), and if necessary also a suitable buffer and the mixture was brought to a total volume of 500 ml by the addition of water. Subsequently the contents of the flask were shaken for 2 hours, after successful sedimentation had occurred, in a test of the remaining solution the concentration of the metal ions which were not absorbed was determined by pulse-polarography determined. The resin (sediment) was transferred to a column and the latter was eluted, as previously described. In the eluate the concentration of the absorbed etal ions was evaluated. From the concentrations thus obtained the alpha-values and from these and from the corresponding alphaO-values alpha' were calculated.

e 1 4 9 Thereby the following is valid for the separation factor alpha of a resin formed according to the invention on a metal M as opposed to a metal

M

2 CM1 resinM1 solution alpha CM2 resin/ M2 solution where C ymol metal/g resin or solution. The values for alpha 0 result analogically with the use of a non-formed resin, which is prepared in the t same way as the resin formed according to the invention, however without the characteristic co-ordination geometry of the matrix i.e. without the addition of the forming metal.

Furthermore, the following is true, as has been described previously: alpha' alpha/alpha 0 Sr BJG/136P 22- The following table 3 gives the relative separation factors alpha' again, which by the use of the above nethod were determined by the respective pH values given.

Table 3 BEcatple 10 Cu/Zn 16 relative separation Cu/Cd 50 factors alpha, Cu/Pb

C

0 C C a 0 anple 11 4.6 Cu/Zn Cu/Cd Cu/Pb 3.1 65 220 Eanle 12 5.5 Pb/Zn Pb/Cd Pb/Cu 6.8 2.8 3.1.

Example 13 5.5 Zn/Cd Zn/Pb Zn/Cu 1.4 1.3 1.6 Exanple 14 5.5 'in/Cd Zn/Pb Zn/Cu 2.7 1.6 1.6 Example 15 4.6 Cu/Zn 1.8 The imcro-orous ion-selective exchange resins prepared by the use of the matrix couplexes corresponding to examrples 10 to 15 each show a distinct ion-selective exchange capacity.

it ii*i(ii-:-~ g 23 Example 16 A resin according to the invention, forrmed with the complex silverrrthacrylate-(4-vinyl pyridine) 2 (AgTL'2) in the system Ag/Zn and in the system Ag/Pb was examined. For caparison a corresponding "blind resin" which contains the sane number and type of adhering groups as the formed resin purely statistically distributed in copolymers was brought into the examination.

09 a 00 0 0 a 00 S0 0 o to 0000 o0D oo a od 0 0 00 0 0 0 0 00 o 0 0 0 00 0 0s Composition of the resins: Forned resin: 40 g (202 mTol) ethylene glycol dimethacrylate (EM1Y1A) 10 nnol of the above named complex AgLL'2 Blind resin: 40 g (202 mol) ethylene glycol dirrmethacrylate (EGDMA) 10 rnol annonium methacrylate 20 mol 4-vinyl pyridine.

Inert substance for both resin's: Benzene/rethanol mixture in the ratio 1 1.

V

Result of the mixed charging Aq/Zn: g of resin both formed resin and blind resin was shaken for 2 hours in 500 ml of a solution, which contained 1 mul each of silver and zinc(II)-nitrate (each =ol netal per g of solution): LL_- 11 24- Fornred resin: '9 a. I I 44 *4 I

C

*44 1 II I 1 I 4 *1 4 a. a a 4 o 4* 9 0 0 a.

0 0 0* 09 a o a a 0 a* pH- c resin c solution c resin c solution alpha Wnil/g p nl/g PirOl/g Prrl/g 4.7 40.9 1.21 1.63 2.01 42 5.7 64.4 0.73 8.04 1.88 20.5 Blind resin: Ag Zn pH c resin 4.7 4.07 5.7 30.8 These result- in the c solution prrl/g c resin ffol/g c solution prtol/g alphao 1.96 1.41 0.12 8.08 2.04 1.88 34.5 5.1 following separation factors alpha' pH alpha# 4 t, Result of the mixed chara:inca AQ/Pb: g of resin both formed resin and blind resin was shaken for 2 hours with 500 ml of a solution, which contained 1 rmol each of silver(I)- and lead(II)-nitrate (2{arol of each metal per g solution).

L 1' -w 25 Formed resin: pH c resin c solution c resin c solution alpha prrol/g prro/g prnl/g 4.7 39.4 1.24 0.77 2.03 83.7 5.7 62.3 0.77 9.56 1.85 15.6 Blind resin: Ag Pb 00 0 0 Oft 0 *0 0004 o 0 4 0* 0 0000 0 0 00 0 40 0 0 0 0 o 00 0 0 0 40 0 0 04 0 *0 0* 4 0 0 0 0.0 00*0 0*40 0*4401 pH c resin nUol/ g 4.7 5.27 5.7 25.4 These result in the c solution Pirol/g c resin pnol/g c solution pa=l/g alphao 1,93 1.52 1.81 17.2 2.00 1.69 following separation factors alpha' pH alphal 27.9 9.8 The formed resin shows a forma~tion effect by both pH values, in which by far the most distirz-t separat:.Ion effect lies in the system Ag/Pb at the pH value 4.7. However, the capacity of the resin in this region is less than at pH 5.7.

'4 -26- Capacity of the resins in grams of metal per kg of resin: pH 4. 7 pH 5. 7 pH 4. 7 pH 5.7 Ag Zn Ag Zn Ag Pb Ag Pb formed resin: blind resin: 4.4 0.44 0.11 0.008 6.9 0.53 3.3 0.53 4.3 0.56 0.16 0.37 6.7 2.7 3.6 eq a a I C a.

aa 4 9 a. I q.4e a a a a o ~O *0 04 a a a C 6.

o aa a a all BJGI1 36P

Claims (19)

1. A macro-porous ion-selective exchange resin, obtained by the cross-linking polymerization of metal complexes, of the general formula MaLbBcXd (I) wherein: M is a main group metal and/or sub group metal; L is a ligand, which can be polymerized; B Is a ligand, which cannot be polymerized; X is an anion, which cannot be polymerized; a is a whole number in the range from 1 to 6; b is a whole number in the range from 1 to 8; c is a whole number in the range from 0 to 4; and d is a whole number in the range from 0 to 6 with at least two polymerizable carbon-carbon- multiple-bonds.

2. A resin according to claim 1, characterized in that the metal complex has the general formula ML 2 ML 3 M 2 L 6 M 2 L 4 B 2 M 4 L 6 B, ML 2 X, ML 4 X 2 or ML 6 X 2

3. A resin according to claim 1 or 2, characterized in that the metal M is zinc, cadmium, lead, nickel, cobalt, copper, silver or another precious metals.

4. A resin according to any one of claims 1 to 3 wherein the ligand which can be polymerized may be any one or more of a vinyl derivative, a styrene derivative or an unsaturated carboxylic acid of the general formula (II): R R" C C (II) R' A wherein R is H, CH 3 or C 6 H

5 R' is H or CH3; R" is H or CH 3 and A is COOH, CH 2 COOH or CO-NH-CH 2 COOH. A resin according to claim 4, wherein the ligand, which can be polymerized, is acrylic acid, methacrylic acid, N-methacryloyl glycine. 4-vinyl pyridine or 1-vinyl imidazole.

6. A resin according to any one of claims 1 to 5, wherein the ligand which cannot be polyermized is oxygen, water or pyridine. :1471R ii i i~i ~imj-~RaRlli 28 0 0 a o al 0 a 0 oa 0 0 0 Ooo 0 00 00 0 a o o 0 0 0 a a 0 0 a Ca« 00 01 j 0 0 0 I oo 00 0 09 0 0 0 0 0 0 9 00 I o o oa i o o o o o 'i o i

7. A resin according to any one of claims 1 to 6, wherein the anion is nitrate, chloride, acetate or sulphate.

8. A resin according to any one of claims 1 to 7, wherein the cross-linking agent is ethylene glycol dimethacrylate or divinyl benzene or a mixture thereof.

9. A resin according to any one of claims 1 to 8, wherein the polymerization is started by a radical initiator.

A resin according to claim 9 wherein the initiator is a diacyl peroxide, a cumene hydroperoxide, t-butyl peroxide or an organic diazo compound.

11. A resin according to any one of claims 1 to 10, wherein the macro-porosity is achieved by the addition of inert agents in the cross-linking polymerization.

12. A resin according to claim 11, wherein the inert agent is benzene, methanol or a mixture thereof.

13. A resin according to claim 11, wherein the inert agent is a benzene/methanol mixture in the ratio of 1:1.

14. A process for the preparation of resins according to any one of claims 1 to 13, wherein a solution or suspension of the metal complex in a mixture of the cross-linking agent is polymerized after the addition of a radical initiator.

15. A process according to claim 14 wherein the inert agent is added to the solution before polymerization.

16. A process according to claim 14 or 15, wherein the polymerizate is ground to the desired particle size and is finally treated with an eluant to remove the inert agent, the metal ions and if present the ligand complexes which cannot be polymerized.

17. The use of resins according to any one of claims 1 to 13 for waste-water purification, concentration of trace metals in metallurgic preparation processes or in recycling processes.

18. Macro-porous ion-selective exchange resins, obtained by the cross-linking polymerization of metal complexes, which can be polymerized substantially as hereinbefore described with reference to any one of the Examples.

19. Process for preparation of macro-porous ion-selective exchange resins substantially as hereinbefore described with reference to any one of the Examples. :1471R 29 DATED this TWENTY-NINTH day of NOVEMBER 1990 Henkel Kommanditgesellschaft auf Aktien Patent Attorneys for the Applicants SPRUSON FERGUSON 00 0 0 0 0 0 0 0 0 040 0 0 0 KX14:1471R