Chemistry: electrical and wave energy – Processes and products
Patent
1991-01-09
1993-04-06
Niebling, John
Chemistry: electrical and wave energy
Processes and products
205317, 2105021, 210687, 210688, 210506, 210507, 210508, B32B 700
Patent
active
052000419
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a composite element incorporating a polyether or copolyether more particularly usable for extracting and/or separating cations.
Over the last few years new materials have been developed having macrocyclic ligands, such as cryptates and crown ethers, which are supported or incorporated into polymers. Such materials can be used in widely differing fields, due to the complexing properties of the macrocyclic ligands and they can consequently be used for such varied purposes as catalysis by two or three-phase transfer and the preparation of ion selective or ion exchange membranes used for producing specific electrodes or ion selective field effect transistors.
When these macrocyclic ligand functions are included in polymers, the properties of the ligand are generally identical, but can nevertheless in certain cases have modifications induced by the constraint of the polymeric material.
However, the incorporating of ligands into a polymeric material by polymerization of the monomer, itself incorporating the ligand function, offers numerous advantages. Thus, unlike in the case of molecular ligands, incorporated ligands are not toxic and also have the practical advantages of supported reagents. Moreover, the material naturally has a very high number of ligands. As they are incorporated into the polymer chain, they are insoluble and consequently there are only minimum risks of the contamination of solutions. They can be very easily separated therefrom, can be regenerated and then reused without any activity loss. This advantage is far from being negligible when considering the relatively high cost and difficulty of preparing most macrocyclic ligands. Furthermore, this incorporation method makes it possible to use these ligands in widely varying form, e.g. in the form of membranes, without any particular production problems.
Among the macrocyclic ligands, a great deal of research has been carried out on crown ethers and it has recently been discovered that it was possible to polymerize crown ethers electrochemically and as described by V. de Barre in J. Electroanal. Chem., 206, 115, 1986, J. Electroanal. Chem., 240, 117, 1988 and Nouveau Journal de Chimie, vol. 9, No. 6-1985, pp 419 to 426.
Thus, the polymers obtained by this method are interesting, but are likely to have steric limitations according to the nature of the ions to be complexed. Moreover, their adhesion to the platinum supports used as the anode during their preparation is not satisfactory. In the same way the access of the reagents in the polymer layer does not take place sufficiently easily for certain applications. The present invention specifically relates to novel composite elements incorporating a support covered by a relatively thick polymer layer obviating the disadvantages of the composite elements described hereinbefore.
According to a first embodiment of the invention, the composite element comprises a support of a product having a polyaromatic electricity conducting structure covered by a polymer or copolymer of a monomeric crown dibenzoether of formula: ##STR2## in which m and n, which can be the same or different, can assume values 0 and 1 to 10, provided that m+n.ltoreq.10.
In this composite element, the use of a support having a polyaromatic structure makes it possible to obtain an improved adhesion between the crown dibenzoether polymer or copolymer and the support. Moreover, with such supports, there is an increase in the performance characteristics of the electrodeposited polymer, because the latter has a much larger specific surface than with metallic supports, which permits an easier access of the reagents in the active sites of the composite element.
Finally, said supports are advantageous because they are generally much else onerous than supports made from platinum or non-corrodable precious metals such as are used at present.
According to a second embodiment of the invention, the composite element comprises a support made from metal or a product with an electricity conducting, polyaromatic struct
REFERENCES:
patent: 4584075 (1986-04-01), Goldstein et al.
patent: 4738757 (1988-04-01), Naarmann
Electroactive Charge-Transfer Polymers from Anodic Coupling of Dibenzo-Crown Ether; Le Berre et al. (1986) pp. 115.130.
Chemcial Abstracts, vol. 108, 1988, (Columbus, Ohio, US), V. Le Berre et al.: "Electrocative Charge Transfer Polymers from Anodic Coupling of Dibenzo-Crown Ethers. Part III. Intrinsic Redox Properties and Preliminary use as electrode Modifiers", p. 558, resume 102876f, & J. Electroanal. Chem. Interfacial Electrochem. 1988, 240 (1 2), 117-32.
Chem. Abst., vol. 108, 1988, p. 558 10286f, Le Berre et al.: "Electroactive Charge Transfer Polymers . . . use as Electrode Modifiers".
Chem. Abst., vol. 108, 1988, p. 75, 131770g, Le Berre et al.: "Anodic Trimerization. A Facile One-Step Synthesis of Tris(15-Crown)Triphenylene" & J. Chem. Soc., Chem. Comun. 1987, (13), 984-6.
Bouas-Laurent Henri
Desvergne Jean-Pierre
Le Berre Veronique
Lysiane Angely
Questaigne Viviane
Centre National de la Recherche Scientifique
Commissariat a l''Energie Atomique
Niebling John
Phasge Arun S,.
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