Polyelectrolytes, polymer-salt complexes

Two general types of polymer electrolytes have been intensively investigated, polymer-salt complexes and polyelectrolytes. A typical polymer-salt complex consists of a coordinating polymer, usually a polyether, in which a salt, e.g. LiC104, is dissolved. Fig. 5.1(a). Both anions and cations can be mobile in these types of electrolytes. By contrast, polyelectrolytes contain charged groups, either cations or anions, covalently attached to the polymer. Fig. 5.1(h), so only the counterion is mobile. 

Since the polyelectrolytes contain only one type of mobile ion, the interpretation of conductivity data is greatly simplified. Polyelectrolytes have significant advantages for applications in electrochemical devices such as batteries. Unlike polymer-salt complexes, polyelectrolytes are not susceptible to the build up of a potentially resistive layer of high or low salt concentration at electrolyte-electrolyte interfaces during charging and discharging. Unfortunately flexible polyelectrolyte films suitable for use in devices have not yet been prepared. 

The viscosity and non-Newtonian flooding characteristics of the polymer solutions decrease significantly in the presence of inorganic salts, alkali silicates, and multivalent cations. The effect can be traced back to the repression of the dissociation of polyelectrolytes, to the formation of a badly dissociating polyelectrolyte metal complex, and to the separation of such a complex fi"om the polymer solution [1054]. 

In a related application, polyelectrolyte microgels based on crosslinked cationic poly(allyl amine) and anionic polyfmethacrylic acid-co-epoxypropyl methacrylate) were studied by potentiometry, conductometry and turbidimetry [349]. In their neutralized (salt) form, the microgels fully complexed with linear polyelectrolytes (poly(acrylic acid), poly(acrylic acid-co-acrylamide), and polystyrene sulfonate)) as if the gels were themselves linear. However, if an acid/base reaction occurs between the linear polymers and the gels, it appears that only the surfaces of the gels form complexes. Previous work has addressed the fundamental characteristics of these complexes [350, 351] and has shown preferential complexation of cationic polyelectrolytes with crosslinked car-boxymethyl cellulose versus linear CMC [350], The departure from the 1 1 stoichiometry with the non-neutralized microgels may be due to the collapsed nature of these networks which prevents penetration of water soluble polyelectrolyte. 

The electrical properties of polyelectrolyte complexes are more closely related to those of biologically produced solids. The extremely high relative dielectric constants at low frequencies and the dispersion properties of salt-containing polyelectrolyte complexes have not been reported for other synthetic polymers. Neutral polyelectrolyte complexes immersed in dilute salt solution undergo marked changes in alternating current capacitance and resistance upon small variations in the electrolyte concentration. In addition, their frequency-dependence is governed by the nature of the microions. As shown in... 

The exchange reactions between salts of polymer adds (bases) and weak polybases (polyadds) in aqueous solutions are accompanied by considerable pH changes and also by the appearance of turbidity, particularly if the components are mixed in equivalent quantities. The copredpitation of polymeric adds and polybases was described first by Fuoss and Sadek This behavior of the mixture of two oppositely charged polyelectrolytes can be explained by the formation of a polyelectrolyte complex, this reaction being accompanied by elimination of a low-molecular weight acid or base. Thus, the exchange reaction between poly(acrylic add) and pdly(4-vinyl-ethylpyridinium bromide) was shown by potentiometry and turbidimetry to result in the precipitation of an insoluble macromolecular product, i.e. the ionic comj ex, and... 

The formation of salt bridges in polyelectrolyte/protein complexes is widely accepted. Direct evidences for the release of counterions upon association of the macromolecular partners are however scarcely reported. Potentio-metric studies were found to reveal the ionization or neutralization of proteins in polymer complexes, i.e., a pKa shift of ionizable residues when an association took place [23,25,30], In the presence of neutral polyethylene glycol, pepsin was shown to take up protons from the solution [30], On the contrary, bovine serum albumin released protons from the addition of poly(diallyldimethylammonium chloride) (Figure 5). Despite the simplicity of both the method and the quantitative measurement of a number of ions released per protein, an interpretation in terms of a number of local bridges... 

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