Sulfonated polystyrene ionomers preparation

Sulfonated polystyrene ionomers (alkali metal salts) with molecular weight below the entanglement molecular weight of polystyrene were prepared. The rheological behavior of the ionomers was characterized by dynamic and steady-state shear experiments. In general, the viscosity of the ionomers increased with sulfonation level and as the size of the cation decreased. Whereas, the starting polystyrenes were Newtonian fluids, the ionomers were non-Newtonian and viscoelastic. 

The ionic aggregates present in an ionomer act as physical crosslinks and drastically change the polymer properties. The blending of two ionomers enhances the compatibility via ion-ion interaction. The compatibilisation of polymer blends by specific ion-dipole and ion-ion interactions has recently received wide attention [93-96]. FT-IR spectroscopy is a powerful technique for investigating such specific interactions [97-99] in an ionic blend made from the acid form of sulfonated polystyrene and poly[(ethyl acrylate - CO (4, vinyl pyridine)]. Datta and co-workers [98] characterised blends of zinc oxide-neutralised maleated EPDM (m-EPDM) and zinc salt of an ethylene-methacrylic acid copolymer (Zn-EMA), wherein Zn-EMA content does not exceed 50% by weight. The blend behaves as an ionic thermoplastic elastomer (ITPE). Blends (Z0, Z5 and Z10) were prepared according to the following formulations [98] ... 

Reference 7 reviews a number of electron microscopy studies of ionomer morphology in the period up to 1979. None of these studies makes a convincing case for the direct imaging of ionic clusters. This is because of the small size of the clusters (less than 5 nm based on scattering studies) and difficulties encountered in sample preparation. The entire problem was reexamined in 1980(21). In this study ionomers based on ethylene-methacrylic acid copolymers, sulfonated polypentenamer, sulfonated polystyrene and sulfonated ethylene-propylene-diene rubber (EPDM) were examined. The transfer theory of imaging was used to interpret the results. Solvent casting was found to produce no useful information about ionic clusters, and microtomed sections showed no distinct domain structure even in ionomers neutralized with cesium. Microtomed sections of sulfonated EPDM, however,... 

The preparation of ionomers involves either the copolymerization of a functionalized monomer with an olefinic unsaturated monomer or direct functionalization of a preformed polymer. Typically, free-radical copolymerization of ethylene, styrene, or other a-olefins with acrylic acid or methacrylic acid results in carboxyl-containing ionomers. The copolymer, available as a free acid, is then neutralized partially to a desired degree with metal hydroxides, acetates, or similar salts. The second route for the preparation of ionomers involves modification of a preformed polymer. For example, sulfonated polystyrene is obtained by direct sulfonation of polystyrene in a homogeneous solution followed by neutralization of the acid to the desired level. Some commercially available ionomers are listed in Table 15.17. 

To be informative, it is desirable that the comparisons of these two different technologies be based on identical polymer backbones, having identical molecular weights, and having comparable levels of ionic functionality present. In addition, it is the purpose of these studies to make such comparisons with the same metal cation and thereby quantify, insofar as possible, the nature of the ionic interactions that exist. To do this, ionomers were prepared based on a polystyrene (PS) hydrocarbon backbone into which the ionic functionality was incorporated. PS was selected as the backbone because of the relative ease of functionalization and the relative freedom of side reactions during the sulfonation or carboxylation reactions. The polymers prepared were designed to come as close as possible in terms of ionic functionality for both sulfonate and carboxylate ionomers over a range of ionic contents. 

Structures of surfactants suitable for insoluble films containing proteins are shown in Fig. 2. The films can be cast onto solid surfaces from aqueous vesicle dispersions prepared by sonication [24,25] or from solutions in organic solvents [11,19]. Films containing proteins have also been prepared from composites of bilayer-forming ionic surfactants with ionic polymers of opposite charge (Fig. 2). Examples include polystyrene sulfonate [24] or the ionomer Nafion with DDAB (cf. Fig. 2) [27]. 

Polyolefins like polyethylene (PE) and PE terephthalate (PET) are the most widely used polymers in many commercial applications. Owing to its excellent chemical and electrochemical stability, low cost, and easy preparation, in the recent decade, some of the researchers have shifted attention to these polymers. Sulfonated poly(arylene ether sulfone), poly(vinylbenzyl chloride) (PVBC), and polystyrene (PS) have been grafted onto PE [41-43], which were designed for DMFC, proton-exchange man-brane fuel cell (PEMFC), or AFC. In addition, PET has also been utilized for DMEC through Nafion ionomer impregnating by Lee and cowoikers [44]. 

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