S. Mani et al., Microstructure of ionomers based on sulfonated block copolymers of polystyrene and poly(ethylene-alt-propylene), MACROMOLEC, 32(11), 1999, pp. 3663-3670
Block copolymer ionomers were prepared by lightly sulfonating the polystyre
ne (PS) blocks of diblock and triblock copolymers of PS and poly(ethylene-a
lt-propylene) (PEP), followed by neutralization of the sulfonic acid groups
with either sodium or zinc. The block copolymers contained between 10 and
50 wt % PS, and as the PS content increased, the mesophase texture varied f
rom PS spheres to hexagonal-close-packed (hcp) PS cylinders to alternating
PS and PEP lamellae. The sulfonation level was varied from 1 to 17 mol % of
the styrene repeat units, which provided a range of functionalization (N-S
) of between 2 and 9 sulfonate groups per molecule. The microstructure was
analyzed by small-angle X-ray scattering (SAXS) and dynamic mechanical ther
mal analysis (DMTA). An ion-rich microphase formed within the PS microdomai
ns, and that hindered the development of a well-ordered block texture. Sulf
onation of a diblock copolymer containing ca. 20 wt % PS resulted in a tran
sition of the block microphase texture from a hcp to lamellar. The order-to
-disorder transition temperature, T-ODT, Of the block copolymer was relativ
ely insensitive to the choice of the cation, and T-ODT increased as N-S inc
reased.