S. Nojima et al., Effects of copolymer composition on the crystallization and morphology of poly(epsilon-caprolactone)-block-polystyrene, POLYM J, 30(12), 1998, pp. 968-975
The morphology and melting behavior of poly(epsilon-caprolactone)-block-pol
ystyrene (PCL-b-PS) copolymers, quenched from the melt or cast from the tol
uene solution, were investigated by small-angle X-ray scattering (SAXS) and
differential scanning calorimetry (DSC) as a function of copolymer composi
tion. The glass transition temperature of PS blocks is higher than the melt
ing temperature of PCL blocks. T-m,T-PCL, in this system, so that the molec
ular motion is extremely restricted when the PCL block crystallizes in temp
eratures below T-m,T-PCL. DSC results showed that the quenched PCL-b-PS did
not crystallize at any temperature when PCL vol%. phi(PCL), was less than
26%, whereas it crystallized partially when phi(PCL) greater than or equal
to 34% and the crystallinity increased with increasing phi(PCL), suggesting
that phi(PCL) affects significantly the crystallizability of PCL blocks. H
owever, crystallization was observed for all PCL-b-PS copolymers cast at 20
degrees C, and the crystallinity decreased appreciably with increasing the
casting temperature. SAXS results revealed that high crystallinity PCL-b-P
S copolymers had an intensity peak arising from the lamellar morphology, an
alternating structure consisting of crystalline lamellae and amorphous lay
ers, whereas low crystallinity PCL-b-PS copolymers did not show any SAXS pe
ak, indicating the morphological difference among crystallized PCL-b-PS cop
olymers. The morphology formed in PCL-b-PS is discussed as a function of ph
i(PCL) in terms of the lamellar morphology observed for crystalline homopol
ymers.