Random copolymers exhibit diverse crystallization behavior
depending
on whether comonomers are excluded or included in the crystalline
phase. To understand the crystallization behavior of crystallizable
isodimorphic random copolymer, in this work, we selected poly[(butylene
succinate)-ran-(ε-caprolactone)], BS
x
CL
y
, copolyesters and
studied their single crystal structure and morphology. The single
crystals of PBS homopolymer and BS-rich copolymers were prepared by
the self-seeding method in o-dichlorobenzene. The
prepared single crystals were characterized by atomic force microscopy
(AFM) and transmission electron microscopy. The suitable seeding temperature
and the dissolution temperature of the copolymers decreased with the
comonomer content. The morphological features, including size, shape,
layer number, and thickness, of the single crystals depend on the
seeding temperature, crystallization temperature, and, most interestingly,
the composition. The size of the single crystals increased with the
seeding temperature, while the aspect ratio increased with the crystallization
temperature. Higher CL content in the copolymers contributed to multilayered
crystals and curved edges. These characteristics were explained by
the difference in growth rate and the number of dislocations, both
of which are expected to be influenced by the comonomers. As revealed
by AFM, the thickness of the single crystals increased with CL contents,
which is the opposite of what has been reported for copolymers with
high degree of comonomer exclusion. Electron diffraction of the single
crystals showed smaller lattice expansion as compared to melt crystallized
samples, indicating a lower degree of comonomer inclusion of CL units.