Synthesis and morphological characterization of poly(ϵ-caprolactone) and poly(2-methyloxazoline) substituted phenyl rings and phenylene oligomers

Poly(ϵ-caprolactone) (PCL) and poly(2-methyloxazoline) (POx) substituted phenyl rings (macromonomers) and the corresponding substituted polyphenylene oligomers have been synthesized in various chemical structures. Macromonomers were synthesized by ring opening polymerization. Poly(phenylene) oligomers were then synthesized by cross-coupling of the macromonomers in Ni-catalyzed polycondensation reactions. The macromonomers and oligomers have been characterized by ¹H-NMR, IR, GPC, and DSC. The effect of side chain chemistry and architecture on the resulting morphology in thin films has been investigated by atomic force micro-scopy and wide angle X-ray scattering. Polyphenylene oligomers showed layered morphologies in thin films. The orientation of the layers depended on the chemistry of the side chains and the backbone architecture. Linear oligomers containing statistically distributed segments having POx or PCL side chains showed layers perpendicular to the underlying substrate. Attachment of polystyrene end block to PCL chain together with the meta-connectivity of the backbone resulted in layers parallel to the substrate. Our results also indicate that substitution of polymeric chains to phenyl rings can induce ordered structures of macromonomers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2091–2104, 2007