Supramolecular Routes to Hierarchical Structures:  Comb-Coil Diblock Copolymers Organized with Two Length Scales

We show that polymeric materials characterized by two length scales are obtained if diblock copolymers are mixed with amphiphilic selective solvents, leading to self-organization which combines the “block copolymer length scale” with a much shorter “nanoscale”. In this work, the amphiphilic compound is 3- n -pentadecylphenol (PDP) which is hydrogen-bonded to the pyridine group of polystyrene- block -poly(4-vinylpyridine), i.e., PS - b -P4VP. The molecular architecture resembles comb-coil diblock copolymers A- block -(B- graft -C) but is obtained using the supramolecular assembly route. The structures were determined with a combination of transmission electron microscopy and small-angle X-ray scattering. On the block copolymer scale (300 Å range), the PS blocks are microphase-separated from the P4VP(PDP) x blocks, where x denotes the ratio between the number of phenol and pyridine groups. For PS- b -P4VP block copolymers having a spherical morphology and P4VP as the minority component, the structure of PS- b -P4VP(PDP) x changes from spherical to hexagonal and further to lamellar as a function of the amount of PDP added. For all comb-coil diblock copolymer morphologies, the P4VP(PDP) x domains are further “nanophase-separated” into lamellar structures due to microphase separation of the comb copolymer-like complex between P4VP and PDP. The morphology diagram is presented for stoichiometric conditions ( x = 1), using a range of different PS- b -P4VP block copolymers.