Ruokolainen, J.; M"kinen, R.; Torkkeli, M.; Makela, T.; Serimaa, R.; ten Brinke, G.; Ikkala, O.; Makinen, R

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 polystyreneblock-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.

Properly selected hydrogen bonding suffices to induce mesomorphic structures in mixtures of flexible polymers and nonmesogenic surfactants. For poly(4-vinylpyridine)-3-pentadecylphenol (P4VP-(PDP)x) complexes, the long period of the lamellar structure decreases as x -1 (x is the number of PDP molecules per P4VP repeat unit) in complete contrast to similar polyelectrolyte systems. Upon cooling from 80 °C to the room temperature, the long period gradually increases and levels off at around 30 °C at a value which is approximately 4 Å above the starting value. After an induction time, a structural transformation occurs in the highly complexed samples, due to the crystallization of the alkyl side chains. It is accompanied by a sudden decrease in the long period of approximately 5 Å. However, the structure is not stable and after an additional induction time both structures are present in the samples. Arguments to explain most of the observed phenomena will be given.