Intermediate Segregation Type Chain Length Dependence of the Long Period of Lamellar Microdomain Structures of Supramolecular Comb−Coil Diblocks

A characteristic intermediate segregation type chain length dependence of the long period D of the lamellar microdomain structure of a class of comb−coil supramolecules is reported. The supramolecular comb−coil diblock copolymers studied consist of a polystyrene (PS) “coil” block and a “comb” block of poly(4-vinylpyridine) (P4VP) either hydrogen bonded to pentadecyl phenol (PDP) (i.e., P4VP(PDP)-b-PS) or first protonated with methanesulfonic acid (MSA) and then hydrogen bonded to PDP (i.e., P4VP(MSA)(PDP)-b-PS). In both cases we find a scaling D ~ <EQUATION><EQNDATA>%@mt;sys@%%@ital@%N%@rsf@%%@sx@%tot%@be@%δ%@sxx@%%@mx@%</EQNDATA> </EQUATION>, δ ≅ 0.8, where N<INF>tot</INF> denotes the total number of monomers of the P4VP-b-PS backbone. In the case of diblock copolymers this would correspond to a characteristic intermediate segregation regime behavior. Pure PS-b-P4VP, on the other hand, shows the expected strong segregation behavior D ~ <EQUATION><EQNDATA>%@mt;sys@%%@ital@%N%@rsf@%%@sx@%tot%@be@%δ%@sxx@%%@mx@%</EQNDATA> </EQUATION>, δ ≅ 0.7.