Theory of homopolymer–oligomer microphase separation

Mesoscopic structure of the periodically alternating layers of stretched-homopolymer chains surrounded by perpendicularly oriented oligomeric tails is studied for the systems with both strong (ionic) and weak (hydrogen) interactions. Our approach is based on the fact that the structure period is determined by alternating associations between the head groups of the oligomer molecules and interacting groups of the homopolymer chains. Distribution of oligomers along the homopolymer chains is described by the effective equation of motion with the segment number playing the role of time. Experimentally observed temperature dependence of the structure period and dependence of the point of order–disorder transition are determined as functions of the oligomeric fraction.