The influence of side-chain conformations on the phase behavior of bottlebrush block polymers

A self-consistent field theory based on the wormlike chain model is implemented in the investigation of the self-assembly behavior of bottlebrush block polymers in the formation of a lamellar phase. We utilize the model in which the semi-flexible side chains of two types A and B are grafted at the semi-flexible backbone of type C to mimic the bottlebrush molecule, particularly allowing for the extended chain conformation due to the high grafting density. We examine the positional and orientational probability distribution for the segments along the backbone and side chains as a function of the grafting density and chain flexibility for all blocks, covering a broad regime spanning from the flexible chain to rigid rod chain. This reveals that the persistence length of side chains λ_SC which intrinsically tunes the chain conformation of bottlebrush polymers plays a pivotal role in determining the manner of the local monomer packing in microphase segregation. As an important adjustable factor, λ_SC has a remarkable impact on the backbone extension and then realizes the effective manipulation of the characteristic structural size of self-assembled microstructures, such as the domain spacing and the interfacial width.