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Extensive experimental studies have shown that numerous ordered phases can beformed via the self-assembly of T-shaped liquid crystalline polymers (TLCPs)composed of a rigid backbone, two flexible end chains and a flexible sidechain. However, a comprehensive understanding of the stability and formationmechanisms of these intricately nano-structured phases remains incomplete. Herewe fill this gap by carrying out a theoretical study of the phase behaviour ofTLCPs. Specifically, we construct phase diagrams of TLCPs by computing the freeenergy of different ordered phases of the system. Our results reveal that thenumber of polygonal edges increases as the length of side chain or interactionstrength increases, consistent with experimental observations. The theoreticalstudy not only reproduces the experimentally observed phases and phasetransition sequences, but also systematically analyzes the stability mechanismof the polygonal phases.

Theory of polygonal phases self-assembled from T-shaped liquid crystalline polymers