Phase diagram of selectively cross-linked block copolymers shows chemically microstructured gel.

We study analytically the intricate phase behavior of cross-linked AB diblock copolymer melts, which can undergo two main phase transitions due to quenched random constraints. Gelation, i.e., spatially random localisation of polymers forming a system-spanning cluster, is driven by increasing the number parameter μ of irreversible, type-selective cross-links between random pairs of A blocks. Self-assembly into a periodic pattern of A/B-rich microdomains (microphase separation) is controlled by the AB incompatibility χ inversely proportional to temperature. Our model aims to capture the system's essential microscopic features, including an ensemble of random networks that reflects spatial correlations at the instant of cross-linking. We identify suitable order parameters and derive a free-energy functional in the spirit of Landau theory that allows us to trace a phase diagram in the plane of μ and χ. Selective cross-links promote microphase separation at higher critical temperatures than in uncross-linked diblock copolymer melts. Microphase separation in the liquid state facilitates gelation, giving rise to a novel gel state whose chemical composition density mirrors the periodic AB pattern.