ИСТИНА

Block copolymer nano-assembly is an important topic in developing new materials. The microphase separation in melts of the coil-comb diblock copolymers [1] and in melts of linear statistical multiblock copolymers [2] is considered theoretically and also in computer simulations. For comb-coil diblock copolymers, the comb-blocks are assumed to be locally amphiphilic with the main chains immiscible with linear blocks and with the side parts miscible with them. The amphiphilic parts of comb-blocks are considered as dimers with freely rotating pendants. In the case of low interfacial activity, the interfacial tension at a flat interface is calculated using density-functional theory. The interfacial activity leads to a decrease in interfacial tension and, hence, to a weakening of the block stretching and decrease in the structure period. In the case of high interfacial activity of amphiphilic dimers and the sharp interfaces, the phase diagrams with the basic morphological types (spheres and inverse spheres of comb-blocks, cylinders and inverse cylinders, and lamellae) are calculated. The characteristic size of the comb-block domains is equal to the side chain length. Different structures are formed, in particular, the micelles from linear blocks separated by thin interconnected layers from comb-blocks are observed in a wide compositional range. The self-assembly of linear statistical multiblock copolymers is simulated using the dissipative particle dynamics. The copolymers were synthesized by irreversible step-growth polymerization beginning from an initial oligomer (macromonomer) mixture. Correlations between macromonomers of different types along the chains are controlled by the reaction probabilities. Macromonomer sequences in linear chains are well described by the first-order Markov statistics. With an increase in the Flory-Huggins parameter , microphase separation into a lamellar structure, for close-to-alternating block copolymers, and into irregularly arranged domains, for Bernoullian sequences of macromonomers, occurs. [1] D. A. Filatov; E. N. Govorun, Soft Matter 2021, 17, 90 [2] V. Yu. Rudyak; D. E. Larin; E. N. Govorun, Macromolecules 2022, 55, 9345