In this work we constructed a detailed phase diagram for the solutions of ideal diblock-copolymers and compared such diagram with that obtained during polymerization-induced self-assembly (PISA); a wide range of polymer concentrations as well as chain compositions was studied. As the length of the solvophobic block nB increases (the length of the solvophilic block nA was fixed), the transition from spherical micelles to cylinders and further to vesicles (lamellae) occurs. We observed a rather wide transition region between the spherical and cylindrical morphology in which the system contains a mixture of spheres and short cylinders, which appear to be in dynamic equilibrium; the transition between the cylinders and vesicles was found to be rather sharp. Next, upon increasing the polymer concentration in the system, the transition region between the spheres and cylinders shifts towards lower nB/nA values; a similar shift but with less magnitude was observed for the transition between the cylinders and vesicles. Such behavior was attributed to the increased number of contacts between the micelles at higher polymer volume concentrations. We also found that the width of the stability region of the cylindrical micelles for small polymer volume concentrations is in good quantitative agreement with the predictions of analytical theory. The obtained phase diagram for PISA was similar to the case of presynthesized diblock copolymer; however, the positions of the transition lines for PISA are slightly shifted towards higher nB/nA values in comparison to the presynthesized diblock copolymers, which is more pronounced for the case of the cylinders-to-vesicles transition. We believe that the reason for such behavior is the polydispersity of the core-forming blocks: The presence of the short and long blocks being located at the micelle interface and in its center, respectively, helps to reduce the entropy losses due to the insoluble block stretching, which leads to the increased stability of more curved micelles.

Nowadays, micellar polymerization is widely used in different fields of industry and research, including modern living polymerization technique. However, this process has many variables and there is no comprehensive model to describe all features. This research presents simulation methodology which describes key properties of such reactions to take a guide through a variety of their modifications. Dissipative particle dynamics is used in addition to Monte Carlo scheme to simulate initiation, propagation, and termination events. Influence of initiation probability and different termination processes on final conversion and molecular-weight distribution are presented. We demonstrate that prolonged initiation leads to increasing in polymer average molecular weight, and surface termination events play major role in conversion limitation, in comparison with recombination. © 2018 Wiley Periodicals, Inc.

Conformation-dependent design of polymer sequences can be considered as a tool to control macromolecular self-assembly. We consider the monomer unit sequences created via the modification of polymers in a homogeneous melt in accordance with the spatial positions of the monomer units. The geometrical patterns of lamellae, hexagonally packed cylinders, and balls arranged in a body-centered cubic lattice are considered as typical microphase-separated morphologies of block copolymers. Random trajectories of polymer chains are described by the diffusion-type equations and, in parallel, simulated in the computer modeling. The probability distributions of block length k, which are analogous to the first-passage probabilities, are calculated analytically and determined from the computer simulations. In any domain, the probability distribution can be described by the asymptote ~ k 3/2 at moderate values of k if the spatial size of the block is less than the smallest characteristic size of the domain. For large blocks, the exponential asymptote exp( const 2 as d ka) is valid, d as being the asymptotic domain length (a is the monomer unit size). The number average block lengths and their dispersities change linearly with the block length for lamellae, cylinders, and balls, when the domain is characterized by a single characteristic size. If the domain is described by more than one size, the number average block length can grow nonlinearly with the domain sizes and the length d as can depend on all of them.