Extensive computer simulation was performed using the bond‐fluctuation model and cellular‐automaton (CA)‐based simulation technique to probe the equilibrium structure and dynamical behavior of comb‐branched polymers in which the flexible side chains of a given length are placed regularly along the backbone and the number of branches increases linearly with total molecular weight. By applying very efficient CA algorithm – the “lattice molecular dynamics” (LMD) method – we have been able to study the properties of sufficiently large structures (up to 5880 monomeric units). Depending on the length of main and side chains as well as on interbranch spacing, we have calculated mean chain dimensions, local fractal dimensionalities, particle scattering functions, time autocorrelation functions, etc. The following main conclusions may be drawn from the results presented in our study: (i) The critical exponent, governing the mean size of the main chain, remains unchanged from its value known for a 3d self‐avoiding walk (SAW). On the other hand, two‐dimensional branched macromolecules with one‐sided branches are effectively in a collapsed state even under conditions of a good solvent, forming specific helical superstructures. (ii) Comparison of the simulated data with the predictions of the scaling model indicates that the latter is valid in describing the mean dimensions of the backbone as a function of side‐chain length and interbranch spacing. (iii) The excluded volume interaction between side chains dramatically slows down the relaxation of the backbone chain.

Conformational properties of comb-like polymers strongly adsorbed on a flat solid surface were investigated using computer simulation and scanning force microscopy. The computer simulation showed that the macromolecules with asymmetric distribution of the side chains relatively to the backbone are effectively in a collapsed state even under conditions of a good solvent. They formed peculiar helical superstructures which could be observed by scanning force microscopy of cylindrical brushes of polymethylmethacrylate on mica.

Using the cellular-automaton-based simulation technique, we study the processes of self-organization in the systems of comblike copolymers with strongly attracting groups located at the ends of side chains. It is found that at a certain critical association energy, dependent both on polymer volume fraction and on the chemical composition of the copolymers, a micellar phase is nucleated. For the combs with large linear grafting density, a weak extension of the macromolecules is observed as attraction between end groups is increased. We find that the micelle formation observed in the sufficiently dense systems is mainly a result of intermolecular association. From the analysis of the static structure factors and snapshot pictures, it is concluded that the system is spatially inhomogeneous on the intermediate length scales related to the average intermicellar distances. Strong attraction stabilizes the aggregates (multiplets) that serve as junction points of a temporary network (micellar gel). We observe the formation of a specific space-filling weblike network in which strongly attracting side-chain ends group into multiplets which are wrapped by neutral polymer sections connecting these multiplets.

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