Macromolecular Theory and Simulations

Cover: How to marry silica and phenolic resin at the nanoscale? A combination of electronic structure calculations and a coarse grained model unravels mechanistic details and key influences on the nanocomposite formation in the Twin Polymerisation. Further details can be found in the article by A. A. Auer,* A. Richter, A. V. Berezkin, D. V. Guseva, and S. Spange on page 615.

Is configurational fluctuation of a polyelectrolyte chain important for counterion condensation? If it is, how will it affect counterion condensation? By inventing a simple model, within which chain's configurational fluctuation is controlled by a stretch effectively, we address this problem analytically. The results show that configurational fluctuation indeed plays its role and drives more counterions to be condensed.

Analysis of the pair distribution function and the overlap distribution within incompatible pairs for several lattice-based polymer systems reveals a universal behavior in the limit of infinite chain-length. Using a semi-empirical method, the pair distribution function may be easily linked to the overlap distribution which in its turn has its theoretical foundations.

The slow polymer layer growth in si-RAFT polymerization can either be attributed to a reduced propagation rate or to radical termination. A kinetic model is presented and the effects of various termination modes on si-RAFT are studied. The termination mechanisms of surface radicals through “rolling” and “hopping” migrations are analyzed.

How to marry silica and phenolic resin at the nanoscale? A combination of electronic structure calculations and a coarse-grained model unravels mechanistic details and key influences on the organic/inorganic nanocomposite formation process in twin polymerization.

The interchange reactions between hyperbranched and linear polycondensate during a melt-mixing process changes the molecular weight and branching distribution and the composition in terms of fragments of the original polymers. A Monte Carlo simulation model is constructed that predicts the MWD shift to happen faster than the reduction of the fragment sizes leading to a finer fragment dispersion.

The co-polymerization with A₂and AB₂type monomers is analyzed by the kinetic mechanism. The analytical expressions of the various molecular parameters of the products have been derived. The design of molecular structure of the products and the adjustment of the critical condition of gelation are expected by changing the reaction conditions.