Macromolecular Theory and Simulations

The principle of microscopic reversibility appears to be extremely important in copolymerization systems. Application of this principle to copolymerization proceeding with the exchange of copolymer segments proves that the rate constants of heterogeneous reshuffling are not independent variables but are functions of the homogeneous exchange rate constants and copolymerization thermodynamics.

A kinetic Monte Carlo (kMC) modeling study is presented for the synthesis of poly(2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene) (MDMO-PPV) via the sulfinyl and dithiocarbamate precursor route, in which the regioregularity is assessed via the simulated triad distribution. It is shown that the sulfinyl route provides a faster way toward highly regioregular MDMO-PPV despite a more difficult synthesis of the premonomers.

Lattice models of copolymers and polymer blends at good solvent conditions are studied by means of Monte Carlo simulations using the Cooperative Motion Algorithm. The percolation threshold is found to be very weakly dependent on the chain length and the main factor that influences this threshold is the screening effect of other parts of chains.