Macromolecular Theory and Simulations

Cover: The cover picture shows a semitransparent surface, which is a chain length/cross-links distribution obtained as the result of a 2-dimensional population balance simulation, in comparison to data obtained with the Monte Carlo method (the white lines). The high precision at the tail, where the Monte Carlo method scatters a lot, is possibly due to the novel simulation method used. Further details can be found in the article by I. Kryven,* and P. D. Iedema on page 89.

A numerical method for investigation of polymer modification systems involving combination reactions leading to branching is introduced. The simulation result is obtained as a distribution in more than one dimension, like molecular weight and number of branch points. Due to selection of suitable functional basis, the numerical algorithm remains computationally inexpensive.

Molecular dynamics simulation is a powerful tool to quantitatively characterize the hydrogen bonds in polymeric materials. It is demonstrated here how to use this technique to study the influence of hydrogen bonding on the static and dynamic properties, and glass transition temperature of maleimide–isobutene alternating copolymer. The simulation results could provide in-depth information on hydrogen bonding which cannot be obtained in the experimental study.

The unique characteristics of an interfacial radical-polymerization-based coating process initiated by a glucose-oxidase-mediated redox system are discussed. Specifically, the influence of the initiation mechanism on the film growth kinetics and the interfacial film attributes such as its structure, permeability, and adhesion to the underlying substrate are investigated.

A detailed investigation of secondary reaction kinetics in n-butyl acrylate free radical polymerization is performed using quantum chemistry. Kinetic parameters of various backbiting reactions are determined, and a highly favorable hydrogen abstraction reaction from a short-branch radical is proposed. Moreover, propagation reactions of secondary and tertiary radicals are investigated, and their competition with backbiting determined.

ICAR ATRP of n-butyl acrylate is analyzed as a function of the initial amount of Cu(II) and targeted chain length. Reactivity differences between secondary and tertiary species are considered and guidelines for selection of industrially relevant conditions are proposed based on overall time, and degree of control over chain length and livingness.