Macromolecular Reaction Engineering

Cover: Organo-soluble trioctylammonium-protected styrene sulfonate monomer (SS-TOA) was statistically copolymerized with styrene by nitroxide-mediated polymerization (NMP) to form resins with narrow molecular weight distributions. SS-TOA was also an effective NMP “controller” monomer for gradient copolymerization with glycidyl methacrylate. Further details can be found in the article by V. Consolante and M. Maric* on page 575.

This issue of Macromolecular Reaction Engineering contains articles of the Special Series “Sensors, Process Control and Modeling”.

A complete continuous-flow microprocess is developed starting from a monomer solution and ending with a colloidal suspension of polymer nanoparticles, including online polymer characterization. Polymethacrylates are synthesized in a microreactor and analyzed online by GPC. The polymer solution is finally nanoprecipitated with the use of a micromixer, which enables to get size-adjustable nanoparticles.

This issue of Macromolecular Reaction Engineering contains articles of the Special Series “Polyolefins - Catalyst and Process Innovations”.

Four simultaneous deconvolution strategies based on different microstructural information of ethylene/1-olefin copolymers were investigated. Deconvolution based on complete bivariate distribution of molecular weight and chemical composition was found to accurately identify the number of site type and provide best estimated mass fraction and kinetic parameters of each site type.

Experimental thermodynamic data of the system ethylene/propane in condensed and supercritical state is presented in this work. Experiments and simulations are focused on temperature and pressure conditions relevant for heterogeneous polymerization of polyethylene as applied in industry. Good description of the experimental data could be achieved by simulations using the Peng–Robinson EOS with a liquid phase density correction.

Trioctylammonium p-styrenesulfonate NMP kinetics are similar to that of styrene, yielding homopolymers and styrene copolymers with <1.1. SS-TOA is tested as a controlling monomer for BlocBuilder-mediated methacrylate copolymerizations. Gradient copolymerization of SS-TOA with GMA results in a monomodal copolymer (=15.7kg·mol⁻¹) with low =1.43 and a GMA content of 85 mol%.

The integrated deconvolution estimation model is used to estimate the reactivity ratios of a heterogeneous Ziegler-Natta catalyst in the presence and absence of hydrogen using two sets of ethylene/1-butene copolymers. A sensitivity analysis for parameter estimation is developed and the effect of the presence of hydrogen on the reactivity ratio per site type is quantified.