The 12 principles of green chemistry are reviewed and applied specifically to polymer production. Examples of how the principles relate to current practice in polymer reaction engineering and which areas show the greatest potential impact for implementation of these principles are discussed. This paper does not attempt to be exhaustive but rather to target specific areas for further development.

The step‐growth polymerization of glycerol to relatively high molecular weight polyglycerol is investigated. Glycerol is a renewable material that can be derived from the transesterification of vegetable oils to biodiesel. Several soluble catalysts and their reaction mechanisms are compared and their effect on polymer molecular weight and microstructure is measured. High‐molecular‐weight PG with multimodal molecular weight distributions is observed using GPC, and partial branching is identified using 13C NMR spectroscopy. Theoretical models are used to predict the gel point and to calculate monomer functionality. magnified image

Cover: The 12 principles of green chemistry enable the transformation towards enhanced sustainability in the field of polymer reaction engineering via environmentally friendly polymerization processes. Further details can be found in the article by M. A. Dubé,* and S. Salehpour http://doi.wiley.com/10.1002/mren.201300103.

In an effort to use clean technologies, fatty acid methyl esters (FAME) produced from canola have been used as a polymerization solvent. Solution polymerizations of four commercially important monomers have been studied using FAME as a solvent. A series of methyl methacrylate (MMA), styrene (Sty), butyl acrylate (BA) and vinyl acetate (VAc) homopolymerizations in FAME were carried out at 60 • C at different solvent concentrations. Chain transfer to solvent rate constants were obtained using the Mayo method. The transfer constants increased in the order: MMA < Sty < BA < VAc. Under the conditions studied, the MMA solution polymerization in FAME was observed to behave as a precipitation polymerization. The estimated chain transfer to solvent rate constants were employed in a polymerization simulator to predict the polymerization rates and average molecular weights.

The sustainable step‐growth polymerization of glycerol is monitored in‐line and off‐line using an ATR‐FTIR spectroscopic probe. The concentration of hydroxyl groups is monitored to provide real‐time conversion data using a univariate method. Traditional off‐line techniques, i.e., hydroxyl value calculation and water production monitoring, are compared to in‐line and off‐line ATR‐FTIR spectroscopy. Fouling of the probe is observed beyond 42 mol% conversion of hydroxyl groups. No statistically significant differences are found between the conversion data from off‐line/in‐line ATR‐FTIR and two other methods at a 95% confidence level prior to fouling, and this confirms that ATR‐FTIR is a reliable tool for monitoring conversion for production of oligoglycerols from a renewable feedstock.