Polystyrene (PS) is a major commodity polymer widely used in various applications ranging from packaging to insulation thanks to its low cost, high stiffness, and transparency as well as its relatively high softening temperature. Similarly to all polymers prepared by radical polymerization, PS is constituted of a C–C backbone and thus is not degradable. To confer degradability to such materials, the copolymerization of vinyl monomers with a cyclic monomer that could undergo radical ring-opening is an efficient method to introduce purposely cleavable bonds into the polymer backbone. Dibenzo­[c,e]-oxepane-5-thione (DOT) is a cyclic thionolactone monomer known for its efficient copolymerization with acrylate derivatives but so far could not be incorporated into PS backbones. From a theoretical study combining density functional theory (DFT) and kinetic models using the PREDICI software, we showed that the modification of experimental conditions could overcome these limitations and that high molar mass degradable polystyrene (M w close to 150 000 g·mol–1) could be prepared via statistical insertion of thioester groups into the polymer backbone. This copolymerization process is compatible with conventional free radical polymerization and reversible deactivation radical polymerization (RDRP) techniques such as nitroxide mediated polymerization (NMP). Thanks to favorable reactivity ratios allowing only a few mol % of thioester units to be randomly incorporated, there was no major modification of the thermal and mechanical properties of the PS. The degradation of such PS could be performed in tetrahydrofuran (THF) at room temperature (RT) in 1 h using 1,5,7-triazabicyclo[4.4.0]­dec-5-ene (TBD) as a base, leading to oligomers with M n close to 2000 g·mol–1. We successfully demonstrate further applicability of these copolymerization systems for the phototriggered decomposition of PS in solution as well as the synthesis of cross-linked PS networks degradable into soluble side products.

Polystyrene (PS) is a major commodity polymer, widely used in various applications ranging from packaging to insulation thanks to its low cost, high stiffness and transparency as well as its relatively high softening temper-ature. Similarly to all polymers prepared by radical polymerization, PS is constituted of a C-C backbone and thus is not degradable. To confer degradability to such materials, the copolymerization of vinyl monomers with cyclic monomer that could undergo radical ring-opening is an efficient methodology to introduce pur-posely cleavable bonds into the polymer backbone. Dibenzo[c,e]-oxepane-5-thione (DOT) is a cyclic thionolac-tone monomer known for its efficient copolymerization with acrylate derivatives but so far could not be incor-porated into PS backbones. From a theoretical study combining DFT and kinetic models using the PREDICI software, we showed that modifying experimental conditions could overcome these limitations and that high molar mass degradable polystyrene (Mw close to 150,000 g.mol-1) could be prepared via statistical insertion of thioester groups into the polymer backbone. Thanks to favorable reactivity ratios allowing only a few mol% of thioester units to be randomly incorporated, there was no major modification of the thermal and mechanical properties of the PS. The degradation of such PS could be performed in THF at RT in one hour using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a base, leading to oligomers with Mn close to 1,000 g.mol-1. We success-fully demonstrate further applicability of these copolymerization systems for the photo-triggered decomposi-tion of PS in solution as well as the synthesis of cross-linked PS networks degradable into soluble side-products

The activity of various additives promoting siloxane equilibration reactions is examined and quantified on model compounds. We found in particular that the "superbase" phosphazene derivative P 4 -t Bu can promote very fast exchanges (a few seconds at 90 °C) even at low concentration (< 0.1 wt %). We demonstrate that permanent silicone networks can be transformed into reprocessable and recyclable dynamic networks by mere introduction of such additives. Annealing at high temperature degrades the additives and deactivates the dynamic features of the silicone networks, reverting them back into permanent networks. A simple rheological experiment and the corresponding model allow to extract the critical kinetic parameters to predict and control such deactivations.