Kinetics of Radical Chain Polymerization: 1. Time-Dependent Distributions of Macroradicals and Oligomers

Phosphine Oxide-Containing Multifunctional Polymer via RAFT Polymerization and Its High-Density Post-Polymerization Modification in Water

“…Phosphorus-containing polymers, whether the phosphorus atom connected to a polymer chain by a P–O bond (polyphosphoester) or a P–C bond (polyphosphine/polyphosphine oxide), have gained considerable attention over the past decades. Owing to their excellent properties, phosphorus-related polymers have been used in various fields such as in fuel cell membranes, adhesives, flame retardant additives, , complexing agents of recovering metal ions from the environment and industrial liquids, − and biomedical materials. − Three strategies have been proposed to incorporate phosphorus functionality into polymer chains: (i) stepwise polycondensation of di-/multifunctional phosphorus-containing monomers, − (ii) chain polymerization of phosphorus-containing polymerizable monomers, − and (iii) introduction of phosphorated moieties via the chemical reaction of reactive polymers (namely, post-polymerization modification). , Among them, the chain polymerization of the corresponding monomer has attracted tremendous attention for its potential to prepare various kinds of polymers with well-defined structures and controllable molecular weight distributions. − In fact, the controlled/living radical chain polymerizations of phosphorus-containing monomers have been developed, and the resulting phosphorus-containing polymers possessed controllable architectures and satisfactory molecular weight distributions.…”

Synthesis of Micrometer-Sized Poly(methyl acrylate) by Temperature-Step Microsuspension Polymerization with Iodoform Based on the “Radical Exit Depression” Effect§

“…In the first step at 70 °C, the molecular weights of PMA grew with conversion (15,500, 20% → 18,100, 50%) but much higher than the theoretical one. It can be ascribed to a lower chain-transfer rate than the propagation rate at 70 °C. − Moreover, the relatively high M w / M n in the range from 1.8 to 2 could be explained by this low chain-transfer reaction. However, in the second temperature step at 80 °C, M n (19,300) nearly unchanged (Figure b), which was significantly lower than M n,th .…”