Reverse Iodine Transfer Polymerization (RITP): From Kinetics and Mechanisms to Macromolecular Engineering

Copolymer Composition Deviations from Mayo–Lewis Conventional Free Radical Behavior in Nitroxide Mediated Copolymerization

“…The terms R x in the rhs identities are defined implicitly from the context of Equation (13)(14)(15) to represent individual rate terms in a simplified way. The d-ps are obtained by solving the system of Equation (5)(6)(7)(8)(9)(10)(11) without approximations (within the accuracy provided by the numerical integration algorithm). In terms of the d-ps, Equation (9) can be re-written (without the primary radical termination term, which is usually negligible) as:…”

“…Concentrations are represented by writing the species in square brackets as usual; species symbols without brackets represent molar quantities. The system of ordinary differential equations (ODE), Equation (5)(6)(7)(8)(9)(10)(11), represents the exact mathematical representation corresponding to Scheme 2, which will be compared with other models in the sections below.…”

“…The variety of monomers that can be used and the mildness of the reaction conditions utilized make CRP more convenient than anionic or cationic polymerizations for precise polymer synthesis. In general terms, CRP techniques can be divided in two categories depending on the mechanism leading to the controlled/living character of the polymerization: i) reversible termination techniques, governed by the persistent radical effect, as in stable free radical polymerization (SFRP), or nitroxide‐mediated polymerization (NMP), and atom transfer radical polymerization (ATRP) and ii) reversible chain transfer methods, as in reversible addition fragmentation chain transfer polymerization (RAFT), and others …”

“…In general terms, CRP techniques can be divided in two categories depending on the mechanism leading to the controlled/living character of the polymerization: i) reversible termination techniques, governed by the persistent radical effect, as in stable free radical polymerization (SFRP), or nitroxidemediated polymerization (NMP), [2,3] and atom transfer radical polymerization (ATRP) [4] and ii) reversible chain transfer methods, as in reversible addition fragmentation chain transfer polymerization (RAFT), [5] and others. [6][7][8] The techniques in the reversible termination class, such as NMP and ATRP, control the growth of the polymeric chains via reversible activation-deactivation steps by which living chains and persistent radicals are transformed back and forth into dormant polymer. In NMP, the persistent radicals are nitroxide radicals, while in ATRP the persistent radicals are transition metals (i.e., Cu II ) with a coordinated ligand.…”

Molecular iodine in monomer and polymer designing

“…M n; theo ¼ ðmass of the monomerÞ=ð2 Â n I2; initial Þ þ M AÀI Lacroix-Desmazes'school excelled in making polymers of controlled architectures using RITP techniques. [91] One of their attractive works resides in conducting polymerization in emulsion [92] and miniemulsion of some vinyl monomers such as styrene. [93] The latter polymerization was induced by bis(4-tert-butylcyclohexyl) peroxydicarbonate as radical initiator at a temperature of 60°C with sodium dodecylsulfate salt (SDS) as surfactant and hexadecane as hydrophobe, giving a stable and uncolored latex.…”