Particle Nucleation in the Initial Stage of Emulsifier‐Free, Emulsion Organotellurium‐Mediated Living Radical Polymerization (Emulsion TERP) of Styrene: Kinetic Approach

Abstract

Kinetic simulations of polymer chain propagation in an aqueous medium in an initial stage of emulsifier‐free, emulsion organotellurium‐mediated living radical polymerization (emulsion TERP) of styrene with sodium poly(methacrylic acid)‐methyltellanyl (PMAA‐TeMe) as a control agent and 4,4′‐azobis(4‐cyanovaleric acid) as a water‐soluble azo‐initiator at various polymerization temperatures, which is carried out experimentally at pH > 9 in a previous article, is performed using PREDICI software from CiTGmbH. The approach based on α‐chain end‐separated kinetic simulation leads us to get important aspects of individual polymer chain growths from both α‐end groups, i.e., initiator and PMAA end groups. The larger number percentage of polystyrene (PS) chain having PMAA end group relative to all PS chains is generated at lower polymerization temperature. In addition, the PS chain growth is also pronounced at lower temperature. In other words, the self‐assembly nucleation, in which the control agents are contained, predominantly occurs at the lower polymerization temperature than the homogeneous nucleation, in which they are not contained. This indicates that the emulsion TERP effectively proceeds at lower temperature, which is well accorded with the experimental result in the previous article.

Supramolecular Radical Switches Regulated by Host‐Guest Chemistry

“…The controlled generation of radicals is highly desirable in the subtle control of radical-related reactions in various fields, including radical polymerization, [1] catalysis, [2] and biomedical applications. [3] Thermal initiators are widely used as radical sources that can generate radicals under thermal stimuli.…”

Synthesis of Micrometer‐Size Poly(Methyl Methacrylate) Particles by Utilizing Microsuspension Iodine Transfer Polymerization (ms ITP): Kinetic Approach

“…As f value of BPO, 1.0 was used. Simulation for ITP of MMA based on the kinetic model was performed using PREDICI software from CiT GmbH (Rasfede, Germany) using kinetic coefficients shown in Table 1 , which are obtained from references shown in Table 2 . Concentrations of MMA, BPO and CHI 3 , which are, respectively, shown as [M], [I] and [CHI 3 ] in Table , used for the simulation are calculated from the recipe of the oil phase (except for PVA aqueous solution as the aqueous medium) of the ms ITP in the previous article: MMA, 5.0 g; BPO, 0.40 g; CHI 3 , 0.06 g (1 wt % PVA aqueous solution, 45.0 g).…”

Reversible chain transfer catalyzed polymerization in miniemulsion systems with tetraiodomethane as a catalyst

“…20 Cheng and Zhu's group reported that triphenylphosphine is an effective catalyst for RTCP, 24 while H-phosphonic acid derivatives have been used as RTCP catalysts by Vana et al 25 An advantage of RDRPs compared with other living polymerization systems, such as anionic and cationic polymerizations, is their high tolerance to water. Hence, the combination of RDRPs and aqueous heterogeneous polymerization systems (such as, miniemulsion, 13,[26][27][28][29][30][31] emulsion, [32][33][34][35][36][37] microemulsion, [38][39][40] and dispersion [41][42][43][44] polymerizations) provides well-defined polymers in particulate states. [45][46][47] Miniemulsion polymerization is an aqueous heterogeneous polymerization strategy involving the formation of monomer droplets in aqueous media prior to polymerization, where polymerization subsequently occurs; the monomer droplets function as nanocontainers for radical polymerization.…”