In Situ NMR and Modeling Studies of Nitroxide Mediated Copolymerization of Styrene and n-Butyl Acrylate

Abstract

In the past 2 decades, much attention has been focused on copolymerizations due to a wide variety of applications that can be served by copolymers. 1À4 In particular, styrene and n-butyl acrylate copolymers obtained via different techniques have been extensively studied and reported. 1,5,6 The use of in situ NMR in studies of living radical homo-and copolymerizations has proven to be very powerful. 7À10 Kinetic parameters such as reactivity ratios have been determined from in situ 1 H NMR data for different systems. 8,9 Information on copolymer composition has also been reported from in situ 1 H NMR data. 2,9

An Update on the Pivotal Role of Kinetic Modeling for the Mechanistic Understanding and Design of Bulk and Solution RAFT Polymerization

“…[47,52,[72][73][74][75][76][77] The most popular deterministic full CLD method is the discretized Galerkin h-p-method (dGhp), as explored by Wulkow et al [76] and applicable via the commercial package PREDICI. [25,33,51,55,[78][79][80][81][82][83] For RAFT polymerization, one of the earliest PREDICI contributions [25] paid attention to the influence of RAFT specific kinetic parameters on the temporal evolution of the CLD and monomer conversion. In this study it was demonstrated that RAFT inhibition can be related to slow reinitiation ( Figure 1e) or SF of the R i X * R 0 species (Figure 1d).…”

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

“…Set of initial concentrations and kinetic parameters used in the simulations of Styrene/n-butyl acrylate (S/B) copolymerization via NMP at 120 8C. [49,50] Parameter/concentration Value Units given the very large value of k BS . This results in an initial low initiation rate of type S radicals (k in;S ( k in;B in spite of the fact that [M S ] 0 ¼ 19 [M B ] 0 ); as their termination rate is relatively high, which causes the value of d IT,S to be initially negative.…”

A Theoretical Exploration of the Potential of ICAR ATRP for One‐ and Two‐Pot Synthesis of Well‐Defined Diblock Copolymers

“…Moreover, controlled ATRPs of acrylates has been found to lead to a much lower amount of branching as compared to FRP 51, 52. Also, recent work of Klumperman and Hlalele53 showed that in CRP copolymerizations involving acrylates the branching amount is further reduced, since other co‐monomers are typically not susceptible to backbiting. On the other hand, for styrene, the influence of thermal self‐initiation and chain transfer reactions can be safely neglected at the considered temperatures in this work 54–58…”