Effect of Scandium Triflate on the RAFT Copolymerization of Methyl Acrylate and Vinyl Acetate Controlled by an Acid/Base “Switchable” Chain Transfer Agent

Abstract

Effect of scandium triflate on the RAFT copolymerization of methyl acrylate and vinyl acetate controlled by an acid/base "switchable" chain transfer agent. Macromolecules, 51 (2). pp. 410-418.

Asymmetric Copolymers: Synthesis, Properties, and Applications of Gradient and Other Partially Segregated Copolymers

“…Spontaneous gradient copolymers have been obtained via catalyst transfer polycondensation, [35] catalyzed copolymerization of olefins [36] and epoxides, [37] diverse RDRP methods (ATRP, [43][44][45][46][47][48] NMP, [49][50][51][52][53][54][55][56] OMRP, [57] RAFT, [22][23][24][58][59][60][61] ) as well as cationic ring opening polymerization. [28][29][30][31][32][33] Also, the gradient-composition backbone can be used as macroinitiators to synthesize high-molecular-weight brushes.…”

“…Many techniques have been used for the preparation of asymmetric copolymers, including anionic [27] and cationic [28][29][30][31][32][33] polymerizations, C1 polymerization, [34] catalyst transfer polycondensation, [35] catalyzed copolymerization of olefins [36] and epoxides, [37] ring-opening metathesis polymerization (ROMP) [38][39][40][41][42] and various RDRP techniques (e.g., atom transfer radical polymerization (ATRP), [43][44][45][46][47][48] nitroxide-mediated polymerization (NMP), [49][50][51][52][53][54][55][56] organometallic-mediated radical polymerization (OMRP), [57] and reversible addition-fragmentation chain transfer (RAFT) [22][23][24][58][59][60][61] ).…”

Ab initio RAFT emulsion polymerization mediated by small cationic RAFT agents to form polymers with low molar mass dispersity

“…The (pyridin-4-yl)carbamodithioates 1 were initially designed for use as switchable RAFT agents that can provide good control over both more and less activated monomers (MAMs and LAMs). [40][41][42][43][44][45][46][47][48][49] In their switched or protonated state, 2, they allow the synthesis of low Ð m poly(MAM)s, e.g., polystyrene with 4, and in their unswitched or neutral state, 1, facile polymerization of LAMs to give low Ð m poly(LAM)s, e.g., poly(VAc) with 3. These RAFT agents also enable the preparation of low Ð m poly(MAM)-block-poly(LAM)s by sequential monomer addition.…”

Effect of the Z‐ and Macro‐R‐Group on the Thermal Desulfurization of Polymers Synthesized with Acid/Base “Switchable” Dithiocarbamate RAFT Agents

“…A prime example are acid/base switchable N ‐pyridyl‐functional dithiocarbamate RAFT agents, which provide the ability to control the polymerization of both more activated monomers (MAMs) and less activated monomers (LAMs). By switching the RAFT agent Z‐group between a neutral pyridyl (e.g., in 1 or 2 ) and a charged pyridinium moiety, (e.g., in 1 ‐H + or 2 ‐H + ) low dispersity block copolymers comprising both MAMs and LAMs can be prepared.…”

“…In our previous investigations, [10,[12][13][14]16] the N-pyridylfunctional dithiocarbamate RAFT agents and their derived polymers were found to be unusually robust. For example, their high hydrolytic stability allows aqueous polymerization in strongly acidic solution (e.g., pH ≤ 2) with no discernible loss of end group functionality.…”