Making the best of it: nitroxide-mediated polymerization of methacrylatesviathe copolymerization approach with functional styrenics

Abstract

The addition of 5 mol% of functional styrenics imparts control to the SG1-mediated polymerization of methacrylates and provides access to nanostructured functional methacrylic materials.

Organic–inorganic hybrid functional materials by nitroxide-mediated polymerization

“…In the early 2000's, drastic improvements were nevertheless made by Charleux et al [86][87][88] who demonstrated that the addition of a small amount of a comonomer with a low activation-deactivation equilibrium constant <K> = Kd/Kc, such as styrene, strongly improved the DEPN-mediated polymerization of MMA. The method was later successfully extended to 4-vinyl pyridine (4VP) [89] and various styrenic compounds [90][91][92]. The role of these controlling comonomers is to reduce the activation-deactivation rate constant, leading to a diminution of the concentration of propagating radicals, and hence to a better control.…”

Controlled Synthesis of Poly(pentafluorostyrene-ran-methyl methacrylate) Copolymers by Nitroxide Mediated Polymerization and Their Use as Dielectric Layers in Organic Thin-film Transistors

“…To increase the number of living propagating chains methacrylate monomers are often copolymerized with a slowly propagating comonomer, which is more compatible with NMP, such as styrenics [28][29][30][31], acrylonitrile [32][33][34][35] or cyclic ketene acetal 2-methylene-4-phenyl-1,3-dioxolane [36,37]. PFS has been demonstrated to behave as a controlling comonomer in the NMP of various methacrylic monomers, such as methacrylic acid [22], 5-methacryloyloxy-2,6-norboranecarbolactone (NLAM) [38], oligo(ethyleneglycol) methacrylate (OEGMA) [39] and, very recently, methyl methacrylate (MMA) [40]. Delaittre and coworkers demonstrated that ≈5 mol% of PFS could control the copolymerization of MMA, leading to a high MMA-containing pseudo-living macroinitiator, suitable for the chain extension of styrene [40].…”

“…PFS has been demonstrated to behave as a controlling comonomer in the NMP of various methacrylic monomers, such as methacrylic acid [22], 5-methacryloyloxy-2,6-norboranecarbolactone (NLAM) [38], oligo(ethyleneglycol) methacrylate (OEGMA) [39] and, very recently, methyl methacrylate (MMA) [40]. Delaittre and coworkers demonstrated that ≈5 mol% of PFS could control the copolymerization of MMA, leading to a high MMA-containing pseudo-living macroinitiator, suitable for the chain extension of styrene [40]. To further characterize this copolymerization at low through high PFS loadings we performed a range of copolymerizations with a target number average molecular weight (M n ) of 25 kg mol −1 in a 50 wt% solution of xylenes at 90 • C, with feed compositions ranging from 5-100 mol%, which is detailed in Table 1.…”

Nitroxide-Mediated Polymerization: A Versatile Tool for the Engineering of Next Generation Materials

“…Furthermore, NMP does not require transition metal catalysts or potentially undesirable thioester/thiocarbonate transfer agents, compared to other RDRP techniques such as reversible addition–fragmentation transfer (RAFT) and atom transfer radical polymerization (ATRP), , suggesting polymers by NMP can be integrated into electronic applications and delicate biological applications without significant additional purification or processing. Historically, NMP was only effective in the polymerization of styrenics; however, over the last two decades, advances in initiator design, such as N- tert -butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] (SG1), 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxy (TIPNO), and 3-(((2-cyanopropan-2-yl)­oxy)-(cyclohexyl)­amino)-2,2-dimethyl-3-phenylpropanenitrile (Dispolreg 007) have led to an increase in potential monomers, such as acrylates, − methacrylates (either copolymerized − or homopolymerized − ), dienes, , vinyl acetate, , acrylamides, , and more, making NMP a desirable technique capable of engineering of next generation materials for emerging applications. The following review builds off recent work and emphasizes emerging applications, which benefit from the use of NMP mainly in the last 5–6 years.…”