N-tert-Butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide as counter radical in the controlled free radical polymerization of styrene: kinetic aspects

Living Radical Polymerization as a Tool for the Synthesis of Polymer‐Protein/Peptide Bioconjugates

“…This nitroxide is efficient with styrenic monomers at relatively high temperatures ( T = 123–135 °C). More recently, an important breakthrough has been the discovery of efficient acyclic nitroxides for NMP such as N ‐ tert ‐butyl‐ N ‐[1‐diethylphosphono‐(2,2‐dimethylpropyl)] nitroxide (SG1),30–33 and N ‐ tert ‐butyl‐ N ‐[1‐phenyl‐2‐(methylpropyl)] nitroxide (TIPNO), (Scheme ) 9, 34–38. This last generation of nitroxides is particularly well‐suited for the polymerization of styrenics,30, 36 alkyl acrylates,30, 36 methyl methacrylate (via a copolymerization approach),36, 39, 40 acrylic acid,41 acrylamides,42, 43 and dienes 34.…”

Hybrid Aluminum Colored Pigments Based on Gradient Copolymers Design

“…In this scope, the initiator was prepared by trapping MAMA on the CC double bond of the n ‐butyl acrylate as a model initiator. Moreover, according to previous studies,38–40 we chose a [SG1]/[alkoxyamine] = 0.05 molar ratio.…”

“…In the present case, k pbutyl acrylate (88 000 L · mol −1 · s −1 , at 120 °C)48 is higher than k pstyrene (2 000 L · mol −1 · s −1 , at 120 °C) 49. The respective value of K and r for S and n ‐BuA are K styrene = 1.9.10 −8 mol · L −1 at 125 °C,39 K butyl acrylate = 1.2 · 10 −10 mol · L −1 at 125 °C50 and r styrene = 0.74, r butyl acrylate = 0.29 51. The high k p,butyl acrylate was counterbalanced by an increase of the 〈 K 〉 related to the high value of K styrene , the difference in the monomer reactivity ratio and the low k p,styrene .…”

Radical Chain Polymerization

“…The general characteristics of ATRP described in Sec. 3-15b apply to NMP, that is, reaction variables control polymerization rate, molecular weight, and PDI in the same way [Ananchenko and Fischer, 2001;Greszta and Matyjaszewski, 1996;Lacroix-Desmazes et al, 2000Lutz et al, 2001;Yoshikawa et al, 2002]. NMP with TEMPO generally requires higher temperatures (125-145 C) and longer reaction times (1-3 days) compared to ATRP, and only styrene and 4-vinylpyridine polymerizations proceed with good control of molecular weight and polydispersity.…”