A minimal amount of acrylonitrile turns the nitroxide‐mediated polymerization of methyl methacrylate into an almost ideal controlled/living system

Abstract

Nitroxide‐mediated controlled/living free‐radical polymerization of methyl methacrylate initiated by the SG1‐based alkoxyamine BlocBuilder was successfully performed in bulk at 80–99 °C with the help of a very small amount of acrylonitrile (AN, 2.2–8.8 mol %) as a comonomer. Well‐defined PMMA‐rich P(MMA‐co‐AN) copolymers were prepared with the number‐average molar mass, Mn, in the 6.1–32 kg mol−1 range and polydispersity indexes as low as 1.24. Incorporation of AN in the copolymers was demonstrated by 1H and 13C NMR spectroscopy, and its effect on the chain thermal properties was evaluated by DSC and TGA analyses. Investigation of chain‐end functionalization by an alkoxyamine group was performed by means of 31P NMR spectroscopy and chain extensions from a P(MMA‐co‐AN)‐SG1 macroinitiator. It demonstrated the very high proportion of SG1‐terminated polymer chains, which opened the door to block copolymer synthesis with a high quality of control. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 34–47, 2010

From one-pot stabilisation to in situ functionalisation in nitroxide mediated polymerisation: an efficient extension towards atom transfer radical polymerisation

“…The polymer is, in fact, a macroinitiator, which can be used to reinitiate the NMP process in the presence of a second monomer, thereby generating block copolymers 29,30 . However, if an end material is sought, the polymerisation thermodynamics might become unfavourable at high temperature as the importance of entropy rises accordingly 31 , which will induce depropagation processes 32,33 .…”

Compatibilization of Poly(styrene‐acrylonitrile) (SAN)/Poly(ethylene) Blends via Amine Functionalization of SAN Chain Ends

“…[65] At 200 °C, 97.0% of the living SAN polymer remained, and 99.5% of the deactivated SAN remained. TGA also showed that 100.0% of the PE remained at 200 °C.…”

“…[65] With the same set-up as described in the previous section, NHS-SAN copolymer °C. The AN molar composition of the SAN copolymer using FTIR was F AN = 0.43.…”

“…[65] Since the SAN was to be blended in an extruder at 200 °C, it was important for it to be thermally stable. The SG1-terminated SAN polymers were deactivated using thiophenol, and TGA was performed on the SAN before and after SG1 removal.…”

From NMP to RAFT and Thiol‐Ene Chemistry by In Situ Functionalization of Nitroxide Chain Ends

“…This can be an advantage for the synthesis of block copolymers as the polymerisation can be reinitiated in presence of a second monomer [9] . However, there is an interest in removing the nitroxide end-group, for example to improve thermal stability [17] or introduce functional groups [1,18,19] . Furthermore, there is a growing trend for combining different polymerisation methods for the synthesis of new copolymers, which cannot be obtained by one technique only [20][21][22] .…”