Controlled Synthesis of Alternating Copolymers by RAFT Copolymerization of N‐Vinylphthalimide with N‐Isopropylacrylamide

Abstract

A nonconjugated N‐vinyl monomer, N‐vinylphthalimide (NVPI), was copolymerized with various comonomers via reversible addition‐fragmentation chain transfer (RAFT) process. Two different chain transfer agents (CTAs), O‐ethyl‐S‐(1‐ethoxycarbonyl) ethyldithiocarbonate (CTA 1) and benzyl 1‐pyrrolecarbodithioate (CTA 2), were compared for these copolymerizations with 2,2′‐azobis(isobutyronitrile) as an initiator. The effects of the nature of CTA, the comonomer structure, and solvent on the copolymerization were investigated in terms of the controlled character of the copolymerization and alternating structure. The copolymerization of NVPI and N‐isopropylacrylamide using CTA 2 in DMF or MeOH afforded well‐defined copolymers with predominantly alternating structure, controlled molecular weights, and low molecular mass distributions.magnified image

Living Radical Polymerization by the RAFT Process – A Third Update

“…A* [103,493] (St) [510,511] (BA) [112] (BA) [511] (MA) [511] NIPAm [112] VAc [512] VPv [513] NVC [514] NVP [103,493,515] NVP [513] NVPip [516] NVC [514,515] VAc/VPv [513] (BA-b-St) [511] (MA-b-St) [511] BA-b-NIPAm [112] NVC-b-Ac [514] NVP-b-NVC [515] NVPip-b-VAc [516] NVC-b-NVP [515] NVC-b-VAc [514] (NIPAm/NVPI) [517] (Continued ) [512] (VAc) [512] (230) [512] (230-b-VAc) [512] 231…”

“…Note, however, that good control over copolymerization of LAMs with MAMs can be obtained with RAFT agents suited to MAMs (e.g. NVPI/NIPAm with 251 [517] ). The polymerization of NVP in aqueous media was reported as problematic due to the sensitivity of the macro-RAFT agent with a terminal NVP unit to hydrolysis.…”

“…[114] 249 PEO macro-RAFT agent [533] 360/BAm [533] 250 N S S A* MMA [534] MA [534] 364 [289] (NES) [290] (BES) [290] 452 [535] NIPAm/NVPI [517] MMA-b-PS [534] MA-b-PS [534] 364-b-387 [289] 251…”

Rylene bisimide-based nanoparticles with cross-linked core and thermoresponsive shell using poly(vinyl amine)-based block copolymers

“…Well-defined thermoresponsive block copolymer, poly(vinyl amine)-b-poly(NIPAM), was synthesized by RAFT polymerization of NIPAM using poly(NVPI) macro-CTA, followed by the deprotection (Scheme 2), according to a previously reported procedure [46,47]. All polymerizations were carried out in a degassed sealed tube.…”

“…Poly(vinyl amine) is one of the simplest and most important primary amine-containing polymers, due to very high content of primary amine groups and significant modification possibilities [44,45]. In this study, we employed poly(vinyl amine)-based block copolymer, which was synthesized by RAFT polymerization of N-vinylphthalimide (NVPI) followed by deprotection (Scheme 2) [46,47]. The preparation of cross-linked nanoparticles was carried out by a single-step imidization reaction of poly(vinyl amine)-b-poly(NIPAM) and arylene dianhydride derivatives, including naphthalene-1,8:4,5-tetracarboxylic dianhydride and perylene-3,4:9,10-tetracarboxylic dianhydride, respectively.…”