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Synthesis of Well-Defined Pyrrolidone-Based Homopolymers and Stimulus-Responsive Diblock Copolymers via RAFT Aqueous Solution Polymerization of 2‑(N‑Acryloyloxy)ethylpyrrolidone
journal contribution
posted on 2018-09-25, 11:45 authored by O. J. Deane, J. R. Lovett, O. M. Musa, A. Fernyhough, S. P. ArmesPoly(N-vinylpyrrolidone) (PNVP) is a well-known,
highly polar, nonionic water-soluble polymer. However, N-vinylpyrrolidone (NVP) usually exhibits strongly non-ideal behavior
when copolymerized with methacrylic or styrenic monomers. Moreover,
NVP is not particularly well-controlled under living radical polymerization
conditions. For these reasons, alternative pyrrolidone-based monomers
have been investigated. For example, the reversible addition–fragmentation
chain transfer (RAFT) polymerization of 2-(N-methacryloyloxy)ethylpyrrolidone
(NMEP) has been recently investigated using various polymerization
formulations. However, PNMEP homopolymers are significantly less hydrophilic
than PNVP and exhibit inverse temperature solubility in aqueous solution.
In the present work, we studied the RAFT aqueous solution polymerization
of 2-(N-acryloyloxy)ethylpyrrolidone (NAEP)
using either AIBN at 70 °C or a low-temperature redox initiator
at 30 °C. PNAEP homopolymers are obtained in high yield (>99%)
with good control (Mw/Mn < 1.20) for target degrees of polymerization (DP)
of up to 400 using the latter initiator, which produced relatively
fast rates of polymerization. However, targeting DPs above 400 led
to lower NAEP conversions and broader molecular weight distributions.
2-Hydroxyethyl acrylate (HEA) and oligo(ethylene glycol) methyl ether
acrylate (OEGA) were chain-extended using a PNAEPx macro-CTA via RAFT aqueous solution polymerization, yielding
double-hydrophilic acrylic diblock copolymers with high conversions
(>99%) and good control (Mw/Mn < 1.31). In addition, a PNAEP95 macro-CTA
was chain-extended via RAFT aqueous solution polymerization of N-isopropylacrylamide (NIPAM) at 22 °C. Dynamic
light scattering (DLS) analysis indicated that heating above the lower
critical solution temperature of PNIPAM led to so-called “anomalous
micellization” at 35 °C and the formation of near-monodisperse
spherical micelles at 40 °C. Finally, 2-(diethylamino)ethyl
methacrylate (DEA) was polymerized using an N-morpholine-functionalized
trithiocarbonate-based RAFT chain transfer agent and subsequently
chain-extended using NAEP to form a novel pH-responsive diblock copolymer.
Above the pKa of PDEA (∼7.3), DLS
and 1H NMR studies indicated the formation of well-defined
PDEA-core spherical micelles.
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Keywords
NMEPPDEAmethyl ether acrylatealternative pyrrolidone-based monomersWell-Defined Pyrrolidone-Based HomopolymersRAFT Aqueous Solution PolymerizationNIPAMPNVPPNAEP x macro-CTADEAsolution polymerizationDLSOEGANVPPNAEP 95 macro-CTAchain-extendedStimulus-Responsive Diblock Copolymersmorpholine-functionalized trithiocarbonate-based RAFT chain transfer agent2- Hydroxyethyl acrylateHEAAIBNPNIPAMDPdouble-hydrophilic acrylic diblock copolymersnovel pH-responsive diblock copolymer1 H NMR studiesPNMEP
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