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Nitroxide mediated polymerization of sustainably sourced isobornyl methacrylate and tridecyl methacrylate with acrylonitrile co‐monomer

Author:
Hajiali, Faezeh, Métafiot, Adrien, Benitez‐Ek, Laura, Alloune, Lea, Marić, Milan
Source:
Journal of polymer science 2018 v.56 no.21 pp. 2422-2436
ISSN:
0887-624X
Subject:
composite polymers, feedstocks, glass transition temperature, molecular weight, polymerization
Abstract:
Nitroxide‐mediated polymerization (NMP) of isobornyl methacrylate (IBOMA) and tridecyl methacrylate (TDMA), derived from sustainable feedstocks, with a low fraction of acrylonitrile (AN) co‐monomer were conducted with unimolecular initiator BlocBuilder‐MA™ (BB) and the succinimidyl ester‐functionalized form, NHS‐BB. IBOMA and TDMA‐rich compositions were both polymerized at 100 °C in a controlled manner (i.e., linear increase in number average molecular weight [Mn] with conversion up to ∼40% and low dispersity, Đ < 1.5). SG1‐terminated poly(IBOMA‐stat‐AN) macroinitiator was then cleanly chain‐extended with poly(TDMA‐stat‐AN) and the diblock copolymers exhibited two distinct glass transition temperatures (Tgs), indicative of microphase separation. IBOMA/TDMA/AN terpolymers with different IBOMA/TDMA molar ratios were also synthesized where terpolymers with higher IBOMA content had higher apparent rate constants and higher Tgs. Moreover, chain growth was linear up to conversions of ∼60% and all Đs were 1.51 to 1.64. Finally, 2‐hydroxyethyl methacrylate (HEMA) was incorporated into the IBOMA/TDMA/AN system, resulting in statistical quadripolymers. The quadripolymer Tg decreased with increasing TDMA content and Mn ranged from 12 to 15.4 kg mol⁻¹ and the Đ were 1.39 to 1.54, suggesting the successful incorporation of sustainably sourced monomers into quadripolymers with a broad range of tunable Tgs via NMP with additional functionalities from HEMA. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2422–2436
Agid:
6198262