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

Hajiali, Faezeh, Métafiot, Adrien, Benitez‐Ek, Laura, Alloune, Lea, Marić, Milan
Journal of polymer science 2018 v.56 no.21 pp. 2422-2436
composite polymers, feedstocks, glass transition temperature, molecular weight, polymerization
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