Journal
MACROMOLECULES
Volume 52, Issue 22, Pages 8577-8586Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.9b01807
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Funding
- Strategic International Collaborative Research Program (SICORP) from The French National Research Agency (ANR), JST
- KAKENHI Grant [19H00911, 17H06453]
- Grants-in-Aid for Scientific Research [17H06453, 19H00911] Funding Source: KAKEN
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In this work, we provide a facile methodology to synthesize AB alternating-rich copolymers made of methacrylic acid (MAA) and alkyl acrylamide units. An extremely bulky tent-alkyl methacrylate carrying ethyl and fenchol substituents (EFMA) was newly designed as a special monomer that is inactive for homopolymerization but active for copolymerization in radical polymerization. Indeed, EFMA showed a unique radical copolymerization behavior to the bulkiness, which was quite different from a general methacrylate (i.e., methyl methacrylate). The copolymerization of EFMA with an electron-deficient acrylate carrying a N-hydroxysuccinimide substituent followed by postreactions (i.e., acidolysis and aminolysis) for both units afforded an alternating-rich copolymer of MAA and alkyl acrylamide units. The sequence was characterized by C-13 NMR analyses in comparison with the statistical copolymers and homopolymers. The reactivity ratio values also supported the process of alternating copolymerization. The thus-obtained alternating-rich copolymers of MAA with isopropyl acrylamide or octadecyl acrylamide showed sequence-driven solubilities and thermal response properties.
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