Bio-Based Functional Styrene Monomers Derived from Naturally Occurring Ferulic Acid for Poly(vinylcatechol) and Poly(vinylguaiacol) via Controlled Radical Polymerization

A naturally occurring vinylphenolic compound, 4-vinylguaiacol (4VG: 4-hydroxy-3-methoxystyrene), which is derived from naturally occurring ferulic acid via decarboxylation, was used for the synthesis of well-defined bio-based poly(vinylguaiacol) and poly(vinylcatechol) with phenolic functions. Through one-step chemical conversions of 4VG, a series of 4VG derivatives protected with acetyl (Ac4VG), tert-butyldimethylsilyl (TBDMS4VG), or triethylsilyl (TBDMS4VG) groups as well as bis(triethylsilyl)-protected vinyl catechol (TES2VC) were synthesized with high yields (>90%). The controlled radical polymerization of these protected bio-based phenolic styrene monomers successfully proceeded in the presence of appropriate reversible addition–fragmentation chain transfer (RAFT) agents or alkoxyamines with or without radical initiators such as 4,4′-azobis(isobutyronitrile) (AIBN) to result in polymers with controlled molecular weights. Bimolecular combination reactions were suppressed even at the high monomer conve...

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