Naturally-derived amphiphilic polystyrenes prepared by aqueous controlled/living cationic polymerization and copolymerization of vinylguaiacol with R-OH/BF 3 ·OEt 2

Abstract

In this study, we investigated direct-controlled/living cationic polymerization and copolymerization of 4-vinylguaiacol (4VG), i.e., 4-hydroxy-3-methoxystyrene, which can be derived from naturally-occurring ferulic acid, to develop novel bio-based amphiphilic polystyrenes with phenol functions. The controlled/living cationic polymerization of 4VG was achieved using the R-OH/BF 3 ·OEt 2 initiating system, which is effective for the controlled/living polymerization of petroleum-derived 4-vinylphenol in the presence of a large amount of water via reversible activation of terminal C-OH bond catalyzed by BF 3 ·OEt 2 , to result in the polymers with controlled molecular weights and narrow molecular weight distributions. The random or block copolymerization of 4VG was also examined using p-methoxystyrene (pMOS) as a comonomer with an aqueous initiating system to tune the amphiphilic nature of the 4VG-derived phenolic polymers. The obtained polymer can be expected not only to be used as a novel styrenic bio-based polymer but also as a material with amphiphilic nature for some applications.