A facile strategy for synthesis of α,α′-heterobifunctionalized poly (ε-caprolactones) and poly (methyl methacrylate)s containing “clickable” aldehyde and allyloxy functional groups using initiator approach

Abstract

Two new initiators, namely, 4-(4-(2-(4-(allyloxy) phenyl)-5-hydroxypentane 2-yl) phenoxy)benzaldehyde and 4-(4-(allyloxy) phenyl)-4-(4-(4-formylphenoxy) phenyl) pentyl 2-bromo-2-methyl propanoate containing “clickable” hetero-functionalities namely aldehyde and allyloxy were synthesized starting from commercially available 4,4′-bis(4-hydroxyphenyl) pentanoic acid. These initiators were utilized, respectively, for ring opening polymerization of e-caprolactone and atom transfer radical polymerization of methyl methacrylate. Well-defined α-aldehyde, α′-allyloxy heterobifunctionalized poly(e-caprolactones) (Mn,GPC: 5900–29,000, PDI: 1.26–1.43) and poly(methyl methacrylate)s (Mn,GPC: 5300–28800, PDI: 1.19–1.25) were synthesized. The kinetic study of methyl methacrylate polymerization demonstrated controlled polymerization behavior. The presence of aldehyde and allyloxy functionality on polymers was confirmed by 1H NMR spectroscopy. Aldehyde-aminooxy and thiol-ene metal-free double click strategy was used to demonstrate reactivity of functional groups on polymers. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013