Preparation and orthogonal postmodification of dual‐clickable polymer precursors bearing both aldehyde and alkyne groups

Abstract

A new styrenic monomer 2-propargyloxy-5vinylbenzaldehyde (PVB) containing both aldehyde and alkyne reactive groups was designed for the synthesis and subsequent orthogonal postfunctionalization of dual-clickable polymer precursor. Reversible addition-fragmentation chain transfer polymerization of PVB afforded a structurally well-defined polymer poly(2-propargyloxy-5-vinylbenzaldehyde) (PPVB) bearing alkyne and aldehyde functionalities that are reactive towards azide-and aminooxy-containing molecules, respectively. Therefore, the resulting PPVB can be served as a dual-clickable polymer scaffold for construction of multiple functional polymers via orthogonal alkyne-azide and aldehyde-aminooxy click reactions. Postpolymerization modification of PPVB sequentially with aminooxy-terminated poly(ethylene oxide)s (H 2 NO-PEO) and azide-functionalized imidazolium-type ionic liquid (N 3 -ILÁTFSI,

Orthogonal synthesis and modification of polymer materials

“…Click reactions are utilized dominantly nowadays in order to tailor complex microstructure in macromolecules 11–25 . Mild reaction conditions, high regio‐ and stereoselectivity, tolerance toward different conditions, and easy purification are prominent advantages for this chemistry 11,12,16,26,27 .…”

“…The advent of RDRP provided simple, versatile and robust methods of incorporating diverse functionalities into polymer materials allowing for facile installation of click‐ready functions to polymer end‐groups and pendant groups. Coupling orthogonal click chemistry with RDRP methodologies such as atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer (RAFT) polymerizations and nitroxide mediated polymerization (NMP), to name a few, has further extended the possible applications and varied topology for these materials, 24 which will be discussed in the following section.…”