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

A new styrenic monomer 2-propargyloxy-5-vinylbenzaldehyde (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 -IL·TFSI, having bis(trifluoromethane)sulfonamide, TFSI, counter-anion) yielded an interesting multicomponent graft polymer PPVB- g -(PEO- and -IL·TFSI). After anion exchange of hydrophobic TFSI counter-anion by bromide (Br) anion, the resulting graft copolymer PPVB- g -(PEO- and -IL·Br) becomes soluble in water, and its imidazolium units can capture negatively charged tetraphenylethylene disulfonate derivative (TPE-2 ) guest molecule via electrostatic complexation to form in situ self-assembled fluorescent nanoaggregates with colloidal stability imparted by hydrophilic PEO chains. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2650–2656