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Click Functionalization of a Dibenzocyclooctyne‐Containing Conjugated Polyimine
Author(s) -
Kardelis Vladimir,
Chadwick Ryan C.,
Adronov Alex
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201508639
Subject(s) - conjugated system , polymer chemistry , click chemistry , azide , chemistry , cycloaddition , monomer , polymer , polymerization , ether , polystyrene , condensation polymer , copolymer , organic chemistry , catalysis
A conjugated poly(phenyl‐ co ‐dibenzocyclooctyne) Schiff‐base polymer, prepared through polycondensation of dibenzocyclooctyne bisamine (DIBO‐(NH 2 ) 2 ) with bis(hexadecyloxy)phenyldialdehyde, is reported. The resulting polymer, which has a high molecular weight ( M n >30 kDa, M w >60 kDa), undergoes efficient strain‐promoted alkyne–azide cycloaddition reactions with a series of azides. This enables quantitative modification of each repeat unit within the polymer backbone and the rapid synthesis of a conjugated polymer library with widely different substituents but a consistent degree of polymerization (DP). Kinetic studies show a second‐order reaction rate constant that is consistent with monomeric dibenzocyclooctynes. Grafting with azide‐terminated polystyrene and polyethylene glycol monomethyl ether chains of varying molecular weight resulted in the efficient syntheses of a series of graft copolymers with a conjugated backbone and maximal graft density.