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Functional‐Polymer Library through Post‐Polymerization Modification of Copolymers Having Oleate and Pentafluorophenyl Pendants
Author(s) -
Maiti Binoy,
Haldar Ujjal,
Rajasekhar Tota,
De Priyadarsi
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201703151
Subject(s) - copolymer , polymer chemistry , chemistry , moiety , methacrylate , surface modification , polymerization , functional polymers , thiol , alkyl , polymer , organic chemistry
Poly[2‐(methacryloyloxy)ethyl oleate‐ co ‐pentafluorophenyl methacrylate] [P(MAEO‐ co ‐PFPMA)] random copolymers with oleate and pentafluorophenyl side‐chain pendants were synthesized. These copolymers were utilized as dual‐reactive polymeric scaffolds in a range of post‐polymerization modification strategies involving thiol‐ene and para ‐fluoro‐thiol substitution, amidation, trans ‐esterification, and epoxidation followed by amidation. The 2‐(methacryloyloxy)ethyl oleate (MAEO) functional handle in the copolymer is open to functionalization at its internal double bond through thermally initiated thiol‐ene reaction, whereas the pentafluorophenyl moiety of the pentafluorophenyl methacrylate (PFPMA) unit undergoes para ‐fluoro‐thiol substitution under basic conditions at room temperature. By means of these modification approaches, the P(MAEO‐ co ‐PFPMA) copolymer was orthogonally ligated with thiol compounds having, for example, alkyl, hydroxyl, and protected amine functional groups. Furthermore, different functional groups such as benzyl, allyl, methacrylate, pyrene, and water‐soluble poly(ethylene glycol) were easily introduced into the side chain of the P(MAEO‐ co ‐PFPMA) copolymer by amidation, trans ‐esterification, and epoxidation followed by amidation. Functionalization of both the reactive pendants with the various organic substituents was confirmed by 1 H and 19 F NMR spectroscopy, gel permeation chromatography, and fluorescence spectroscopy.