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 ε‐caprolactone and atom transfer radical polymerization of methyl methacrylate. Well‐defined α‐aldehyde, α′‐allyloxy heterobifunctionalized poly(ε‐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

A convenient synthesis of α,α′‐ homo‐ and α,α′‐hetero‐bifunctionalized poly(ε‐caprolactone)s by ring opening polymerization: The potentially valuable precursors for miktoarm star copolymers

“…However, thiol‐ene and CuAAC orthogonal reactions are scarcely used for this purpose. We previously reported the synthesis of α, α′‐ hetero‐bifunctionalized poly(ε‐caprolactone)s containing clickable aldehyde and allyloxy groups . In continuation of our work on functional polymers by ROP, we report herein the synthesis of α‐allyl, α′‐allyloxy and α‐allyl, α′‐propargyloxy bifunctionalized poly(ε‐caprolactone)s and their potential utility for preparation of miktoarm star copolymers using orthogonal chemistry approach.…”

Thermally Crosslinkable and Chemically Modifiable Aromatic Polyesters Possessing Pendant Propargyloxy Groups

“…The combination of step‐growth polymerization and click chemistry modification has been put to use for synthesis of a range of graft copolymers and functionalized polymers . Click chemistry modifications of aliphatic polyesters containing pendant clickable groups such as alkyne, azide, alkene, and so on have been widely explored . Until now, to the best of our knowledge, limited information is available on click chemistry modification of aromatic polyesters with a notable exception of polyesters with pendant azido groups or alkene groups …”

The preparation of α‐bis and α,ω‐tetrakis aromatic oxazolyl‐ and carboxyl‐functionalized polymers using 1,1‐bis[4‐(2‐(4,4‐dimethyl‐1,3‐oxazolyl))phenyl]ethylene in atom transfer radical polymerization reactions

“…In addition, , '-heterodifunctionalized polymers with well-defined molecular weight and chain-end functionality were prepared using a combination of the functionalized initiator approach in ATRP reactions and the post-ATRP chemical modification of the functional group at the -terminus of the polymer chain. 30,31 To our knowledge, the direct regiospecific syntheses of -bis (oxazolyl) and , -tetrakis(oxazolyl) polystyrenes as well as the corresponding well-defined -bis(carboxyl) and , -tetrakis (carboxyl) polystyrenes by ATRP methods have not been reported in the literature. Herein, the synthesis of a new symmetrically disubstituted 1,1-diphenylethylene derivative, 1,1-bis[4-(2-(4,4-dimethyl-1,3-oxazolyl))phenyl]ethylene (1), as well as its utility in ATRP reactions for the preparation of aromatic bis(oxazolyl)-functionalized polymers are reported.…”

“…For example, a series of difunctionalized initiators were employed in the initiation of the polymerization of styrene and methacrylate derivatives by ATRP methods to form chain‐end‐functionalized polymers with two functional groups, such as dihydroxyl, diester and dicarboxyl, tertiary diamine, primary diamine, bis(fluorobenzoyl) and bis(bromophenyl), introduced directly and quantitatively at the α ‐terminus of the polymer chain. In addition, α , α '‐heterodifunctionalized polymers with well‐defined molecular weight and chain‐end functionality were prepared using a combination of the functionalized initiator approach in ATRP reactions and the post‐ATRP chemical modification of the functional group at the α ‐terminus of the polymer chain …”