Synthesis of terpyridine end-modified polystyrenes through atrp for facile construction of metallo-supramolecular p3ht-b-ps diblock copolymers
Journal
Polymers
Journal Volume
12
Journal Issue
12
Pages
1-9
Date Issued
2020
Author(s)
Tu T.-H
Abstract
Complementary complexation between 2,2′:6′,2”-terpyridine (tpy) and 6,6”-dianthracenyl-substituted tpy in the presence of Zn(II) ions provided an efficient strategy for construction of metallo-supramolecular diblock copolymers. To synthesize well-defined tpy-modified polystyrenes (PSs), an Fe(II) bis(tpy) complex bearing α-bromoester as a metallo-initiator was applied to atom transfer radical polymerization (ATRP) to avoid poisoning the Cu(I) catalyst. Subsequently, a series of tpy-functionalized PSs was obtained after the decomplexation of <tpy-Fe(II)-tpy> junction by tetrakis(triethylammonium) ethylenediaminetetraacetate (TEA-EDTA) under mild conditions. The metallo-supramolecular poly(3-hexylthiophene) (P3HT)-block-PS diblock copolymers were prepared by simply mixing the corresponding terminally tpy-modified homopolymers with Zn(II) ions, and further characterized by1H NMR and diffusion ordered spectroscopy (DOSY) experiments. The approach using metallo-initiators for ATRP offers an opportunity to construct tpy-functionalized polymers with controllable molecular weights and low polydispersities. Through the spontaneous heteroleptic complexation, a variety of metallo-supramolecular diblock copolymers with tunable block ratios can be easily constructed. ? 2020 by the authors. Licensee MDPI, Basel, Switzerland.
Subjects
Atom transfer radical polymerization; Block copolymers; Catalyst poisoning; Copper compounds; Free radical reactions; Metals; Polydispersity; Polystyrenes; Supramolecular chemistry; Tea; Zinc compounds; Zinc metallography; Complementary complexation; Decomplexations; Diffusion ordered spectroscopies; Efficient strategy; Functionalized; Functionalized polymers; Metallo-supramolecular; Poly-3-hexylthiophene; Iron compounds
Type
journal article