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Open AccessArticle

Controlled ATRP Synthesis of Novel Linear-Dendritic Block Copolymers and Their Directed Self-Assembly in Breath Figure Arrays

by Xin Liu 1, Tina Monzavi 1,2 and Ivan Gitsov 1,3,*
1
Department of Chemistry, State University of New York–College of Environmental Science and Forestry, Syracuse, NY 13210, USA
2
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA
3
The Michael M. Szwarc Polymer Research Institute, Syracuse, NY 13210, USA
*
Author to whom correspondence should be addressed.
Polymers 2019, 11(3), 539; https://doi.org/10.3390/polym11030539
Received: 5 March 2019 / Revised: 18 March 2019 / Accepted: 19 March 2019 / Published: 21 March 2019
Herein, we report the formation and characterization of novel amphiphilic linear-dendritic block copolymers (LDBCs) composed of hydrophilic dendritic poly(ether-ester), PEE, blocks and hydrophobic linear poly(styrene), PSt. The LDBCs are synthesized via controlled atom transfer radical polymerization (ATRP) initiated by a PEE macroinitiator. The copolymers formed have narrow molecular mass distributions and are designated as LGn-PSt Mn, in which LG represents the PEE fragment, n denotes the generation of the dendron (n = 1–3), and Mn refers to the average molecular mass of the LDBC (Mn = 3.5–68 kDa). The obtained LDBCs are utilized to fabricate honeycomb films by a static “breath figure” (BF) technique. The copolymer composition strongly affects the film morphology. LDBCs bearing acetonide dendron end groups produce honeycomb films when the PEE fraction is lower than 20%. Pore uniformity increases as the PEE content decreases. For LDBCs with hydroxyl end groups, only the first generation LDBCs yield BF films, but with a significantly smaller pore size (0.23 μm vs. 1–2 μm, respectively). Although higher generation LDBCs with free hydroxyl end groups fail to generate honeycomb films by themselves, the use of a cosolvent or addition of homo PSt leads to BF films with a controllable pore size (3.7–0.42 μm), depending on the LDBC content. Palladium complexes within the two triazole groups in each of the dendron’s branching moieties can also fine-tune the morphology of the BF films. View Full-Text
Keywords: linear-dendritic copolymer; amphiphilic; self-assembly; ATRP; breath figure linear-dendritic copolymer; amphiphilic; self-assembly; ATRP; breath figure
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Liu, X.; Monzavi, T.; Gitsov, I. Controlled ATRP Synthesis of Novel Linear-Dendritic Block Copolymers and Their Directed Self-Assembly in Breath Figure Arrays. Polymers 2019, 11, 539.

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