Polymethylene-Based Eight-Shaped Cyclic Block Copolymers

Embargo End Date
2020-12-31

Type
Article

Authors
Jiang, Yu
Hadjichristidis, Nikos

KAUST Department
Chemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Polymer Synthesis Laboratory

Online Publication Date
2019-12-31

Print Publication Date
2020-01-14

Date
2019-12-31

Abstract
A new strategy was developed for the synthesis of well-defined eight-shaped polymethylene (PM, equivalent to polyethylene)-based cyclic block copolymers, [c-(PM-b-PCL)]2, according to the following four steps: (a) synthesis of a B-thexyl-boracyclic initiator by cyclic hydroboration of 1,4-pentadiene-3-yl 2,2,5-trimethyl-1,3-dioxane-5-carboxylate with thexylborane; (b) polyhomologation of dimethylsulfoxonium methylide using this boracyclic initiator to afford α,ω-dihydroxyl linear PM (PM-OH)2; (c) synthesis of 4-miktoarm star block copolymers, (PM-alkyne)2-(PCL-N3)2, by esterification, deprotection, and ring-opening polymerization (ROP); and (d) intramolecular cyclization of (PM-alkyne)2-(PCL-N3)2, under high-dilution condition by copper-catalyzed “click” chemistry. All intermediates and final products were characterized by high-temperature gel permeation chromatography, proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and differential scanning calorimetry. Initial studies on the thermal and self-assembly behavior of the cyclic block copolymers and their corresponding precursors revealed a significant influence of the cyclic structure on the properties.

Citation
Jiang, Y., & Hadjichristidis, N. (2019). Polymethylene-Based Eight-Shaped Cyclic Block Copolymers. Macromolecules. doi:10.1021/acs.macromol.9b02571

Acknowledgements
Research reported in this publication was supported by King Abdullah University of Science and Technology (KAUST).

Publisher
American Chemical Society (ACS)

Journal
Macromolecules

DOI
10.1021/acs.macromol.9b02571

Additional Links
https://pubs.acs.org/doi/10.1021/acs.macromol.9b02571

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