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Effect of Spacer Stiffness on the Properties of Hyperbranched Polymers

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Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India
*E-mail [email protected] (S.R.).
Cite this: Macromolecules 2017, 50, 21, 8536–8543
Publication Date (Web):October 18, 2017
https://doi.org/10.1021/acs.macromol.7b01401
Copyright © 2017 American Chemical Society

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    Abstract

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    A series of peripherally clickable hyperbranched polyesters were prepared wherein the stiffness of the spacer segment between branching junctions was systematically varied. Three different four-carbon spacers were studied: one was fully saturated (HBPC4-S), another bears a double bond (HBPC4-DBc), and a third carries a triple bond (HBPC4-TB); in the case of the sample with a double bond c indicates cis-rich isomer. The glass transition temperatures of the HB polyesters were seen to increase with the stiffness of the spacer segment from 27 to 60 °C. Furthermore, when the peripheral propargyl groups of the HB polyesters were quantitatively clicked with a crystallizable docosyl (C-22) azide, all the derivatives exhibited sharp melting/crystallization peaks in the DSC traces, indicative of segregation and colocalization of the peripheral segments. WAXS data confirmed the crystallization of the alkyl segments in a paraffinic lattice, while SAXS profiles revealed the formation of a lamellar morphology; the interlamellar spacing reflected the compactness of the HB polymeric core and also the adaptability of the core toward the self-segregation. Whereas the effect of such structural variations in linear polyesters has been examined extensively, this represents the first study that reveals the implications chain stiffness and geometry on the properties of hyperbranched polymers.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.7b01401.

    • Detailed synthetic methods, WAXS profiles, GPC chromatograms, and additional NMR spectral data (PDF)

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    Cited By

    This article is cited by 3 publications.

    1. Arun Kumar Gayen, Suresh Kumar Perala, Dominik Schauenburg, Tanja Weil, S. Ramakrishnan. Amphiphilic Polymer Hydrogel‐supported Catalysts: Tuning the Accessibility to the Catalytic Site by Molecular Jacketing. Chemistry – An Asian Journal 2023, 18 (12) https://doi.org/10.1002/asia.202300143
    2. Suresh Kumar Perala, S. Ramakrishnan. Orthogonally clickable hyperbranched polymers: effect of reactant size and polarity on core-functionalization of peripherally jacketed HBPs. Polymer Chemistry 2019, 10 (13) , 1626-1635. https://doi.org/10.1039/C8PY01499J
    3. In-Yup Jeon, Hyuk-Jun Noh, Jong-Beom Baek. Hyperbranched Macromolecules: From Synthesis to Applications. Molecules 2018, 23 (3) , 657. https://doi.org/10.3390/molecules23030657

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