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A Molecular Picture for the Thermo-Reversibility of Gels Formed by Isophthalic Acid-Ended Telechelic Polymers

Li, Boyu and Kim, Joey and Kornfield, Julia A. (2015) A Molecular Picture for the Thermo-Reversibility of Gels Formed by Isophthalic Acid-Ended Telechelic Polymers. In: Supramolecular Materials-Assembly and Dynamics. MRS Proceedings. No.1794. Materials Research Society , Pittsburgh, PA, pp. 9-14.

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We demonstrate that isophthalic acid-ended telechelic poly(1,5-cyclooctadiene)s (A-PCODs) form thermo-reversible gels in non-polar solvent with a unique molecular mechanism for their thermo-reversibility. Like other associative telechelic polymers, A-PCODs form “flower-like” micelles at low concentration and form gels through bridging at higher concentration which exhibit linear viscoelasticity. However, unlike the widely studied hydrophobically end-capped PEOs, A-PCODs show clear thermo-reversibility in viscosity and dynamic modulus around 30 °C due to the hydrogen-bonding end groups. In addition, they differ from other reported thermo-reversible gelators (eg. Pluronics, PNIPAm containing block copolymers, etc.): neither the end group nor the backbone in the present system has a critical solution temperature within the measured temperature range (0 °C to 60 °C), indicating that the present system has a unique mechanism for its thermo-reversibility. To obtain a molecular picture of the mechanism, rheology and small angle neutron scattering (SANS) studies were implemented. Topological changes above the transition temperature (30 °C) were observed in both oscillatory rheology and SANS. SANS reveals that the size of clusters, which are formed by interacting micelles, depends highly on temperature (T) but independent of polymer concentration. These results cannot be explained by current theories on associative telechelic polymers which assume constant and large aggregation number of end groups at all temperatures and concentrations. We hypothesize that the temperature-sensitive sol-gel transition is due to a decrease in aggregation number for T above the critical temperature in our system, and this temperature-dependence of aggregation number is further determined by the chemical structure and hydrogen-bonding property of isophthalic acid ends.

Item Type:Book Section
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URLURL TypeDescription
Kim, Joey0000-0002-3359-4875
Kornfield, Julia A.0000-0001-6746-8634
Additional Information:© 2015 Materials Research Society.
Series Name:MRS Proceedings
Issue or Number:1794
Record Number:CaltechAUTHORS:20151020-080830474
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61301
Deposited By: Tony Diaz
Deposited On:20 Oct 2015 19:03
Last Modified:04 Feb 2021 01:02

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