Hydrogen Bonding Aggregation in Acrylamide: Theory and Experiment

Elena Patyukova, Taylor Rottreau, Robert Evans, Paul D. Topham, Martin J. Greenall

Research output: Contribution to journalArticlepeer-review


Hydrogen bonding plays a role in the microphase separation behavior of many block copolymers, such as those used in lithography, where the stronger interactions due to hydrogen bonding can lead to a smaller period for the self-assembled structures, allowing the production of higher resolution templates. However, current statistical thermodynamic models used in descriptions of microphase separation, such as the Flory–Huggins approach, do not take into account some important properties of hydrogen bonding, such as site specificity and cooperativity. In this combined theoretical and experimental study, a step is taken toward the development of a more complete theory of hydrogen bonding in polymers, using polyacrylamide as a model system. We begin by developing a set of association models to describe hydrogen bonding in amides. Both models with one association constant and two association constants are considered. This theory is used to fit IR spectroscopy data from acrylamide solutions in chloroform, thereby determining the model parameters. We find that models with two constants give better predictions of bond energy in the acrylamide dimer and more realistic asymptotic behavior of the association constants in the limit of high temperatures. At the end of the paper, we briefly discuss the question of the determination of the Flory–Huggins parameter for a diblock copolymer with one self-associating hydrogen bonding block and one non-hydrogen bonding block by means of fitting the scattering function in a disordered state.
Original languageEnglish
Pages (from-to)7032-7043
Issue number18
Early online date4 Sept 2018
Publication statusPublished - 25 Sept 2018

Bibliographical note

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.macromol.8b01118. This article was published online 4 September 2018. The embargo expires 4 March 2019.

Funding: This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 704459.


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