Molecular tailoring of thermoreversible copolymer gels: some new mechanistic insights

Badiger, M. V. ; Lele, A. K. ; Bhalerao, V. S. ; Varghese, S. ; Mashelkar, R. A. (1998) Molecular tailoring of thermoreversible copolymer gels: some new mechanistic insights Journal of Chemical Physics, 109 (3). pp. 1175-1184. ISSN 0021-9606

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We earlier reported the role of hydrophobic and hydrogen bonding interactions on the transition temperatures of thermoreversible copolymer gels. We show here that the chemical structure of the hydrophobe and its concentration determine the transition temperatures [lower critical solution temperature (LCST)] and the heat of transition of new hydrophobically modified poly(N-isopropyl acrylamide) [PNIPAm] copolymer gels. The gels, prepared by copolymerizing NIPAm monomer with hydrophobic comonomers containing increasing lengths of alkyl side groups and a terminal carboxyl acid group, showed lower LCST and lower heat of transition when compared to pure PNIPAm gel. The experimental results were also compared with theoretical calculations based on a lattice-fluid-hydrogen-bond [LFHB] model. We show experimentally and theoretically that a linear correlation exists between the transition temperature and length of the hydrophobic alkyl side group. Also, in apparent contradiction to previous work, we found a reduction in the heat of transition with increasing hydrophobicity. We propose that the presence of the terminal carboxyl acid group on the hydrophobic side chain of the comonomer prevents the association of water molecules around the hydrophobe, thereby causing a reduction in the heat of transition. The LFHB model supports this argument.

Item Type:Article
Source:Copyright of this article belongs to American Institute of Physics.
ID Code:22123
Deposited On:23 Nov 2010 08:19
Last Modified:17 May 2016 06:13

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