Hydrogen-Bonding Interactions in Hard Segments of Shape Memory Polyurethane : Toluene Diisocyanates and 1,6-Hexamethylene Diisocyanate. A Theoretical and Comparative Study

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

Detail(s)

Original languageEnglish
Pages (from-to)12241-12255
Journal / PublicationJournal of Physical Chemistry A
Volume118
Issue number51
Online published15 Dec 2014
Publication statusPublished - 26 Dec 2014
Externally publishedYes

Abstract

In this study, the hydrogen-bonding interactions of three widely used diisocyanate-based hard-segment (HS) models in polyurethane, 2,4-toluenediisocyanate-methanol (2,4-TDI-MeOH), 2,6-toluenediisocyanate-methanol (2,6-TDIMeOH), and 1,6-hexamethylenediisocyanate-methanol (HDI-MeOH), were investigated theoretically by density functional theory (DFT). The B3LYP/6-31G ∗ method was used to calculate the equilibrium structures, Mulliken charges, hydrogen-bonding energies, and infrared (IR) spectra, in good agreement with previous experimental data. The HS models with benzene ring have much longer hydrogen bonds (HB), due to steric hindrance of benzene ring, whereas the aliphatic model forms much shorter hydrogen bonds. Different positions of the methyl group on the benzene ring for 2,4-TDI-MeOH and 2,6-TDI-MeOH result in different types of hydrogen bonds with various strengths. The style of hydrogen bonding for HDI-MeOH is more flexible due to simple aliphatic chemical structure without the benzene ring. The charge transfer on atoms N, H, and O involved in hydrogen bonding occurs with the forming of a hydrogen bond. The hydrogen bonding of 2,4-TDI-MeOH is much stronger than the others, and 2,6-TDI-MeOH froms the weakest hydrogen bonds. This study can supply guidance for the selection of a hard segment in the design of polyurethane and in-depth understanding of the hydrogen-bonding mechanism in the hard segments of polyurethane.

Citation Format(s)

Hydrogen-Bonding Interactions in Hard Segments of Shape Memory Polyurethane : Toluene Diisocyanates and 1,6-Hexamethylene Diisocyanate. A Theoretical and Comparative Study. / Zhang, Cuili; Hu, Jinlian; Li, Xun; Wu, You; Han, Jianping.

In: Journal of Physical Chemistry A, Vol. 118, No. 51, 26.12.2014, p. 12241-12255.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review