Infrared spectroscopy studies of CH⋯O hydrogen bondings and thermal behavior of biodegradable poly(hydroxyalkanoate)

Harumi Sato, Rumi Murakami, Adchara Padermshoke, Fuminobu Hirose, Kenichi Senda, Isao Noda, Yukihiro Ozaki

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202 Citations (Scopus)

Abstract

Infrared (IR) spectra of new types of bacterial copolyester, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), P(HB-co-HHx) (HHx = 2.5, 3.4, and 12 mol %), and poly(3-hydroxybutyrate) (PHB) were measured over a temperature range of 20°C to higher temperatures (PHB, 185°C; HHx = 2.5 mol %, 160°C; HHx = 3.4 mol %, 160°C; HHx = 12 mol %, 140°C) to explore their structure and thermal behavior. The temperature-dependent IR spectral variations were analyzed for the CH stretching, C=O stretching, CH 3 deformation, and C-O-C stretching vibration regions, and bands characteristic of crystalline and amorphous parts were identified in each region. It has been found from the anomalous frequencies of the CH 3 asymmetric stretching bands of the four polymers and the X-ray crystallographic structure of PHB that there is an inter- or intramolecular interaction (C-H⋯O hydrogen bond) between the C=O group in one helical structure and the CH 3 group in the other helical structure in PHB and P(HB-co-HHx). The bonding energy of the C-H⋯O hydrogen bond seems to be smaller than 4 kJ/mol, but considering the heat of fusion (12.5 kJ/mol) of PHB, it is likely that a chain of C-H⋯O hydrogen bond pairs link two parallel helical structures in the crystalline parts. The temperature-dependent IR spectral variations have shown that the crystallinity of P(HB-co-HHx) (HHx = 12 mol %) decreases gradually from a fairly low temperature (about 60°C), while the crystallinity of PHB and P(HB-co-HHx) (HHx = 2.5 and 3.4 mol %) remains almost unchanged until just below their melting temperatures. It has also been revealed from the present study that the weakening of the C-H⋯O interaction starts from just above room temperature and proceeds gradually with increase in temperature, but the collapse of helical structure occurs at a much higher temperature for all the polymers investigated.

Original languageEnglish
Pages (from-to)7203-7213
Number of pages11
JournalMacromolecules
Volume37
Issue number19
DOIs
Publication statusPublished - Sep 21 2004
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

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