Variable-temperature Fourier transform infrared spectroscopic investigations of poly(3-hydroxyalkanoates) and perturbation-correlation moving-window two-dimensional correlation analysis. Part I: Study of non-annealed and annealed poly(3-hydroxybutyrate) homopolymer.
Generalized two-dimensional correlation spectroscopy (2DCOS) and perturbation-correlation moving-window two-dimensional (PCMW2D) correlation spectroscopy were applied to explore the melting behavior of non-annealed and annealed poly(3-hydroxybutyrate) (PHB) homopolymer as studied by variable-temperature Fourier transform infrared (FT-IR) spectroscopy. The absorption band of the C=O stretching vibration was employed to investigate the structural changes during the heating process (30-200 degrees C). Non-annealed PHB showed a recrystallization process in the temperature range 30-120 degrees C. In the asynchronous 2D correlation spectrum we clearly captured the existence of two components in the crystallinity-sensitive wing of the C=O stretching mode: a well-ordered crystalline state at lower wavenumbers (1718 cm(-1)) and a less ordered crystalline state at higher wavenumbers (1724 cm(-1)). These crystallinity-sensitive bands at 1718 and 1724 cm(-1), which are not readily detectable in the one-dimensional (1D) FT-IR spectra, share asynchronous cross-peaks with bands at around 1737 and 1747 cm(-1) assignable to the C=O stretching absorptions due to the amorphous components. In the case of the melting process of non-annealed PHB in the temperature range 120-200 degrees C, it is helpful to use the PCMW2D correlation analysis, which indicates the recrystallization between 40 and 110 degrees C by the shift of the C=O stretching band from 1726 cm(-1) to 1722 cm(-1) and the sharp change to the broad amorphous C=O stretching absorption at 1747 cm(-1) at the melting temperature of PHB around 190 degrees C. For an annealed sample of PHB only the melting behavior was observed in the PCMW2D correlation analysis by the sharp transition from the crystalline to the amorphous C=O stretching band.
Department of Physical Chemistry, University of Duisburg-Essen, Schuetzenbahn 70, 45117 Essen, Germany.
Miriam
M
Unger
Shigeaki
S
Morita
Harumi
H
Sato
Yukihiro
Y
Ozaki
Heinz W
HW
Siesler
D006358:Hot Temperature; D006885:Hydroxybutyrates / Q000737:chemistry* / Q000378:metabolism; D011091:Polyesters / Q000737:chemistry* / Q000378:metabolism; D017550:Spectroscopy, Fourier Transform Infrared / Q000295:instrumentation* / Q000379:methods*; D000094122:Polyhydroxybutyrates
D006885:Hydroxybutyrates; D011091:Polyesters; C003182:poly-beta-hydroxybutyrate; D000094122:Polyhydroxybutyrates