Dynamics of concentrated solutions of low molecular weight phenolics and poly(2-vinylpyridine): Role of intermolecular hydrogen bonding

Pornpen Atorngitjawat, Robert J. Klein, Amanda G. McDermott, Kevin A. Masser, Paul C. Painter, James Runt

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The molecular dynamics of solutions of poly(2-vinylpyridine) (P2VPy) and a series of low molecular weight phenols containing from one to six hydroxyl groups were investigated using broadband dielectric spectroscopy (DRS). Dynamic mechanical analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, small-angle X-ray scattering and wide-angle X-ray diffraction were employed in a complementary role. Segmental relaxation times for the α processes of all solutions follow expectations from Tgs derived from DSC experiments. For three of the model mixtures at 30 and 50 mol% [i.e., those containing bis (4-hydroxyphenyl) methane, 2,6 dihydroxynaphthalene, and 2,2-methylenebis[6-(2-hydroxy-5-methylbenzyl)-p-cresol] significantly broadened dielectric α relaxation time distributions were observed, indicating dynamic heterogeneity. On the other hand, 4-ethyphenol-P2VPy solutions display dynamic homogeneity. P2VPy with 10 mol% 2,3,3,4,4,5-hexahydroxybenzophenone behaved differently than all mixtures investigated in this study: it displayed a Tg (and Tα) significantly higher than that of the neat components, a small SAXS scattering peak, and an additional dielectric relaxation that we propose originates from Maxwell-Wagner-Sillars interfacial polarization. We propose that this behavior is a result of a phase separation of different types of hydrogen-bonded complexes, one rich in P2VPy and the other involving the type of 2,3,3,4,4,5-hexahydroxybenzophenone hydrogen-bonded structures found in the neat state. Intermolecular hydrogen bonding in all of the P2VPy-phenol mixtures suppresses, in some cases completely, the local P2VPy β relaxation by decreasing the mobility of the pyridine side groups.

Original languageEnglish (US)
Pages (from-to)2424-2435
Number of pages12
JournalPolymer
Volume50
Issue number11
DOIs
StatePublished - May 22 2009

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Hydrogen bonds
Dielectric relaxation
Molecular weight
Relaxation time
Phenols
Dielectric spectroscopy
Hydrogen
Dynamic mechanical analysis
X ray scattering
Phase separation
Pyridine
Fourier transform infrared spectroscopy
Molecular dynamics
Differential scanning calorimetry
Methane
Scattering
Polarization
X ray diffraction
Phenol
Hydroxyl Radical

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

Cite this

Atorngitjawat, Pornpen ; Klein, Robert J. ; McDermott, Amanda G. ; Masser, Kevin A. ; Painter, Paul C. ; Runt, James. / Dynamics of concentrated solutions of low molecular weight phenolics and poly(2-vinylpyridine) : Role of intermolecular hydrogen bonding. In: Polymer. 2009 ; Vol. 50, No. 11. pp. 2424-2435.
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abstract = "The molecular dynamics of solutions of poly(2-vinylpyridine) (P2VPy) and a series of low molecular weight phenols containing from one to six hydroxyl groups were investigated using broadband dielectric spectroscopy (DRS). Dynamic mechanical analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, small-angle X-ray scattering and wide-angle X-ray diffraction were employed in a complementary role. Segmental relaxation times for the α processes of all solutions follow expectations from Tgs derived from DSC experiments. For three of the model mixtures at 30 and 50 mol{\%} [i.e., those containing bis (4-hydroxyphenyl) methane, 2,6 dihydroxynaphthalene, and 2,2-methylenebis[6-(2-hydroxy-5-methylbenzyl)-p-cresol] significantly broadened dielectric α relaxation time distributions were observed, indicating dynamic heterogeneity. On the other hand, 4-ethyphenol-P2VPy solutions display dynamic homogeneity. P2VPy with 10 mol{\%} 2,3,3,4,4,5-hexahydroxybenzophenone behaved differently than all mixtures investigated in this study: it displayed a Tg (and Tα) significantly higher than that of the neat components, a small SAXS scattering peak, and an additional dielectric relaxation that we propose originates from Maxwell-Wagner-Sillars interfacial polarization. We propose that this behavior is a result of a phase separation of different types of hydrogen-bonded complexes, one rich in P2VPy and the other involving the type of 2,3,3,4,4,5-hexahydroxybenzophenone hydrogen-bonded structures found in the neat state. Intermolecular hydrogen bonding in all of the P2VPy-phenol mixtures suppresses, in some cases completely, the local P2VPy β relaxation by decreasing the mobility of the pyridine side groups.",
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Dynamics of concentrated solutions of low molecular weight phenolics and poly(2-vinylpyridine) : Role of intermolecular hydrogen bonding. / Atorngitjawat, Pornpen; Klein, Robert J.; McDermott, Amanda G.; Masser, Kevin A.; Painter, Paul C.; Runt, James.

In: Polymer, Vol. 50, No. 11, 22.05.2009, p. 2424-2435.

Research output: Contribution to journalArticle

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AU - Atorngitjawat, Pornpen

AU - Klein, Robert J.

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