Molecular miscible blend of poly(2-cyano-1,4-phenyleneterephthalamide) and polyvinylpyrrolidone characterized by two-dimensional correlation FTIR and solid state 13C NMR spectroscopy

Abstract

Miscibility of blends of poly(2-cyano-1,4-phenyleneterephthalamide/polyvinylpyrrolidone) (CN-PPTA/PVP) was investigated by dilute solution viscometry, two-dimensional (2D) correlation Fourier transformed infrared (FTIR) spectroscopy and solid state 13C NMR spectroscopy. It was shown that a large proportion of the PVP, the water-soluble component, could not be removed from CN-PPTA by extraction with water, and even with boiling water for blend films, suggesting that the flexible aliphatic PVP chain forms a blend with the rigid aromatic CN-PPTA chain through strong intermolecular interaction making it too difficult to dissolve even in boiling water. Viscometry on a polymer mixture of dilute solution showed that [ η] exp exhibited larger value than [ η] theo in all mixtures used in this experiment, suggesting occurrence of a strong attractive interaction between the two polymers. 2D correlation FTIR spectroscopy revealed that the carbonyl absorption band of PVP at 1675 cm −1 shifted to a new low frequency absorption band at 1640 cm −1 with a change of 35 cm −1, suggesting strong hydrogen bonding with NH (amide II) proton of CN-PPTA. Another new absorption band at 1685 cm −1 was due to the carbonyl absorption band of CN-PPTA shifting to a higher frequency than that at 1662 cm −1, indicating that some of the carbonyl groups in the CN-PPTA components of the blends were in a free state or in a non-hydrogen bonded state as a consequence of the participation of NH proton of CN-PPTA in hydrogen bonding, resulting in the absorption bands of NH bend deformation of CN-PPTA at 1542 and 1313 cm −1 being shifted to higher wavenumber of 1556 and 1324 cm −1, respectively. Solid state 13C NMR spectroscopy revealed a chemical shift for C O of the PVP component in the blend fiber changing down-field (shift to left) at 177.346 ppm with a difference of 1.812 ppm; this was due to a lower electron density around the carbon atom of C O of lactam via hydrogen bonding with NH proton of amide in the CN-PPTA component, suggesting that a homogeneous blend of the CN-PPTA and PVP was produced on a molecular scale via hydrogen bonding.