Nylon 6 9 can crystallize with hydrogen bonding in two and in three interchain directions

摘要

Nylon 6 9 has been shown to have structures with interchain hydrogen bonds in both two and in three directions. Chain-folded lamellar crystals were studied using transmission electron microscopy and sedimented crystal mats and uniaxially oriented fibers studied by X-ray diffraction. The principal room-temperature structure shows the two characteristic (interchain) diffraction signals at spacings of 0.43 and 0.38 nm, typical of alpha-phase nylons; however, nylon 6 9 is unable to form the alpha-phase hydrogen-bonded sheets without serious distortion of the all-trans polymeric backbone. Our structure has c and c* noncoincident and two directions of hydrogen bonding. Optimum hydrogen bonding can only occur if consecutive pairs of amide units alternate between two crystallographic planes. The salient features of our model offer a possible universal solution for the crystalline state of all odd-even nylons. The nylon 6 9 room-temperature structure has a C-centered monoclinic unit cell (beta = 108 degrees) with the hydrogen bonds along the C-face diagonals; this structure bear's a similarity to that recently proposed for nylons 6 5 and X3. On heating nylon 6 9 lamellar crystals and fibers, the two characteristic diffraction signals converge and meet at 0.42 nm at the Brill temperature, T-B. T-B for nylon 6 9 lamellar crystals is slightly below the melting point (T-m), whereas T-B for nylon 6 9 fibers is congruent to 100 degrees C below T-m. Above T-B, nylon 6 9 has a hexagonal unit cell; the alkane segments exist in a mobile phase and equivalent hydrogen bonds populate the three principal (hexagonal) directions. A structure with perturbed hexagonal symmetry, which bears a resemblance to the reported gamma-phase for nylons? can be obtained by quenching from the crystalline growth phase (above T-B) to room temperature. We propose that this structure is a "quenched-in" perturbed form of the nylon 6 9 high-temperature hexagonal phase and has interchain hydrogen bonds in all three principal crystallographic directions. In this respect it differs importantly from the gamma-phase models. (C) 1998 John Wiley & Sons, Inc. [References: 33]