POLYAMIDES WITH A CHOICE OF STRUCTURE AND CRYSTAL SURFACE CHEMISTRY - STUDIES OF CHAIN-FOLDED LAMELLAE OF NYLONS 8 10 AND 10 12 AND COMPARISON WITH THE OTHER 2N 2(N+1) NYLONS 4 6 AND 6 8

摘要

Nylons 8 10 and 10 12 have been synthesized and. crystallized as chain-folded lamellae from 1,4-butanediol and the results compared with previous studies on Nylons 4 6 and 6 8. In 2N 2(N + 1) Nylons, the lengths of the two alkane segments are equal and two different hydrogen-bonded sheet schemes are possible: progressive or alternating shear. At room temperature, Nylons 8 10 and 10 12 adopt the progressive scheme and the adjacent re-entry folds in the crystals must be in the alkane chain segments. In contrast, Nylons 4 6 and 6 8 lamellae, crystallized from the same solvent, exhibit the alternating hydrogen bonding scheme and each adjacent re-entry fold must contain an amide group. The transition in the chemical nature of the lamellar surface, from the amide fold to the alkane fold, occurs in passing from Nylon 6 8 to 8 10. Thus, the progressive hydrogen-bonded sheet/alkane fold structure is energetically more favorable, provided the alkane-folding geometry is sufficiently relaxed; this comes with increasing alkane segment length. For each hydrogen-bonded sheet structure there are still two principal intersheet stacking modes in lamellar crystals: the progressively sheared alpha-phase or the alternatingly sheared beta-phase, both of which have been found in the 8 10 and 10 12 Nylons. The 2N 2(N + 1) Nylons have the choice of four possible structures. The melting points of solution grown crystals of Nylons 4 6, 6 8, 8 10, and 10 12 decrease with decreasing intrachain amide density. When lamellar crystals of these Nylons are heated, the two characteristic interchain diffraction signals move together and meet at their Brill temperature; for Nylon 10 12 it appears to be close to the melting point. [References: 31]