The crystallization of ultralong normal paraffins: the onset of chain folding.

The nature of chain folding in polymers and the determination of the chain length at which folding occurs have been central questions in polymer science. The study of the formation of lamellar polymer crystals through chain folding has received a new impetus as a result of the recent synthesis of normal alkanes of strictly uniform chain lengths up to C(390) H(782). Chain folding is found in all such paraffins starting with C(150)H(302). As with polyethylenes obtained by conventional polymerization, the fold length in the normal alkanes varies with crystallization temperature, but it is always an integral reciprocal of the full chain length. This behavior indicates that the methyl end groups are located at the lamellar surface and that the fold itself must be sharp and adjacently reentrant.