The crystallization behavior of a butene-1/ethylene random copolymer with 9.88 mol % ethylene counits was investigated by means of differential scanning calorimetry, wide- and small-angle X-ray scattering, and polarized optical microscopy. Unlike in its homopolymer counterpart which crystallizes always into a metastable form II from the melt state, the random copolymer was found to crystallize either into form II or stable form I′ directly from its melt state after being cooled down. The occurrence of either crystalline form only depended on the temperature where the crystalline material was molten before cooling down. Even though the material was brought to temperatures higher than the equilibrium melting temperature, heterogeneities of segmental segregation character were preserved which promoted massive nucleation of form I′ crystallites, which makes it possible that the material is able to crystallize into pure form I′. Only if when the melt temperature was high enough where all heterogeneities of the above-mentioned character were erased can the material be crystallized into pure form II. The effect is found independent of the previous crystalline form, meaning that the helical conformation of chains in the heterogeneous melt does not affect the nucleation of stable form I′.

Stretching-induced structural changes in polybutene-1 with stable crystalline modification of form I at elevated temperature was investigated by means of the in-situ synchrotron wide-angle X-ray diffraction technique. It was found that oriented metastable form II crystallites with the polymer chain aligned along the stretching direction gradually appear during tensile deformation. Based on the fact that a solid state I to II phase transition cannot take place due to the restriction in chain conformations and lattice dimensions in both phases, the observed occurrence of transition from form I to form II must proceed via a two-step process. First, those form I crystallites with their polymer chain direction tilted with respect to the stretching direction undergo a stress-induced melting process because they experience larger shear stress than the rest. Second, the freed polymer chain segments which have lost their conformational memory in stable form I recrystallize into metastable form II crystallites with their chain direction preferentially aligned along the stretching direction. This result is considered to provide a direct evidence for the stress-induced melting−recrystallization mechanism during tensile deformation of semicrystalline polymers.