Abstract
The viscoelastic properties of polytetramethylene oxide—polytetramethylene terephthalate block polymers are strongly influenced by phase separation of the 4GT hard blocks into crystalline domains. Thermal analysis reveals a single Tg which increases with increasing 4GT content. This suggests that short sequences of hard segments form a compatible interlamellar amorphous phase with the polyether component. The Gordon-Taylor equation was found to model Tg behavior accurately, provided that the crystalline polyester component was not included in the definition of the hard segment. The melting point of the polytetramethylene terephthalate blocks depends on the average block length of crystallizable segment. Incorporating non-crystallizing polytetramethylene 1,4-cyclohexanedicarboxylate into the hard segment reduces the 4GT melting point and degree of crystallinity. The morphological features of the copolymers depend on sample composition and fabrication procedure. The basic structure is spherulitic. Three different types of spherulite were observed: positive and negative spherulites, as well as spherulites which have their optical axis 45° to their radial direction. The different spherulite types are relatively stable; annealing the samples at elevated temperatures does not alter their morphology. Annealing does increase the degree of crystallinity somewhat and produces crystallites in equilibrium at the annealing temperature. Infrared dichroism studies reveal that, at low deformations, the hard segment lamellae orient as a whole in the stretching direction. This is refleeted by the initial negative orientation of the hard segments. At this stage of elongation, the deformation of the crystallites is nearly reversible. At higher strain levels, the lamellae are disrupted and the hard segments orient positively with a high degree of orientational hysteresis. The soft segments, however, orient almost reversibly in the stress direction at all strain levels studied. It is concluded that the extensive stress softening is brought about by plastic deformation of the crystalline hard segments.
Microhardness under strain, 4. Reversible microhardness in polyblock thermoplastic elastomers with poly(butylene terephthalate) as hard segments