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In poly(ε-caprolactone)-block-polyethylene (PCL-b-PE) diblock copolymers, the crystallizable temperature of PE blocks is sufficiently higher than that of PCL blocks, and accordingly, PE blocks crystallize first on quenching to form a crystallized lamellar morphology (PE lamellar morphology), followed by the crystallization of PCL blocks. We have investigated the crystallization behavior and crystal orientation of PCL blocks spatially confined in the PE lamellar morphology with different crystallinities of PE blocks χPE and layer thicknesses of PCL blocks dPCL as a function of crystallization temperature Tc,PCL, where χPE and dPCL are related to the rigidity and confinement size of the PE lamellar morphology, respectively. We found from differential scanning calorimetry results that the crystallization behavior of PCL blocks in PCL-b-PE with higher χPE and smaller dPCL was significantly different from that in other PCL-b-PE copolymers. We also found using two-dimensional wide-angle X-ray diffraction that the orientation of PCL crystals changed moderately by changing Tc,PCL in PCL-b-PE with higher χPE and smaller dPCL, whereas it did not change substantially in PCL-b-PE with lower χPE or larger dPCL. These results indicate that the rigidity and confinement size of the crystallized lamellar morphology, both of which can be controlled through the crystallization of the first blocks, are key factors for the crystallization of the second blocks in crystalline–crystalline diblocks with different crystallizable temperatures.

polymer journal

Crystallization of poly(ɛ-caprolactone) blocks confined in crystallized lamellar morphology of poly(ɛ-caprolactone)-block-polyethylene copolymers: effects of polyethylene crystallinity and confinement size