期刊
MACROMOLECULES
卷 48, 期 23, 页码 8526-8533出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.5b02042
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资金
- Ministry of Science and Technology of the Republic of China, Taiwan [MOST 104-2221-E-110-073]
Manipulation of crystalline textures of biocompatible block copolymers is critical for the applications in the medical field. Here, we present the control of multiple-crystalline morphologies with flat-on chain orientation in biocompatible poly(ethylene oxide)-block-poly(epsilon-caprolactone)-block-poly(L-lactide) (PEO-PCL-PLLA) triblock copolymer thin films using melt and solvent-induced crystallizations. Only single-crystalline morphologies of the first-crystallized blocks can be obtained in the melt-crystallized thin films due to the confinement effect. With solvent annealing by PCL-selective toluene, single-crystalline PLLA to double-crystalline PLLA/PCL and to triple-crystalline PLLA/PCL/PEO layered crystals in sequence are observed for the first time. With the control of solvent selectivity, different sequential crystallization involving first-crystallized PCL transferring to double-crystalline PCL/PLLA is obtained using PEO-selective n-hexanol for annealing. Surprisingly, the crystalline growth of the trilayered single crystal exhibits specific layer-by-layer epitaxial relationship. As a result, the multiple-crystalline textures of the PEO-PCL-PLLA thin films can be carried out by controlling solvent and polymer interaction.
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