In this paper, the poly(ε-caprolactone)/glycerol tristearate (PCL/C18) composites were prepared through multistage biaxial-stretching extrusion, and the hydrophobic C18 was transformed significantly from small spheres into sheet-like structures. The hydrophobicity of the material was enhanced, and the diffusion path for the penetration of the small molecules was significantly increased, resulting in an improvement in the oxygen and water vapor barrier performance. Compared with conventional PCL/C18 blends with the same C18 content (10%), the oxygen and water vapor barrier performance of the modified composites further increased by 63.7% and 39.6%, respectively. Furthermore, when the relative humidity (RH) increased from 50% to 90%, the water vapor permeability (WVP) of sample C18-6 increased slightly from 6.94 × 10−14 g·cm·cm−2·s−1·Pa−1 to 7.66 × 10−14 g·cm·cm−2·s−1·Pa−1, exhibiting excellent stability to high humidity. Meanwhile, our materials have good biodegradability and mechanical properties, which can be well applied in the food and medicine packaging fields.
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