Reflective thermal insulation layers can offer an energy-efficient strategy for preventing temperature rises by reflecting sunlight on surfaces. Our previous study presented a novel solvent-based method to prepare porous polypropylene (PP) with high solar reflectivity. However, the stiffness and strength of the neat porous PP were insufficient for thermal insulation applications, as mechanical loads from installation and environmental factors limit the applicability of such products. This paper addresses this gap by applying our solvent-based surface modification technology to glass fiber (GF)-reinforced PP composite sheets, creating a previously unexplored system. While the enhanced modulus and strength aligned with expectations, the micro- and nano-structured porous outer layers situated below the skin layer of the sheets, the refractive index mismatch between the PP matrix and the GF, and the size of the GF delivered a notable advancement in reflective thermal insulation performance. The combined effect of 30 wt% GF, nucleating agents, and surface modification resulted in a highly porous surface layer featuring spherulite sizes of 0.5–2.0 μm. With these combined effects, we achieved a modulus value of ~4 GPa, a tensile strength of 60 MPa, and an average solar reflectance of up to 94%. Thermal insulation performance measurements demonstrated that the registered inner temperature was lower by 24.1 °C compared to neat PP sheets. These combined effects demonstrate the potential of our solvent-based surface modification technology to develop cost-effective, porous PP composite sheets for efficient reflective thermal insulation.
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