To address the weak binding force and poor dispersion stability of carbon (C) nanoparticles in current non-covalent modification methods, we employed organic amine-grafted styrene maleic anhydride copolymers (SMA-N) to modify C nanoparticles (C@SMA-N) through π–π conjugation and positive charge interactions. The obtained C@SMA-N has excellent dispersion in N, N-dimethylacetamide (DMAc), which is attributed to the enhanced steric hindrance and electrostatic repulsion from the grafted organic amine chains. To study the impact of surface modification on the electromagnetic interference shielding effectiveness (EMI SE), C@SMA-N was used as a conductive filler in polyvinyl chloride (PVC) composite films, which exhibits a higher EMI SE performance than pristine C nanoparticles. Particularly, the obtained C@SMA-N using polyether amine (PEA) (C@SMA-PEA) exhibits a better EMI SE performance. By optimizing the SMA-PEA grafting parameters, the PVC/C@SMA-PEA composite films transition from insulators to conductors at a C@SMA-PEA content of 0.3 wt%. To achieve a higher EMI SE performance, the filler content, mixed filler composition, and film thickness were optimized. The results indicate that with a total filler content of 20 wt% and a mixed filler comprising fibrous form carbon nanotubes (CNT) and particles form carbon black (CB) in a 10:1 mass ratio (CB@SMA-PEA to CNT@SMA-PEA), the composite film has a thickness of 0.08 mm and an EMI SE value of 20.2 dB. Increasing the thickness to 0.2 mm enhances the EMI SE value to 31.5 dB. These findings indicate that thinner films have a higher EMI SE performance and promising application prospects in the field of electromagnetic shielding.
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