Molecularly Imprinted Polymer and Computational Study of (E)-4-(2- cyano-3-(dimethylamino)acryloyl)benzoic Acid from Poly(ethylene terephthalate) Plastic Waste

Abstract

Background: Molecularly imprinted polymers (MIPs) are utilized in the separation of a pure compound from complex matrices. A stable template-monomer complex generates MIPs with the highest affinity and selectivity for the template. In this investigation, degradation of Poly(ethylene terephthalate) PET afforded the (E)-4-(2-cyano-3-(dimethylamino) acryloyl) benzoic acid (4) (TAM) which used TAM as template which interacts with Methacrylic Acid (MAA) monomer, in the presence of CH3CN as progen. The TAM-MMA complex interactions are dependent on stable hydrogen bonding interaction between the carboxylic acid group of TAM and the hydroxyl group of MMA with minimal interference of porogen CH3CN. The DFT/B3LYP/6-31+G model chemistry was used to optimize their structures and frequency calculations. The binding energies between TAM with different monomers showed the most stable molar ratio of 1:4 which was confirmed through experimental analysis. Methods: The present work describes the synthesis of (E)-4-(2-cyano-3-(dimethylamino) acryloyl) benzoic acid (4) (TAM) from PET waste and formation of molecularly imprinted polymer from TAM with the methacrylic acid monomer. The optimization of molecular imprinted was stimulated via DFT/B3LYP/6-31G (d). The imprinted polymer film was characterized via thermal analysis, pore size, FT-IR and scanning electron microscopy. Results: The most stable molecularly imprinted polymers (MIPs) showed binding energy of TAM(MMA4)=-2063.456 KJ/mol with a small value of mesopores (10-100 Å). Also, the sorption capability of TAM-MIPs showed 6.57 mg/g using STP-MIP-9VC. Moreover, the average pore size ranged between 0.2-1 nm with the BET surface about 300 m2/g. Conclusion: The proposed TAM exhibited a high degree of selectivity for MMA in comparison with other different monomers through hydrogen bond interaction, which was thermally stable, good reproducibility and excellent regeneration capacity and elucidated in the computational study and analytical analysis.