Flexible and rigid block copolymers from recyclable polyesters

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The paper addresses a study on the thermoplastic elastomers (TPE) that can be synthesized using monomers retrieved from the chemically recycled semi-aromatic polyesters, such as terephthalic acid from low value stream recyclable polyethylene terephthalate (rPET). In contrast to PET, because of their physical and mechanical properties, TPEs are often used as an engineering polymer in automotive and consumer goods. The understanding of the crystallization and phase behavior of these materials is crucial to fine-tune the molecular structure and properties. We explore the interplay between the crystallization and phase separation in these materials by performing experiments on model thermoplastic elastomers consisting of polybutylene terephthalate (PBT) and polytetrahydrofuran (PTHF). A common denominator in the synthesis of PBT is terephthalic acid that can be obtained from Dimethyl Terephthalate (DMT) or recycling used PET. We show that by varying the compositions and block length of different blocks, in PBT-PTHF block copolymers, morphological variations from spherulites to dendrites can be induced, which could be captured using optical microscopy. By performing rheological and small angle X-ray scattering studies, we correlate these morphological variations at microscopic length scales, to the chain architecture at nanometer length scales. Our observations reveal that at the higher rigid PBT content, the process of phase separation strongly influences the crystallization kinetics that promotes the lamellar structure of the semi-crystalline polymer, observed at room temperature. On the other hand, in the presence of higher soft block content, the crystal growth occurs with minimal influence of the microphase separation. In broader generality, no morphological differences in the TPEs synthesized using the terephthalic acid from rPET are found. However, when the monomer from rPET is used, enhancement in crystallization rate occurs in the TPEs having similar molar mass and molecular configuration. We attribute the enhanced crystallization rate to the catalyst residues present in the terephthalic acid obtained fom rPET.