Catalyst switch strategy enabled a single polymer with five different crystalline phases

• Published in: Nature communications Vol. 14; no. 1; pp. 7559 - 11
• Main Authors: Zhang, Pengfei, Ladelta, Viko, Abou-hamad, Edy, Müller, Alejandro J., Hadjichristidis, Nikos
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 20.11.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 639/301/923/1028; 639/638/455/958; 639/638/455/959; Calorimetry; Catalysts; Chemical synthesis; Crystallites; Crystallization; Crystals; Differential scanning calorimetry; Ethylene oxide; Humanities and Social Sciences; Magnetic resonance spectroscopy; Material properties; Mechanical properties; Melting point; Melting points; multidisciplinary; NMR; NMR spectroscopy; Nuclear magnetic resonance; Phase separation; Physics; Poly(L-lactide); Polycaprolactone; Polyethylene oxide; Polyglycolic acid; Polylactic acid; Polymerization; Polymers; Ring opening polymerization; Science; Science (multidisciplinary); Self-assembly; X-ray diffraction
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-42955-3

Well-defined multicrystalline multiblock polymers are essential model polymers for advancing crystallization physics, phase separation, self-assembly, and improving the mechanical properties of materials. However, due to different chain properties and incompatible synthetic methodologies, multicrystalline multiblock polymers with more than two crystallites are rarely reported. Herein, by combining polyhomologation, ring-opening polymerization, and catalyst switch strategy, we synthesized a pentacrystalline pentablock quintopolymer, polyethylene- b -poly(ethylene oxide)- b -poly( ε -caprolactone)- b -poly(L-lactide)- b -polyglycolide (PE- b -PEO- b -PCL- b -PLLA- b -PGA). The fluoroalcohol-assisted catalyst switch enables the successful incorporation of a high melting point polyglycolide block into the complex multiblock structure. Solid-state nuclear magnetic resonance spectroscopy, X-ray diffraction, and differential scanning calorimetry revealed the existence of five different crystalline phases. Well-defined multicrystalline multiblock polymers are essential model polymers for advancing the physics of crystallization but due to the different chain properties and incompatible synthetic methodologies, multicrystalline multiblock polymers with more than two crystallites are rarely reported. Here the authors combine polyhomologation, ring-opening polymerization and a catalyst switch strategy to synthesize a pentacrystalline pentablock quintopolymer.