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

Pengfei Zhang; Viko Ladelta; Edy Abou-Hamad; Alejandro J Müller; Nikos Hadjichristidis

doi:10.1038/s41467-023-42955-3

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

Nat Commun. 2023 Nov 20;14(1):7559. doi: 10.1038/s41467-023-42955-3.

Authors

Pengfei Zhang¹, Viko Ladelta¹, Edy Abou-Hamad², Alejandro J Müller³, Nikos Hadjichristidis⁴

Affiliations

¹ Polymer Synthesis Laboratory, KAUST Catalysis Center, Chemistry Program, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955, Saudi Arabia.
² Imaging and Characterization Core Lab, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955, Saudi Arabia.
³ Department of Polymers and Advanced Materials, Physics, Chemistry and Technology, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel de Lardizabal 3, 20018, Donostia-San Sebastián, Spain.
⁴ Polymer Synthesis Laboratory, KAUST Catalysis Center, Chemistry Program, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955, Saudi Arabia. nikolaos.hadjichristidis@kaust.edu.sa.

Abstract

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.