A Computational Procedure for Atomistic Modelling of Polyphosphazenes towards Better Capturing Molecular-Level Structuring and Thermo-Mechanical Properties

Abstract

Poly(phosphazenes)(PZ) are versatile polymers due to their tunable properties that can be tailored for specific applications. Despite extensive experimental research, not all properties are tested, and the list of PZs studied via molecular simulations is limited. Further, a general procedure to generate and test PZ systems is lacking. We present an in situ polymerization procedure developed to make, test, and tune the thermo-mechanical properties of four PZs—poly(dichlorophosphazene)(PZ-DC), poly[bis(2,2,2-trifluoroethoxy)]phosphazene (PZ-TFE), poly(2,2,2-trifluoroethoxy-5,6-diazidohexanoxy) phosphazene (PZ-Azido), and poly(2,2,2-trifluoroethoxy-5,6-dinitratohexanoxy)phosphazene (PZ-Nitrato) via molecular dynamics simulations. The predicted thermo-mechanical properties (i.e., density and glass transition temperature) agreed with experimental values when a direct comparison of PZ systems was possible. This demonstrates the reproducibility and reliability of our procedure which will help understand the behaviour of PZs at the molecular scale.

Cyclo- and Polyphosphazenes for Biomedical Applications

“…All these aspects are crucial when these polymers are used to control drug release [ 80 ], in drug delivery applications [ 81 , 82 ], or as a microencapsulation material, as well as an immunoadjuvant [ 15 ]. In very recent work, Wang et al rationalized the effect of the side groups on the glass transition polymers starting from a system with 150 repeat units [ 83 ], but a great advance in the MD simulations has been made by Chen et al [ 84 ]. In this study, the DREIDING force field with the Lennard–Jones potential was used, and they obtained an in situ dynamic polymerization procedure to make, test, and tune the thermos-mechanical properties of polyphosphazenes via MD simulations, which was obtained.…”

Rational Design of Solid Polymer Electrolyte Based on Ionic Liquid Monomer for Supercapacitor Applications via Molecular Dynamics Study

“…Thanks to the increase in computational power, computer tools such as density functional theory (DFT) calculations and molecular dynamics (MD) simulations are useful means to fully capture the atomistic and molecular-level behaviour of materials, including pure polymers [ 20 , 21 , 22 ] and polymer mixtures [ 23 ], polymer composites [ 24 ], solid-state electrolytes [ 25 , 26 ] and supercapacitors [ 9 ]. Despite numerous experimental works on the investigation of SPEs, the number of computational studies focusing on the elucidation of the molecular-level behaviour of the IL-polymer matrix as SPE used in supercapacitor models is limited.…”