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Water Sorption by Polyheteroarylenes.

Anatoly E Chalykh1, Tatiana F Petrova1, Igor I Ponomarev2

  • 1Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences (IPCE RAS), 31, Bld.4 Leninsky Prospect, 119071 Moscow, Russia.

Polymers
|June 10, 2022
PubMed
Summary

Rigid-chain glassy polymers, specifically polynaphthoyleneimidobenzimidazole (PNIB) and copolymers, exhibit strongly bounded water sorption. Their diffusion characteristics are influenced by molecular structure and thermal history, aiding in predicting sorbent properties.

Keywords:
diffusiondiffusion coefficientshydrate numbers of functional groupspolyheteroarylenespolynaphthoyleneimidobenzimidazolesorption of water vapor

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Area of Science:

  • Polymer Science
  • Materials Science
  • Physical Chemistry

Background:

  • Rigid-chain glassy polymers, polyheteroarylenes (PHAs), are advanced materials with potential applications as sorbents.
  • Understanding their interaction with water is crucial for optimizing their performance in various environments.
  • Previous studies have explored PHA properties, but detailed sorption-diffusion characteristics require further investigation.

Purpose of the Study:

  • To investigate the sorption-diffusion behavior of water vapor in rigid-chain glassy polymers, specifically polynaphthoyleneimidobenzimidazole (PNIB) and its copolymers.
  • To determine the influence of relative humidity, temperature, and polymer structure on water sorption and diffusion.
  • To characterize the states of water within the polymer matrix and their dependence on thermal prehistory.

Main Methods:

  • Experimental determination of water vapor sorption isotherms for PNIB and its copolymers across a range of relative humidity.
  • Calculation of water diffusion coefficients and analysis of their concentration and temperature dependencies.
  • Application of the Arrhenius equation to describe the temperature dependence of diffusion and determination of activation energy.

Main Results:

  • Water molecules sorbed by PNIB and its copolymers are strongly bounded, indicating significant interactions.
  • Water diffusion coefficients were found to be in the range of 10^-9 to 10^-8 cm^2/s for all studied PHAs.
  • Diffusion coefficients increase with temperature, consistent with the Arrhenius equation, with an average activation energy of 24.3–25.9 kJ/mol.

Conclusions:

  • The sorption and diffusion of water in rigid-chain PHAs are significantly influenced by macromolecular structure and thermal prehistory.
  • Water exists in both mobile and cluster states within the polymer matrix, with their proportions depending on polymer characteristics.
  • The determined sorption-diffusion parameters enable predictions for the performance of heterocyclic macromolecular sorbents with complex architectures.