Structure-Property Relationship on the Example of Gas Separation Characteristics of Poly(Arylene Ether Ketone)s and Poly(Diphenylene Phtalide).

Alexandre Alentiev,Mikhail Buzin,Victoria Ryzhikh,Sergey Salazkin,Vera Shaposhnikova,Sergey Chirkov,Nikolay Belov,Oleg Miloserdov,Roman Nikiforov

doi:10.3390/membranes11090677

Abstract

Three poly(arylene ether ketone)s (PAEKs) with propylidene (C1, C2) and phtalide (C3) fragments, and one phtalide-containing polyarylene (C4), were synthesized. Their chemical structures were confirmed via 1H NMR, 13C NMR and 19F NMR spectroscopy. The polymers have shown a high glass transition temperature (>155 °C), excellent film-forming properties, and a high free volume for this polymer type. The influence of various functional groups in the structure of PAEKs was evaluated. Expectedly, due to higher free volume the introduction of hexafluoropropylidene group to PAEK resulted in higher increase of gas permeability in comparison with propylidene group. The substitution of the fluorine-containing group on a rigid phtalide moiety (C3) significantly increases glass transition temperature of the polymer while gas permeation slightly decreases. Finally, the removal of two ether groups from PAEK structure (C4) leads to a rigid polymer chain that is characterized by highest free volume, gas permeability and diffusion coefficients among the PAEKs under investigation. Methods of modified atomic (MAC) and bond (BC) contributions were applied to estimate gas permeation and diffusion. Both techniques showed reasonable predicted parameters for three polymers while a significant underestimation of gas transport parameters was observed for C4. Gas solubility coefficients for PAEKs were forecasted by “Short polymer chain surface based pre-diction” (SPCSBP) method. Results for all three prediction methods were compared with the ex-perimental data obtained in this work. Predicted parameters were in good agreement with ex-perimental data for phtalide-containing polymers (C3 and C4) while for propylidene-containing poly(arylene ether ketone)s they were overestimated due to a possible influence of propylidene fragment on indices of oligomeric chains. MAC and BC methods demonstrated better prediction power than SPCSBP method.

Highlights

Over the past twenty years, the separation of gas mixtures has been one of the most rapidly developing and knowledge-intensive areas of membrane technology
All the polymers synthesized in the work have high glass transition temperatures (Tg) (Table 2)
It is obvious that the presence of trifluoromethyl groups in the structure of the polymer C2 should reduce the interchain interactions [68] in the polymer, compared to C1, and, subsequently, reduce the Tg. This effect is inferior to the influence of the chain stiffness, which causes a slight increase in the glass transition temperature for the polymer C2

Summary

Introduction

Over the past twenty years, the separation of gas mixtures has been one of the most rapidly developing and knowledge-intensive areas of membrane technology. In the majority of membrane gas separation processes, asymmetric or composite polymer membranes are used, the materials of the thin selective layer [5] of which, as a rule, are glassy amorphous polymers. Mass transfer in such membranes is carried out by the solution-diffusion mechanism. The stationary gas flow through the membrane is directly proportional to the pressure drop and inversely proportional to the thickness of the membrane In this case, the proportionality coefficient is the gas permeability coefficient (P) for the material of the selective membrane layer. P for the polymer–gas system is determined by the gas diffusion coefficient D and gas solubility coefficient S of the material [6], as follows:

Methods

Results

Conclusion