Molecular Modeling and Gas Permeation Properties of a Polymer of Intrinsic Microporosity Composed of Ethanoanthracene and Tro?ger?s Base Units

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F14%3A43897446" target="_blank" >RIV/60461373:22340/14:43897446 - isvavai.cz</a>

Výsledek na webu

<a href="http://pubs.acs.org/doi/abs/10.1021/ma501469m" target="_blank" >http://pubs.acs.org/doi/abs/10.1021/ma501469m</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/ma501469m" target="_blank" >10.1021/ma501469m</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Molecular Modeling and Gas Permeation Properties of a Polymer of Intrinsic Microporosity Composed of Ethanoanthracene and Tro?ger?s Base Units

Popis výsledku v původním jazyce

Polymers of intrinsic microporosity (PIMs) are receiving increasing attention from the membrane community because of their high gas and vapor permeability. Recently a novel ethanoanthracene-based PIM synthesized by Troegers base formation (PIM-EA-TB) was reported to have exceptional transport properties, behaving as a polymer molecular sieve membrane. In this work, an extensive investigation of the structural, mechanical, and transport properties of this polymer, both by experimental analysis and by molecular simulation, offers deep insight into the behavior of this polymer and gives an explanation for its remarkable performance as a membrane material. Transport properties were determined by the time-lag method or MS gas analysis, and by gravimetric sorption measurements, yielding all basic transport parameters, permeability (P), diffusivity (D), and solubility (S). Upon alcohol treatment, PIM-EA-TB exhibited a much stronger permeability increase than archetypal PIM-1, with performance above the 2008 Robeson upper bound for several gas pairs. This is in part due to an extremely high gas solubility in PIM-EA-TB, higher than in PIM-1. The experimental data were supported by extensive modeling studies of the polymer structure and the spatial arrangement of its free volume. Modeling confirms that the high gas permeability must be attributed to the large fractional free volume of the polymer. The simulated free volume size distribution in PIM-EA-TB is in agreement with the average experimental free volume elements size determined by PALS and 129Xe NMR analysis. The modeled spatial arrangement of the free volume revealed a slightly lower interconnectivity of the FV elements in PIM-EA-TB compared to PIM-1. Along with its higher chain rigidity, determined by analysis of the torsion angles in the polymer model, this was identified as the main reason for its stronger size sieving behavior and relatively high permselectivity.

Název v anglickém jazyce

Molecular Modeling and Gas Permeation Properties of a Polymer of Intrinsic Microporosity Composed of Ethanoanthracene and Tro?ger?s Base Units

Popis výsledku anglicky

Polymers of intrinsic microporosity (PIMs) are receiving increasing attention from the membrane community because of their high gas and vapor permeability. Recently a novel ethanoanthracene-based PIM synthesized by Troegers base formation (PIM-EA-TB) was reported to have exceptional transport properties, behaving as a polymer molecular sieve membrane. In this work, an extensive investigation of the structural, mechanical, and transport properties of this polymer, both by experimental analysis and by molecular simulation, offers deep insight into the behavior of this polymer and gives an explanation for its remarkable performance as a membrane material. Transport properties were determined by the time-lag method or MS gas analysis, and by gravimetric sorption measurements, yielding all basic transport parameters, permeability (P), diffusivity (D), and solubility (S). Upon alcohol treatment, PIM-EA-TB exhibited a much stronger permeability increase than archetypal PIM-1, with performance above the 2008 Robeson upper bound for several gas pairs. This is in part due to an extremely high gas solubility in PIM-EA-TB, higher than in PIM-1. The experimental data were supported by extensive modeling studies of the polymer structure and the spatial arrangement of its free volume. Modeling confirms that the high gas permeability must be attributed to the large fractional free volume of the polymer. The simulated free volume size distribution in PIM-EA-TB is in agreement with the average experimental free volume elements size determined by PALS and 129Xe NMR analysis. The modeled spatial arrangement of the free volume revealed a slightly lower interconnectivity of the FV elements in PIM-EA-TB compared to PIM-1. Along with its higher chain rigidity, determined by analysis of the torsion angles in the polymer model, this was identified as the main reason for its stronger size sieving behavior and relatively high permselectivity.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10404 - Polymer science

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2014

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Macromolecules

ISSN

0024-9297

e-ISSN

—

Svazek periodika

47

Číslo periodika v rámci svazku

22

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

17

Strana od-do

7900-7916

Kód UT WoS článku

000345552700023

EID výsledku v databázi Scopus

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