Hyper Cross-Linked Polymers as Additives for Preventing Aging of PIM-1 Membranes.

Federico Begni,Geo Paul,Chiara Bisio,Elsa Lasseuguette,Maria-Chiara Ferrari,Giorgio Gatti,Leonardo Marchese

doi:10.3390/membranes11070463

Federico Begni, Geo Paul + Show 5 more

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https://doi.org/10.3390/membranes11070463

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Abstract

Mixed-matrix membranes (MMMs) are membranes that are composed of polymers embedded with inorganic particles. By combining the polymers with the inorganic fillers, improvements can be made to the permeability compared to the pure polymer membranes due to new pathways for gas transport. However, the fillers, such as hyper cross-linked polymers (HCP), can also help to reduce the physical aging of the MMMs composed of a glassy polymer matrix. Here we report the synthesis of two novel HCP fillers, based on the Friedel–Crafts reaction between a tetraphenyl methane monomer and a bromomethyl benzene monomer. According to the temperature and the solvent used during the reaction (dichloromethane (DCM) or dichloroethane (DCE)), two different particle sizes have been obtained, 498 nm with DCM and 120 nm with DCE. The change in the reaction process also induces a change in the surface area and pore volumes. Several MMMs have been developed with PIM-1 as matrix and HCPs as fillers at 3% and 10wt % loading. Their permeation performances have been studied over the course of two years in order to explore physical aging effects over time. Without filler, PIM-1 exhibits the classical aging behavior of polymers of intrinsic microporosity, namely, a progressive decline in gas permeation, up to 90% for CO2 permeability. On the contrary, with HCPs, the physical aging at longer terms in PIM-1 is moderated with a decrease of 60% for CO2 permeability. 13C spin-lattice relaxation times (T1) indicates that this slowdown is related to the interactions between HCPs and PIM-1.

Highlights

Membrane-based materials have played an important role in the field of gas separation [1]
The presence of aluminum and bromine is to be attributed to unreacted catalyst species, which is present in higher quantities in ABT01
Dichloroethane and a higher temperature resulted in higher specific surface area and pore volumes

Summary

Introduction

Membrane-based materials have played an important role in the field of gas separation [1]. A promising area of development for gas separation is the use of hybrid membranes or mixed-matrix membranes (MMMs). MMMs are composite membranes made by combining a filler (dispersed phase) and a polymer matrix (the continuous phase). By using two materials with different transport properties, these membranes have the potential to synergistically combine the easy processability of polymers and the superior gas-separation performance of filler materials, and provide separation properties surpassing the Robeson upper bound [8]. The addition of porous fillers in the continuous phase plays an important role in the transport properties of MMMs, providing new pathways for gas transport, increasing gas permeability [16,17,18,19,20,21]. The incorporation of fillers might be a solution to tackle the physical aging of glassy polymers [22,23,24,25,26,27]

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