Membranes
are particularly attractive for lowering the energy intensity
of separations as they eliminate phase changes. While many tantalizing
polymers are known, limitations in selectivity and stability slightly
preclude further development. Mixed-matrix membranes may address these
shortcomings. Key to their realization is the intimate mixing between
the polymer and the additive to eliminate nonselective transport,
improve selectivity, and resist physical aging. Polymers of intrinsic
microporosity (PIMs) have inherently promising gas transport properties.
Here, we show that porous additives can improve transport and resist
aging in PIM-1. We develop a simple, low-cost, and scalable hyper-cross-linked
polymer (poly-dichloroxylene, pDCX), which was hydroxylated to form
an intimate mixture with the polar PIM-1. Solvent variation allowed
control of physical aging rates and improved selectivity for smaller
gases. This detailed study has allowed many interactions within mixed
matrix membranes to be directly elucidated and presents a practical
means to stabilize porous polymers for separation applications.
Conspectus
Since the discovery of polymers
of intrinsic microporosity (PIMs)
in 2004, the fast size-selective interconnected pore cavities of the
polymers have caused the upper bound of membrane performance to be
revised, twice. Simultaneously, porous materials have meant that mixed
matrix membranes (MMMs) are now a relatively simple method of enhancing
transport properties. While there are now reliable routes with mixed
matrices to improve the fundamental transport properties of membrane
materials, many of the other properties crucial for separation applications
remain largely unaddressed. Physical aging severely affects membrane
performance over time, especially for those prepared from high fractional
free volume polymers. Gradual densification of the glassy polymer
chains causes the connected pore channels present in these materials
to constrict. Studies now suggest that aging of superglassy polymer
materials is a two-step process; a rapid densification occurs within
the first few days, followed by a gradual rearrangement of packed
chains over longer time frames toward a theoretical equilibrium state.
Although advantageous in terms of size selectivity, the considerable
drop in permeation over the days and weeks after manufacture greatly
impacts material applicability. While often still permeating faster
than traditional membrane materials, the continuous gradual collapse
of cavities in these polymers are a significant challenge in the application
of high free volume polymer membranes. In 2014, we discovered that
the porous aromatic framework PAF-1 not only greatly improved the
membrane’s void space and speed of gas transport but also seemingly
froze several glassy polymers in a low-density state, holding the
polymer’s pore channels open, a process termed as Porosity
Induced Side chain Adsorption (PISA).
This discovery of PISA
fundamentally challenged the conventional
wisdom at the time that the aging rate could only be addressed by
densification of the polymer. Unlike other high-performance glassy
polymers, membranes containing PAF-1 can retain their high permeability
for more than a year. Several other examples of antiaging behavior
have been subsequently reported by the team, where control of aging
rate as a function of gas penetrant, selectivity increases, and stability
at higher pressures was reported. These works also demonstrate that
these mixed matrix systems had applicability for several other separations,
including pervaporation, solvent nanofiltration, and as separators
for energy applications. In our subsequent studies, the antiaging
mechanism has been elucidated as an effect of the interaction between
the polymer’s accessible pendant methyl group and the aromatic
pore surface of PAF-1 or other antiaging additives. In otherwise identical
MMMs, where this hypothesized methyl−π interaction is
either absent or interrupted, we find that the antiaging behavior
expected by the fixation of the polymer chains to the pore surface
and PAF-1 does not occur. As a design approach for mixed matrix membranes,
targ...
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