Short Report 1: Functionalized Membrane Development in Yamaguchi Group

Membrane technology has drawn numerous attention because it can be an alternative to

reduce energy consumption1. Many researchers had made functionalized membranes to
achieve some goals in separation process or to mimic the nature.
In 1991, Yamaguchi et al proposed a new concept of pore-filling membrane. HDPE was used as
hard porous substrate and filled by poly(methyl acrylate). Swelling of poly(methyl acrylate)
can be restricted due to mechanically stable HDPE matrix 2. Pore-filling membrane concept
was shown in figure 1. Grafting process itself had been reported successfully using Plasmainduced graft polymerization (PIGP) method 234567. This method is convenience to treat
thermally labile monomer because its mild thermal conditions on acidic environment 4. Grafted
copolymer composition as well as its solubility can be regulated by monomer composition
variation6.

Figure 1. Concept of Pore- Filling Membrane2

Ulbricht et al reported on 1997 that pore-filling concept had been successfully applied to
polyacrylonitrile (PAN) asymmetric membrane for pervaporation process 8. His group was using
UV irradiation instead of plasma. Pore-filling membrane also can be prepared using inorganic
substrate like porous glass9.
Ten years after the first paper about pore filling membrane, the concept was employed on
hollow fiber membrane10,11 and microcapsule12. Not just for pervaporation, in 2005 Yamaguchi
et al were successfully demonstrated the capability of pore-filling membrane to do Reverse
Osmosis process. It can be achieved using crosslinked grafting polymer 13.
The further development of pore filling membrane was smart responsive gating membrane.
The idea was to create something like a door in substrate pores than can be open or closed
depend on the stimuli. Other work by Yamaguchi et al showed that copolymer Nisopropylacrylamide (NIPAM) -- benzo[18]crown-6-acrylamide (BCAm) grafted on porous HDPE
substrate can response Ba2+ ion3. This concept of ion-gating membrane can be modelled using
some governing equations14.
The same group then developed biomolecule-recognition gating system to responds signals of
biomolecules by using of biorecognition cross-linking and polymer phase transition on same
porous substrate15. Some improvements were made to the responsive polymer or the door
of the gating membrane. NIPAM as primary backbone of the door was combined with cyclodextrin16 and DNA17 to broaden its capability to sense variety of molecules. The gating
membrane can also be modified in order to respond pH using ion- recognition polyampholyte
like poly(acrylic acid-co-crown ether)5.
Other example of functionalized membrane is using ceramic membrane for gas separation.
Yamaguchi et al demonstrated the great potential of zeolitic-imidazolate frameworks (ZIF)-8
to be used as a material for the membrane separation of propylene/propane on the basis of
their diffusivity difference1.

References
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