Ultramicroporous polyimides obtained from bio-based anhydrides were synthesized for gas separation mem-branes. Two novel dianhydrides, 5,5'-(mesitylmethylene)bis(4-methylphthalic anhydride) (MMDA) and 5,5'-(9H-fluorene-9,9-diyl)bis(4-methylphthalic anhydride) (FDDA), were successfully synthesized from guaiacol, a lignin-based bio-material. Due to the fixed center of o-methyltriphenylmethane and o-methyldiphenylfluorene units, the bio-based dianhydrides had high energy barriers to rotation, resulting in highly rigid polymer chains. After polymerization with a Troeuroger's Base (TB)-containing diamine using a one-step imidization, two kinds of bio-based polyimides incorporating TB units (Bio-TBPI-1 and Bio-TBPI-2) were prepared with reasonable mo-lecular weights and outstanding thermal properties. Bio-TBPIs demonstrated a microporous structure determined by high BET surface areas of-500 m(3) g(-1), high fractional free volumes (FFVs) of-0.2, and d-spacings of-0.7 nm. In addition, Bio-TBPIs exhibited narrow cavity size distributions around 0.5 nm, and molecular sieving characteristics due to the ultramicroporosity. Bio-TBPI membranes displayed excellent gas separation perfor-mance, which was located near the upper bounds of important gas pairs such as H-2/CH4, H-2/N-2, O-2/N-2, and CO2/CH4. The gas separation performance of Bio-TBPIs was better than that of corresponding TB-based poly-imides containing commercial dianhydrides. The effect of physical aging on gas transport behaviors of Bio-TBPIs was monitored for 200 days, resulting in loss of permeability and enhanced selectivities
