Hisao Hachisuka

New type asymmetric membranes having almost defect free hyper-thin skin layer and sponge-like porous matrix

Abstract We have developed a new type of asymmetric membrane that has a hyper-thin skin layer and sponge-like porous matrix. 6FDA-BAAF polyimide was used as one of the membrane materials. The skin layer had hardly any defects and the thickness of the membrane was 40–60 nm. The skin layer and sponge-like porous matrix, which had a finger-void-free morphology, were formed as one body. The interface between them was found to be clearer than with other asymmetric membranes and the skin layer did not form as a graded density skin. It is suggested that the formation of such hyper-thin skin layers depends on the dissolution property between a dope solvent and water as a solidification solvent. Namely, solvents such as diethylene glycol dimethyl ether (DGDE; used in this study) are miscible in water, but a sharp interface between DGDE and water forms for a while like between water and oil. The hyper-thin skin layer having hardly any defects is possibly formed by solidification at the sharp interface. It is obvious that such solvent properties might depend on the dielectric constant and/or dipole moment. The selectivity and permeation rate of the 6FDA-BAAF polyimide asymmetric membrane had an α of 27 for CO 2 CH 4 and a permeation rate of 1.3 [Nm3/m2 h atm] (=5.5×10−4 [cm3(STP)/cm2 s cmHg]) for CO2. (The maximum value had an α of 35 for CO 2 CH 4 and a permeation rate of 1.6 [Nm3/m2 h atm] (=5.8×10−4 [cm3(STP)/cm2 s cmHg])).

Gas permeation properties of new type asymmetric membranes

We have developed a new type of asymmetric membranes having a homogeneous hyperthin skin layer, which was used as a polyimide synthesized by 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 2,2-bis(4-amino phenyl) hexafluoro-propane (BAAF). The skin layer thicknesses of the 6FDA-BAAF polyimide asymmetric membranes were 40-60 nm, and the porosity was 10 -6 % when a defect size was assumed as 5 nm. The permselectivity of 6FDA-BAAF polyimide asymmetric membranes after silicone coating had α of 40 for CO 2 /CH 4 and a flux of 1.0 [Nm 3 /m 2 -h-atm] (=3.7 x 10 -4 [cm 3 (STP)/cm 2 s cmHg]) for CO 2 , α of 4.3 for O 2 /N 2 and a flux of 2.0 X 10 -1 [Nm 3 /m 2 /h/atm] (=7.1 X 10 -5 [cm 3 (STP)/cm 2 s cmHg] for O 2 . These values were constant for large-scale manufacturing.

SYNTHESIS AND PROPERTIES OF COPOLYMERS FROM 1-[3,5-BIS(TRIMETHYLSILYL)PHENYL]-2-PHENYLACETYLENE

Copolymerization of 1-[3,5-bis(trimethylsilyl)phenyl]-2-phenylacetylene (m,m-(Me3Si)2DPA) with other diphenylacetylene derivatives and their copolymer properties were investigated. Homopolymerization of m,m-(Me3Si)2DPA by TaCl5─n-Bu4Sn (1:2) did not give the polymer due to steric hindrance. However, m,m-(Me3Si)2DPA copolymerized with diphenylacetylene (DPA), 1-phenyl-2-[p-(trimethylsilyl)phenyl]acetylene (p-Me3Si DPA), and 1-phenyl-2-[m-(trimethylsilyl)phenyl]acety-lene (m-Me3SiDPA) in the presence of TaCl5─n-Bu4Sn at various feed ratios to give copolymers in moderate yields. The formed copolymers were yellow to orange solids, which were soluble in common organic solvents such as toluene and CHCl3. The highest weight-average molecular weights (Mw) of these copolymers reached ca. 6 × 105 and tough films could be obtained by solution casting. Their onset temperatures of weight loss in air were observed around 400°C, indicating high thermal stability. The oxygen permeability coefficients at 25°C of copoly(m,m-(Me3Si)2 DPA/DPA) (feed ratio 1:1) and copoly(m,m-(Me3Si)2DPA/p-Me3SiDPA) (feed ratio 1:2) were 21 and 100 barrers, respectively, medium in magnitude among polymers from substituted acetylenes.