Synthesis and properties of halogen- or methyl-containing poly(diphenylacetylene) membranes

Novel diphenylacetylenes with both trimethylsilyl groups and other substituents (R2C6H3CCC6H4-p-SiMe3, R = m,p-Cl,Cl, m,m-Cl,Cl, m,p-Br,Br, m,m-Br,Br, m,p-Me,Me, m,m-Me,Me, 1a–f, respectively) were polymerized with TaCl5–n-Bu4Sn to produce solvent-soluble polymers (2a–f). Most polymers (2a–e) had high molecular weight over 1 × 106, and gave free-standing membranes by the solution casting method. Desilylation of these Si-containing polymer membranes was carried out with trifluoroacetic acid (TFA), which afforded solvent-insoluble desilylated polymer membranes (3a–e). According to thermogravimetric analysis (TGA), both Si-containing and desilylated polymers showed high thermal stability (T0 ≥ 420 °C). The fractional free volume (FFV) of both Si-containing and desilylated polymer membranes (2a–d, 3a–d) were fairly large (ca. 0.27–0.32), while the FFVs of membranes (2e, 3e) were rather small (0.28 and 0.24). The oxygen permeability coefficients (PO2PO2) of 2a was as high as 5400 barrers, which is the largest among all the poly(diphenylacetylene) derivatives. Polymers 2b–d also exhibited high oxygen permeability, and their desilylated ones 3b–d retained similar high oxygen permeability. On the other hand, the PO2PO2 values of 2e and 3e were 1200 and 530 barrers, respectively, which are smaller than those of the halogen-containing polymers (2a–d and 3a–d).