Functionalized hyper-cross-linked porous homopolymers of ring-substituted 1,3-diethynylbenzenes and their physisorption activity

An atom-economic one-step chain-growth coordination homopolymerization providing high yields of functionalized hyper-cross-linked polyacetylenes with a permanent micro/mesoporous texture and a BET area of up to 1062 m2/g is reported. Substituted 1,3-diethynylbenzenes used as monomers in this synthesis simultaneously provide both functionalization and hyper-cross-linking of the resulting products. The homopolymerization is highly compatible with the heteroatom groups of the monomers and allows the preparation of well-defined porous networks with a wide spectrum of univalent groups (-F, -Cl, -Br, -NO2, -COOCH3, -CH2OH, -COOH) present in the networks in a high content of 7.87 mmol/g. The physisorption activity of the prepared networks is significantly affected by the character of the functional groups. Functional groups generally increase the capacity of reversible CO2 capture. Networks with oxygen-containing groups show high and potentially applicationinteresting capacities of cyclic reversible capture of water vapour from the air (capacity up to 314 mg/g, at a relative humidity of 90 %). Halogenated networks, on the other hand, are highly active in the reversible capture of benzene vapour (capacity up to 971 mg/g at room temperature).