Transition-Metal-Catalyzed Chain-Growth Polymerization of 1,4-Diethynylbenzene into Microporous Crosslinked Poly(phenylacetylene)s: the Effect of Reaction Conditions

0432425 - ÚFCH JH 2015 RIV DE eng J - Journal Article
Slováková, E. - Zukal, Arnošt - Brus, Jiří - Balcar, Hynek - Brabec, Libor - Bondarev, D. - Sedláček, J.
Transition-Metal-Catalyzed Chain-Growth Polymerization of 1,4-Diethynylbenzene into Microporous Crosslinked Poly(phenylacetylene)s: the Effect of Reaction Conditions.
Macromolecular Chemistry and Physics. Roč. 215, č. 19 (2014), s. 1855-1869. ISSN 1022-1352. E-ISSN 1521-3935
R&D Projects: GA ČR(CZ) GAP108/11/1661
Institutional support: RVO:61388955 ; RVO:61389013
Keywords : Conjugated microporous polymers * Conjugated polymers * Microporous organic polymers
Subject RIV: CF - Physical ; Theoretical Chemistry; CD - Macromolecular Chemistry (UMCH-V)
Impact factor: 2.616, year: 2014

Chain-growth polymerization of 1,4-diethynylbenzene into conjugated crosslinked polyacetylene-type poly(1,4-diethynylbenzene)s (PDEBs) is reported. While metathesis catalysts (WCl6/Ph4Sn, MoCl5/Ph4Sn, Mo Schrock carbene) fail in this polymerization, insertion Rh catalysts ([Rh(nbd)acac], [Rh(nbd)Cl]2) provide microporous PDEBs in high yields. The Brunauer-Emmett-Teller (BET) surface, SBET, of PDEBs prepared with [Rh(nbd)acac] increases, in dependence on the polymerization solvent, in the order: THF < pentane < benzene < methanol < CH2Cl2. SBET further increases with both increasing monomer concentration and increasing polymerization temperature and reaction time, reaching a highest value of 1469 m2 g-1. In addition to micropores, PDEBs contain mesopores. The mesopore volume and average mesopore diameter increase with the time and the temperature of the polymerization up to 2.52 cm3 g-1 and 22 nm (72 h, 75 °C). The post-polymerization thermal treatment of PDEB (280 °C) results in formation of new crosslinks and modification of PDEB texture and sorption behavior manifested mainly by enhancement of H2 adsorption capacity up to 4.55 mmol g-1 (77 K, 750 Torr).
Permanent Link: http://hdl.handle.net/11104/0236780