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

Abstract

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).

Sulfonated Hyper‐cross‐linked Porous Polyacetylene Networks as Versatile Heterogeneous Acid Catalysts

“…Two phenylene‐rich hyper‐cross‐linked microporous polymer networks, poly(1,4‐diethynylbenzene), P(1,4‐DEB) and poly(1,3‐diethynylbenzene), P(1,3‐DEB) were prepared as parent materials for the modification by sulfonation (Scheme ). The networks were synthesized by the chain‐growth homopolymerizations of respective monomers, 1,4‐DEB and 1,3‐DEB as described previously . Prepared P(1,4‐DEB) and P(1,3‐DEB) consisted of the polyene (polyacetylene) chains hyper‐cross‐linked by either 1,4‐phenylene or 1,3‐phenylene links, as shown in Scheme .…”

“…The networks were synthesized by the chain-growth homopolymerizations of respective monomers, 1,4-DEB and 1,3-DEB as described previously. [32,34] building blocks. [25] The sulfonated networks were labelled as P(1,4-DEB)-SO 3 H and P(1,3-DEB)-SO 3 H. Table 1 shows the amount of SO 3 H groups introduced into P(1,4-DEB)-SO 3 H and P (1,3-DEB)-SO 3 H as a function of the amount of chlorosulfuric acid supplied for the sulfonation of P(1,4-DEB) and P(1,3-DEB).…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…378) could be converted to various dialkyne block copolymers by treatment with another dialkyne monomer. Simple alkyne polymerization of 1,4-diethynylbenzene was successfully initiated by [Rh(norbornadiene)Cl] 2 / Et 3 N, however the Schrock catalyst was not effective in this process [864]. Alkyne polymerization using a Bu 4 Sn / TaCl 5 catalyst system was also reported [865].…”

Ionic π‐Conjugated Polyelectrolytes by Catalyst Free Polymerization of Bis(pyridyl)acetylenes and Bis[(pyridyl)ethynyl]benzenes

“…The π‐conjugated polymers (CP), e.g., polyacetylenes, poly(arylene)s, poly( para ‐phenylenevinylene)s, and poly( para ‐phenyleneethynylene)s have become an important class of materials with a wide variety of applications, including light‐emitting diodes (LEDs), light‐emitting electrochemical cells (LECs), plastic lasers, solar cells, field‐effect transistors (FETs) and porous materials …”

“…materials with a wide variety of applications, [1][2][3][4][5][6][7][8] including light-emitting diodes (LEDs), [ 9 ] light-emitting electrochemical cells (LECs), [ 10 ] plastic lasers, [ 11 ] solar cells, [ 12 ] fi eld-effect transistors (FETs) [ 13 ] and porous materials. [ 14,15 ] The π-conjugated polyelectrolytes (CPEs) represent a special subclass of CPs.…”