Unexpectedly Facile Rh(I) Catalyzed Polymerization of Ethynylbenzaldehyde Type Monomers: Synthesis of Polyacetylenes Bearing Reactive and Easy Transformable Pendant Carbaldehyde Groups

0473558 - ÚFCH JH 2018 RIV DE eng J - Journal Article
Sedláček, J. - Havelková, L. - Zedník, J. - Coufal, R. - Faukner, T. - Balcar, Hynek - Brus, Jiří
Unexpectedly Facile Rh(I) Catalyzed Polymerization of Ethynylbenzaldehyde Type Monomers: Synthesis of Polyacetylenes Bearing Reactive and Easy Transformable Pendant Carbaldehyde Groups.
Macromolecular Rapid Communications. Roč. 38, č. 8 (2017), č. článku 1600792. ISSN 1022-1336. E-ISSN 1521-3927
R&D Projects: GA ČR(CZ) GA15-09637S
Institutional support: RVO:61388955 ; RVO:61389013
Keywords : Ethynylbenzaldehydes * Inhibition of polymerization * Polyacetylenes
OECD category: Physical chemistry; Polymer science (UMCH-V)
Impact factor: 4.441, year: 2017

The chain coordination polymerization of (ethynylarene)carbaldehydes with unprotected carbaldehyde groups, namely ethynylbenzaldehydes, 1-ethynylbenzene-3,5-dicarboxaldehyde, and 3-[(4-ethynylphenyl)ethynyl]benzaldehyde, is reported for the first time. Polymerization is catalyzed with various Rh(I) catalysts and yields poly(arylacetylene)s with one or two pendant carbaldehyde groups per monomeric unit. Surprisingly, the carbaldehyde groups of the monomers do not inhibit the polymerization unlike the carbaldehyde group of unsubstituted benzaldehyde that acts as a strong inhibitor of Rh(I) catalyzed polymerization of arylacetylenes. The inhibition ability of carbaldehyde groups in (ethynylarene)carbaldehydes seems to be eliminated owing to a simultaneous presence of unsaturated ethynyl groups in (ethynylarene)carbaldehydes. The reactive carbaldehyde groups make poly[(ethynylarene)carbaldehyde]s promising for functional appreciation via various postpolymerization modifications. The introduction of photoluminescence or chirality to poly(ethynylbenzaldehyde)s via quantitative modification of their carbaldehyde groups in reaction with either photoluminescent or chiral primary amines under formation of the polymers with Schiff-base-type pendant groups is given as an example.
Permanent Link: http://hdl.handle.net/11104/0270693