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Issue 7, 2012
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Control of reactivity of constitutional isomers of pentafluorophenyl ethynylbenzoates for the synthesis of functional poly(phenylacetylenes)

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Abstract

Two series of constitutional isomers of monosubstituted ethynylbenzoates were synthesized. The series of the constitutional isomers were based on methyl ethynylbenzoates (M1–M3) and pentafluorophenyl ester ethynylbenzoates (M4–M6), respectively. Rhodium-based catalysts as well as a tungsten-based catalyst were used to polymerize the monomers M1–M6. While the tungsten catalyst could successfully polymerize all six monomers, the ortho-substituted active ester monomer M4 could not be polymerized with rhodium based catalysts. The polymers were obtained in variable molecular weights ranging from 7000 to 200 000 g mol−1 with molecular weight distributions smaller than 3.6 (mostly Mw/Mn < 1.9). The configuration of the polymeric backbone was characterized by 1H NMR and Raman spectroscopy and it was found that polymers synthesized using the rhodium catalyst possessed a cistransoid structure, while polymers synthesized with tungsten based catalysts featured a transtransoid sequence as their major structure. Further, post-polymerization modifications of the reactive polymers with various amines have been investigated and it was found that the polymers showed a different reactivity towards amines depending on the isomer, i.e. the position of the ester moiety at the phenyl ring. Moreover, the UV-vis spectra of the polymers before and after conversion with amines revealed a distinct shift of the UV-vis band maximum of up to 150 nm, accompanied by an apparent colour change indicating a pronounced effect of the side-group onto the conjugated polymer backbone.

Graphical abstract: Control of reactivity of constitutional isomers of pentafluorophenyl ethynylbenzoates for the synthesis of functional poly(phenylacetylenes)

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Publication details

The article was received on 25 Oct 2011, accepted on 20 Nov 2011 and first published on 16 Dec 2011


Article type: Paper
DOI: 10.1039/C2PY00503D
Citation: Polym. Chem., 2012,3, 1769-1782
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    Control of reactivity of constitutional isomers of pentafluorophenyl ethynylbenzoates for the synthesis of functional poly(phenylacetylenes)

    A. C. Pauly and P. Theato, Polym. Chem., 2012, 3, 1769
    DOI: 10.1039/C2PY00503D

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