Phosphorescent Oxygen Sensors Utilizing Sulfur−Nitrogen−Phosphorus Polymer Matrixes: Synthesis, Characterization, and Evaluation of Poly(thionylphosphazene)-b-Poly(tetrahydrofuran) Block Copolymers
- 17 March 2000
- journal article
- research article
- Published by American Chemical Society (ACS) in Analytical Chemistry
- Vol. 72 (8) , 1894-1904
- https://doi.org/10.1021/ac9909610
Abstract
We examine the use of thionylphosphazene-based block copolymers as matrixes for oxygen sensor applications. Poly(aminothionylphosphazene)-b-poly(tetrahydrofuran) (PATPy−PTHFx) block copolymers were prepared via reaction of ring-opened poly(chlorothionylphosphazene) with THF and subsequently with excess n-butylamine (to form PBATPy−PTHFx) or methylamine (to form PMATPy−PTHFx). The block copolymers were characterized by NMR, gel permeation chromatography, and differential scanning calorimetry. Films of PBATPy−PTHFx block copolymers containing platinum octaethylporphyrin or [Ru(dpp)3]Cl2 (dpp = 4,7-diphenyl-1,10-phenanthroline) as the oxygen-sensitive chromophore were prepared, and time-scan experiments were carried out to determine the diffusion coefficients, DO2, and solubilities, SO2, of oxygen therein. Despite microphase separation, the data fit well to a simple Fick's law description of oxygen diffusion and gave DO2 values smaller than that for the n-butylamino-substituted PBATP635. For films freshly annealed above the melting point of PTHFx, the DO2values were 35−50% (dye-dependent) larger than after aging 3 days at room temperature. Films with [Ru(dpp)3]Cl2 as the dye were evaluated as media for phosphorescent pressure-sensing. The dye-containing polymer films exhibit linear Stern−Volmer-like plots, even at high dye concentrations, as well as good photostability, and significantly higher sensitivity to oxygen quenching than simple mixtures of the analogous homopolymers.Keywords
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