Synthesis and characterisation of pyrene-labelled polydimethylsiloxane networks: towards the in situdetection of strain in silicone elastomers

Abstract

Pyrene-substituted polyhydromethylsiloxanes (PHMS-Py_x) were synthesised by the hydrosilylation reaction of prop-3-enyloxymethylpyrene with polyhydromethylsiloxane (M_n = 3700). The ratio of pyrene substituent to Si–H unit was varied to afford a range of pyrene-functionalised polysiloxanes. These copolymers were subsequently incorporated into polydimethylsiloxane (PDMS) elastomers by curingvia either Pt(0) catalysed hydrosilylation with divinyl-terminated PDMS (M_n = 186) and tetrakis(dimethylsiloxy)silane, or Sn(II) catalysed condensation with α,ω-dihydroxyPDMS (M_n = 26 000) and tetraethoxysilane. An alternative method involving the synthesis and integration of [3-(pyren-1-ylmethoxy)propyl]triethoxysilane (Py-TEOS) into PDMS elastomers was also investigated: a mixture of α,ω-dihydroxyPDMS (M_n = 26 000), tetraethoxysilane, and Py-TEOS was cured using an Sn(II) catalyst. Certain of the resulting fluorescent pyrene-labelled elastomers were studied by differential scanning calorimetry and dynamic mechanical analysis. No significant changes were observed in the thermal or mechanical properties of the elastomers containing pyrene when compared to otherwise identical samples not containing pyrene. All of the pyrene-containing elastomers were demonstrated to be fluorescent under suitable excitation in a photoluminescent spectrometer. Two of the elastomers were placed in a photoluminescence spectrometer and subjected to cycles of extension and relaxation (strain = 0–16.7%) while changes in the emission spectra were monitored. The resulting spectra of the elastomer containing the PHMS-Py₅₀ copolymers were variable and inconsistent. However, the emission peaks of elastomers containing Py-TEOS displayed clear and reproducible changes in fluorescence intensity upon stretching and relaxation. The intensity of the monomer and excimer emission peaks was observed to increase with elongation of the sample and decrease upon relaxation. Furthermore, the ratio of the intensities of the excimer : monomer peak decreased with elongation and increased with relaxation. In neither case was there appreciable hysteresis, suggesting that fluorescent labelling of elastomers is a valid approach for the non-invasive in situ monitoring of stress and strain in such materials.