Determining Entanglement Molar Mass of Glassy Polyphenylenes Using Mechanochromic Molecular Springs

Molecular force transduction in tough and glassy poly(meta,meta,para-phenylene) (PmmpP) was investigated as a function of Mn using covalently incorporated mechanochromic donor–acceptor torsional springs based on an ortho-substituted diphenyldiketopyrrolopyrrole (oDPP). Blending oDPP-PmmpP probe chains with long PmmpP matrix chains allowed us to investigate molar-mass-dependent mechanochromic properties for a series of specimens having mechanically identical properties. In the strain-hardening regime, the mechanochromic response (Δλmax,em) was found to be a linear function of the acting stress and fully reversible, making oDPP-PmmpP a real-time and quantitative stress sensor. For entangled and nonentangled probe chains, distinctly different values of Δλmax,em were observed, yielding a critical molar mass of Mc ≈ 11 kg mol–1 for PmmpP. Once physical cross-linking of oDPP in the network of PmmpP was ensured, Δλmax,em was found to be independent of Mn. The resulting value of Mc is in very good agreement with results from rheology.