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 M_n 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 (Δλ_max,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 Δλ_max,em were observed, yielding a critical molar mass of M_c ≈ 11 kg mol^-1 for PmmpP. Once physical cross-linking of oDPP in the network of PmmpP was ensured, Δλ_max,em was found to be independent of M_n. The resulting value of M_c is in very good agreement with results from rheology.