A self-healing polymer network based on reversible covalent bonding

• Published in: Reactive & functional polymers 2013-02, Vol.73 (2), p.413-420
• Main Authors: Scheltjens, G., Diaz, M.M., Brancart, J., Van Assche, G., Van Mele, B.
• Format: Article
• Language: English
• Subjects: Bismaleimides; Diels–Alder; Elastomers; Furans; Gel-point; Kinetics; Mathematical models; Networks; Reaction kinetics; Repeatability; Sealing; Self-healing coatings; Spacers
• ISSN: 1381-5148
• DOI: 10.1016/j.reactfunctpolym.2012.06.017

A self-healing polymer network for potential coating applications was designed based on the concept of the reversible Diels–Alder (DA) reaction between a furan functionalized compound and a bismaleimide. The network allows local mobility in a temperature window from ca. 80°C to 120°C by shifting the DA equilibrium towards the initial building blocks. Changing the spacer length in the furan functionalized compound leads to tailor-made properties. Elastomeric model systems were chosen to evaluate the kinetic parameters by Fourier transform infrared spectroscopy. For the DA reaction a pre-exponential factor ln(ADA in kgmol−1s−1) equal to 13.1±0.8 and an activation energy (EDA) of 55.7±2.3kJmol−1 are found. For the retro-DA reaction, ln(ArDA) and ErDA are 25.8±1.8s−1 and 94.2±4.8kJmol−1, respectively. The enthalpy and entropy of reaction are calculated as −38.6kJmol−1 and −105.3Jmol−1K−1. The kinetic results are validated by micro-calorimetry. Non-isothermal dynamic rheometry provides the gel-point temperature of the reversible network. The sealing capacity is evaluated by atomic force microscopy for micro-meter sized defects. Repeatability of the non-autonomous healing is checked by micro-calorimetry, ruling out side-reactions below 120°C.