Novel crosslinking system for poly-chloroprene rubber to enable recyclability and introduce self-healing

Kaur, Anureet and Gautrot, Julien E. and Cavalli, Gabriele and Watson, Douglas and Bickley, Alan and Akutagawa, Keizo and Busfield, James J.C. (2021) Novel crosslinking system for poly-chloroprene rubber to enable recyclability and introduce self-healing. Polymers, 13 (19). 3347. ISSN 2073-4360 (

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The introduction of dynamic bonds capable of mediating self-healing in a fully cross-linked polychloroprene network can only occur if the reversible moieties are carried by the cross-linker itself or within the main polymer backbone. Conventional cross-linking is not suitable for such a purpose. In the present work, a method to develop a self-healable and recyclable polychloroprene rubber is presented. Dynamic disulfide bonds are introduced as part of the structure of a crosslinker (liquid polysulfide polymer, Thiokol LP3) coupled to the polymer backbone via thermally initiated thiol-ene reaction. The curing and kinetic parameters were determined by isothermal differential scanning calorimetry and by moving die rheometer analysis; tensile testing was carried to compare the tensile strength of cured compound, healed compounds and recycled compounds, while chemical analysis was conducted by surface X-ray Photoelectron Spectroscopy. Three formulations with increasing concentrations of Thiokol LP-3 were studied (2, 4, 6 phr), reaching a maximum ultimate tensile strength of 22.4 MPa and ultimate tensile strain of 16.2 with 2 phr of Thiokol LP-3, 11.7 MPa and 10.7 strain with 4 phr and 5.6 MPa and 7.3 strain with 6 phr. The best healing efficiencies were obtained after 24 h of healing at 80◦C, increasing with the concentration of Thiokol LP-3, reaching maximum values of 4.5% 4.4% 13.4% with 2 phr, 4 phr and 6 phr, respectively, while the highest recycling efficiency was obtained with 4 phr of Thiokol LP-3, reaching 11.2%.