Orthogonal dynamic covalent boroxine-crosslinked poly(disulfide) networks for chemically recyclable encryption materials.

[Display omitted] • Simple building blocks enable orthogonal solvent-free coupling of DCBs. • Poly(TABA) shows relatively high mechanical robustness (E = 1.1 GPa, σ t = 30 MPa). • Rheological kinetic analysis reveals intrinsic temperature range of bond exchange. • A fluorescent and shape-memorable dual-encryption material is constructed by design. • Multi-ways (decrosslinking and depolymerization) employed to recycle this material. Replacing the "inert" chemical bonds in traditional materials with dynamic bonds brings opportunities in designing renewable materials that repair, reprocess and recycle. Despite the many efforts made in covalent adaptable networks by elaborating a single type of dynamic covalent chemistry, the fabrication of double dynamic covalent polymeric networks, especially using simple small-molecule building blocks, still remains challenging. Here we report the solvent-free construction of a thermosetting material by combining 1,2-dithiolane-based reversible polymerization and dynamic covalent boroxine chemistry as crosslinkers. The resulting materials exhibit tunable mechanical properties, mechanical reprocessability, shape memory ability and closed-loop chemical recyclability. Quantitative kinetic analysis reveals the temperature-dependent apparent activation energy for the bond exchange of the resulting network as a result of the simultaneous integration of the two dynamic covalent bonds. Meanwhile, the boroxine units also act as a luminescent center to enable an emissive "organic glass" that can be used as a dual encryption material taking advantage of the reprogrammable shape-memory behavior of the dynamic network. Benefitting from the simple design, tunable variables and multi-functions, we envision that this double dynamic chemistry offers a robust scaffold and great chemical spaces for the design of dynamic polymeric materials. [ABSTRACT FROM AUTHOR]