Hydrogen-Bonded and Multiple-Supramolecular Photopolymer Networks: Association Strength, Rate Dependence and Fatigue Recovery

Hydrogen-bonded and other supramolecular photopolymer networks use reversible non-covalent association to dissipate energy, recover interfaces and create stimuli-responsive printed materials. Unlike dynamic covalent networks, the load-bearing state can change without bond- breaking chemistry, so association strength, lifetime, density and environmental sensitivity become primary state variables. This review examines single and multiple hydrogen-bond motifs, deep-eutectic and ionogel-like photocurable systems, dual covalent/supramolecular networks and other reversible associations relevant to vat photopolymerisation. Published DLP-compatible systems demonstrate improved toughness, self-healing, assembly welding, reprocessability and stimuli response, while also showing strong sensitivity to humidity, solvent, temperature, pH and strain rate. The main qualification challenge is therefore rate dependence: a network may appear strong in a rapid tensile test yet creep under sustained load, or may heal in a solvent environment while losing dimensional stability. A framework is proposed that separates association kinetics from permanent crosslink density and couples mechanical testing across strain rate and frequency with humidity conditioning, damage recovery, fatigue, creep and dimensional metrology.

ER-318 · Version 0.5.