Upconversion particle-assisted NIR polymerization enables microdomain gradient photopolymerization at inter-particulate length scale.

High crosslinking and low shrinkage stress are difficult to reconcile in the preparation of performance-enhancing photopolymer materials. Here we report the unique mechanism of upconversion particles-assisted NIR polymerization (UCAP) in reducing shrinkage stress and enhancing mechanical properties of cured materials. The excited upconversion particle emit UV-vis light with gradient intensity to the surroundings, forming a domain-limited gradient photopolymerization centered on the particle, and the photopolymer grows within this domain. The curing system remains fluid until the percolated photopolymer network is formed and starts gelation at high functional group conversion, with most of the shrinkage stresses generated by the crosslinking reaction having been released prior to gelation. Longer exposures after gelation contribute to a homogeneous solidification of cured material, and polymer materials cured by UCAP exhibit high gel point conversion, low shrinkage stress and strong mechanical properties than those cured by conventional UV polymerization techniques.