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The purpose of this paper is to evaluate the properties of several thiol-acrylate photosensitive systems and compare with corresponding acrylate free-radical systems. The potential stereolithography applications of thiol–ene photosensitive systems are also discussed.

In the both thiol–ene and acrylate free-radical photosensitive systems, various key performances were characterized. The function group conversions were characterized by real-time Fourier transform infrared spectroscopy. The tension strength was determined according to the standard ASTM D638-2003, the flexible strength was determined according to ASTM D790-07 and the hardness was measured according to ASTM D2240-05. The volume shrinkage was measured by dilatometer method. The glass transition temperature was analyzed by differential scanning calorimeter.

As adding mercapto propionates into acrylate system, the inhibition of polymerization by oxygen was controlled and the flexible performance was improved. In addition, the photosensitive resin showed better tension strength, higher elongation at break and lower volume shrinkage. Among the four mercapto propionates, rigid TEMPIC showed most obvious affect, followed hexa-functional DPMP, tetra-functional PETMP and tri-functional TMMP.

Although the thiol–ene photosensitive resin has unmatched advantages in performance, there are no reports on the thiol–ene photosensitive resin in the stereolithography application. In this study, thiol–ene photopolymerization material was first tentatively implemented in stereolithography area. Several critical performance parameters were compared between thiol–ene and acrylate free-radical photosensitive systems.