In the present research, a type of cycloaliphatic silicone–epoxy resin is synthesized and then compounded with acrylates as well as photoinitiators to obtain hybrid photopolymers. The photocuring rate of the hybrid photopolymers, the morphology, thermal and mechanical properties of the cured samples with different silicone–epoxy/acrylate ratios are studied in detail. Scanning electron microscopy images prove that interpenetrating polymer network structure is formed. To improve the mechanical properties, diglycidyl ether of bisphenol A is added and finally a type of hybrid photopolymer suitable for stereolithography 3D printing is obtained. Fourier‐transform infrared spectroscopy and photo‐differential scanning calorimeter measurements show that the hybrid photopolymer has a high curing rate, while thermal property tests prove that the cured sample has high thermal stability. Mechanical property tests show that the cured samples have a tensile strength of 40.3 MPa with a break elongation of 6.7%. The objects printed with the hybrid photopolymer exhibit high resolution and dimension accuracy.
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