Abstract Photosensitive resins are the research and development foundation of photopolymerization 3D printed products. We have found that cyclic trimethylolpropane formal acrylate (CTFA) and 2‐phenoxy ethyl acrylate (PHEA) resins are suitable for UV‐curable 3D printing consumables. Their photopolymers exhibit excellent shape memory characteristics at shape change temperature, shape recovery speed, shape extension limit, and shape maintenance ability. Moreover, we have analyzed the internal and external factors affecting these shape memory characteristics through several tests, including multi‐scale structure observation, thermal analysis, and mechanical tests. Furthermore, the complex hollow model design and multiple heat transfer media are adopted to expand the concept of additive manufacturing, and improve the practicability of 4D printing intelligent products.
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