Structure–Property Relationships of Shape Memory, Semicrystalline Polymers Fabricated by In Situ Polymerization and Crosslinking of Octadecyl Acrylate/Polybutadiene Blends

The current work presents the study of a semicrystalline, shape memory polymer synthesized by simultaneous free radical polymerization and crosslinking in a blend of polybutadiene (PB) and octadecyl acrylate. Blending elastomers and phase change materials provide a modular method for new smart materials, such as shape memory polymers. In this system, grafted, side‐chain crystalline poly(octadecyl acrylate) (PODA) fixes a programmed shape in the shape memory cycle, while crosslinked polybutadiene drives shape recovery. This work focuses on improving material parameters important for shape memory (crystallinity, gel fraction, melting temperature) by tuning the processing and formulation parameters (amount of crosslinker and PB weight fraction). The result is a shape memory PB‐PODA copolymer that can be fabricated by melt processing and programmed without cooling below ambient temperature. It is found that good shape memory (i.e., high shape fixity and recovery) is obtained at a low PB weight fraction where a percolating PODA crystal network is formed at room temperature. The optimized sample shows excellent shape memory properties (fixity > 99%, recovery = 96%). It is shown that it is possible to mold this material into complex 3D shapes or topography with potential use in anticounterfeiting and antitampering applications. The development of a semicrystalline, shape memory polymer is synthesized by simultaneous free radical polymerization and crosslinking in a blend of polybutadiene and octadecyl acrylate, enabling the melt fabrication of complex 3D molded shapes with potential use in anticounterfeiting and antitampering applications.