3D Printable Modular Soft Elastomers from Physically Crosslinked Homogeneous Associative Polymers

Three-dimensional (3D) printing of elastomers enables the fabrication of many technologically important structures and devices. However, there remains a critical need for the development of reprocessable, solvent-free soft elastomers that can be printed without the need for post-treatment. Here, we report modular soft elastomers suitable for direct ink write (DIW) printing by physically crosslinking associative polymers with a high fraction of reversible bonds. We design and synthesize linear-associative-linear (LAL) triblock copolymers; the middle block is an associative polymer carrying amide groups that form double hydrogen bonding, and the end blocks aggregate to hard glassy domains that effectively act as physical crosslinks. The amide groups do not aggregate to form nanoscale clusters and only slow polymer dynamics without changing the shape of the linear viscoelastic spectra; this enables molecular control over energy dissipation by varying the fraction of the associative groups. Exploiting the more ordered microstructures afforded by block copolymer self-assembly increases the network stiffness by >100 times without significantly compromising extensibility. We use a high-temperature DIW printing platform to print these LAL polymers and manufacture complex, highly deformable 3D structures. Our printing process uses melt processing and is solvent-free, and the printed parts do not require any post-print processing. We create elastomers with Young’s moduli ranging from 8 kPa to 8 MPa while maintaining tensile breaking strain around 150%. Our elastomers represent the softest melt reprocessable materials for DIW printing. The developed LAL polymers synergize emerging homogeneous associative polymers with high fraction of reversible bonds and classical block copolymer self-assembly to form a dual-crosslinked network, providing a versatile platform for the modular design and development of soft, melt reprocessable elastomeric materials for practical applications.