4D Printing of Self-Immolative Polymers

DOI

4D printing has emerged as a powerful technique for fabricating complex 3D structures that evolve over time in response to external stimuli. In particular, "living" 4D printing strategies enable dynamic, reversible modulations of material properties such as size and mechanical stiffness via post-printing chemical modifications. However, current systems suffer from slow response times and limited reversibility, which restrict their practical applications. Herein, we present a new approach to address these limitations by integrating self-immolative polymers with light-based 3D printing. These polymers are programmed to undergo complete depolymerization in response to an external stimulus, providing a unique mechanism of “living” degrowth that expands the toolbox of adaptive transformations. To this aim, we synthesize photopolymerizable self-immolative polymers consisting of silyl end-capped poly-o-phthalaldehyde on the multi-gram scale and employ them in inks for digital light processing. Upon exposure to fluoride ions, which cleave the silyl end-caps, rapid depolymerization of the polymers results in significant degrowth of fabricated objects, accompanied by modulations of mechanical stiffness and optical transparency. Subsequent repolymerization enables regrowth of the objects. This study establishes self-immolative polymers as a platform for 4D printing and lays the groundwork for future development of dynamic, reconfigurable systems.

Identifier
DOI https://doi.org/10.11588/DATA/0ZMOTG
Related Identifier IsSupplementTo https://doi.org/10.1002/adfm.202520642
Metadata Access https://heidata.uni-heidelberg.de/oai?verb=GetRecord&metadataPrefix=oai_datacite&identifier=doi:10.11588/DATA/0ZMOTG
Provenance
Creator Markhart, Johannes ORCID logo; Mainik, Philipp; Klee, Pia S. ORCID logo; Blasco, Eva ORCID logo
Publisher heiDATA
Contributor Blasco, Eva
Publication Year 2025
Funding Reference Deutsche Forschungsgemeinschaft EXC-2082/1-390761711, INST35/1503-1FUGG ; Carl Zeiss Foundation Carl-Zeiss-Foundation-Focus@HEiKA ; Fonds der Chemischen Industrie Kekulé Fellowship ; Ministerium für Wissenschaft, Forschung und Kunst Baden-Württemberg SDS@hd
Rights CC BY 4.0; info:eu-repo/semantics/openAccess; http://creativecommons.org/licenses/by/4.0
OpenAccess true
Contact Blasco, Eva (Institute for Molecular Systems Engineering and Adv. Mater. (IMSEAM), Heidelberg University)
Representation
Resource Type Dataset
Format application/zip
Size 22469; 162581; 221625; 141129; 10981533; 34489; 24164
Version 1.0
Discipline Chemistry; Natural Sciences; Polymer Materials; Polymer Research