3D-Printing of High-κ Thiol-Ene Resins with Spiro-Orthoesters as Anti-Shrinkage Additive

Philipp Marx, Angelo Romano, Ignazio Roppolo, Angela Chemelli, Inge Mühlbacher, Wolfgang Kern, Sunny Chaudhary, Thomas Andritsch, Marco Sangermano*, Frank Wiesbrock

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Tri(ethylene glycol) divinyl ether and the spiro-orthoester 2-((allyloxy)methy)-1,4,6-trioxospiro[4.4]nonane can be formulated in different ratios and crosslinked by thiol-ene reactions. The spiro-orthoester is used as anti-shrinkage additive, enabling shrinkage reduction of up to 39%. Addition of a radical photoinitiator for the thiol-ene reaction and a cationic photoinitiator for the double ring-opening of the spiro-orthoester enables dual-curing for application in 3D-printing. The formulation free of the spiro-orthoester shows gelation during the printing process and, correspondingly, low resolution. The formulations containing the spiro-orthoester exhibit higher resolutions in the range of 50 µm. The resins containing mixtures of tri(ethylene glycol) divinyl ether and the spiro-orthoester show permittivities as high as 104. The dielectric loss factor of the resins is in the range of 0.5–7.6, and the conductivity in the range of 1.3⋅10−11 to 2.0⋅10−11 S cm−1. These high-κ materials can be 3D-printed by digital light processing for the next generation of electronic materials.

Original languageEnglish
Article number1900515
Number of pages10
JournalMacromolecular Materials and Engineering
Issue number12
Publication statusPublished - 1 Dec 2019


  • anti-shrinkage additives
  • high-κ dielectrics
  • photopolymerization
  • spiro-orthoesters
  • thiol-ene click reaction

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

Fields of Expertise

  • Advanced Materials Science


  • NAWI Graz


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