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

Research output: Contribution to journalArticleResearchpeer-review

Abstract

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
Volume304
Issue number12
DOIs
Publication statusPublished - 1 Dec 2019

Fingerprint

Ethylene Glycol
Ethylene glycol
Sulfhydryl Compounds
Printing
Ethers
Resins
Gelation
Dielectric losses
Curing
Permittivity
Processing
vinyl ether
nonane

Keywords

  • 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

Cooperations

  • NAWI Graz

Cite this

3D-Printing of High-κ Thiol-Ene Resins with Spiro-Orthoesters as Anti-Shrinkage Additive. / Marx, Philipp; Romano, Angelo; Roppolo, Ignazio; Chemelli, Angela; Mühlbacher, Inge; Kern, Wolfgang; Chaudhary, Sunny; Andritsch, Thomas; Sangermano, Marco; Wiesbrock, Frank.

In: Macromolecular materials and engineering, Vol. 304, No. 12, 1900515, 01.12.2019.

Research output: Contribution to journalArticleResearchpeer-review

Marx, Philipp ; Romano, Angelo ; Roppolo, Ignazio ; Chemelli, Angela ; Mühlbacher, Inge ; Kern, Wolfgang ; Chaudhary, Sunny ; Andritsch, Thomas ; Sangermano, Marco ; Wiesbrock, Frank. / 3D-Printing of High-κ Thiol-Ene Resins with Spiro-Orthoesters as Anti-Shrinkage Additive. In: Macromolecular materials and engineering. 2019 ; Vol. 304, No. 12.
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