Synthesis and Characterization of Thiol-yne and Thiol-yne-methacrylate Derived Photo-curable Resins

Johannes Wiener

Research output: ThesisMaster's Thesis

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The patient specific manufacturing of biomedical devices by UV-based 3D-printing technologies is a rapidly growing segment of market and research. The subject of the present thesis is the synthesis of thiol-yne and thiol-yne-methacrylate derived compounds for such UV-based 3D-printing applications. A commercial bifunctional acrylate was successfully converted into a tetrafunctional alkyne by utilizing the Michael addition reaction. In addition, two hybrid monomers were created by functionalizing Hydroxyethyl methacrylate with two different alkyne moieties. The photoreactive properties of various compounds containing the novel monomers were investigated with photo-differential scanning calorimetry (Photo-DSC) and real-time Fourier transform infrared spectroscopy (FTIR). A commercial methacrylate was investigated in the same way so the results could be compared. The photopolymers of resins containing the novel monomers were investigated with dynamic mechanical analysis (DMA) and crack tip opening angle measurements (CTOA). A commercial acrylate was investigated in the same way so the results could be compared. The binary thiol-yne system exhibited good reaction rate as well as high monomer conversion. The ternary systems containing the hybrid monomers showed very good conversions despite the presence of methacrylate. The initially slow reaction rate could be significantly improved by adding Urethane dimethacrylate (UDMA) without influencing monomer conversions. The photocured thiol-yne formulation provided the highest storage modulus and glass transition temperature of the investigated novel resins. Although the glass transition temperature of a comparable acrylate could not be reached, a higher storage modulus could be achieved. The thiol-yne derived compound proved to have tougher material behavior than a comparable acrylate, resulting in a larger crack tip opening angle. In conclusion, the novel compounds represent a suitable substitution and/or valuable supplement for commercial (meth)acrylate systems for UV-based 3D-printing applications.
Translated title of the contributionSynthese und Charakterisierung von Thiol-In und Thiol-In-Methacrylat basierten lichthärtenden Harzen
Original languageEnglish
  • Grießer, Thomas, Supervisor (internal)
Award date30 Jun 2017
Publication statusPublished - 2017

Bibliographical note

embargoed until 25-05-2018


  • Thiol-yne polymerization
  • Thiol-yne-methacrylate systems
  • Polymer photochemistry

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