Influence of the organic matrix composition on the polymerization behavior and bulk properties of resin composites containing thiourethane-functionalized fillers

Ana Paula Fugolin, Ana Rosa Costa, Emilie Kono, Eleanor Quirk, Jack L. Ferracane, Carmem S. Pfeifer

Research output: Contribution to journalArticlepeer-review

8 Scopus citations


Objectives: The incorporation of thiourethane-based oligomeric additives into resin composite formulations leads to improvement in mechanical properties and reduction in polymerization stress, but may increase viscosity. The objective of this study was to functionalize filler particle surfaces with thiourethane silane molecules and determine the impact of the inorganic filler loading and surface treatment on the behavior of experimental resin composites with systematically-varied organic matrices. Methods: Thiourethane oligomer was synthesized de novo, and grafted to the surface of 0.7um barium glass. BisGMA and TEGDMA (BT) were combined (at 30:70, 50:50 or 70:30 wt%) to 50 or 75 wt% of methacrylate (MA-Sil – control) or thiourethane-silanized (TU-Sil) particles. Composites were made polymerizable by the addition of 0.2 wt% BAPO and 0.05 wt% BHT was added as inhibitor. A mercury arc lamp (320–500 nm) at 800 mW/cm2 was used for all curing procedures. Kinetics of polymerization was assessed by near-IR spectroscopy in real time. Polymerization stress was determined with a cantilever system in real time (Bioman). Flexural modulus and strength were determined in 3-point bending (25 × 2 × 2 mm). Water sorption and solubility and film thickness were tested according to ISO 4049. Polymeric network characteristics were analyzed by dynamic mechanical analysis (DMA). Data was analyzed with two-way ANOVA/Tukey's test (95%). Results: Viscosity increased with the increase in BisGMA and/or filler amounts. Overall, TU-Sil containing composites showed delayed vitrification and higher final DC. Filler concentration did not affect DC neither flexural strength. DC decreased with increasing BisGMA content. Polymerization stress reduced and flexural modulus increased for higher filler content, especially for formulations containing TU-Sil particles. The water stability was positively affected by the increase in amount of BisGMA and inorganic filler particles. In terms of polymeric network, the addition of TU-Sil particles increased the Tg and decreased the E′ and cross-link density. Conclusions: With the exception of flexural modulus, all tested properties were significantly impacted by the matrix viscosity and/or the addition of TU-Sil filler particles. In general, the use of thiourethane oligomers as a silane coupling agent was able to reinforce the materials and reduce the polymerization stress without negatively affecting the viscosity of the system.

Original languageEnglish (US)
Article number109664
JournalEuropean Polymer Journal
StatePublished - May 5 2020


  • Dynamic mechanical analysis
  • IR spectroscopy
  • Polymer properties
  • Polymerization kinetics
  • Silica filler functionalization
  • Thiourethane oligomer

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry


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