Junghwan Shin

Direct RAFT polymerization of an unprotected isocyanate-containing monomer and subsequent structopendant functionalization using “click”-type reactions

The controlled reversible addition–fragmentation chain transfer (RAFT) homopolymerization of an unprotected isocyanate-containing monomer, in this case 2-(acryloyloxy)ethylisocyanate (AOI), is reported. The polymerization conditions were optimized in terms of the choice of RAFT chain transfer agent (CTA), polymerization temperature and the reaction medium. Direct RAFT polymerization of AOI requires a neutral CTA, and relatively low reaction temperature to yield AOI homopolymers with low polydispersities. Efficient side-chain functionalization of poly(2-(acryloyloxy)ethylisocyanate) (PAOI) homopolymers was achieved via reaction with model amine, thiol and alcohol compounds yielding urea, thiourethane and urethane derivatives, respectively. Reactions with amines and thiols (in the presence of base) were rapid, quantitative and efficient. However, the reaction with alcohols catalyzed by dibutyltin dilaurate (DBTDL) was relatively slow but proceeded to completion. Selective reaction pathways for the addition of difunctional ethanolamine and mercaptoethanol were also investigated.

Characterization of mouthguard materials: Thermal properties of commercialized products

OBJECTIVES Several mechanisms have been purported to describe how mouthguards protect the orofacial complex against injury. As the properties needed for these mechanisms to be effective are temperature and frequency dependent, the specific aim of this study was to provide a comprehensive thermal characterization of commercial mouthguard materials. METHODS Five commercially representative thermoplastic mouthguard materials (Essix Resin, Erkoflex, Proform-regular, Proform-laminate, and Polyshok) were tested. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) techniques were implemented to measure thermal transitions and mechanical properties. Measurements were conducted three times per sample. One-way ANOVA and one-sample t-tests were used to test for differences between commercial products on selected mean thermal property values. RESULTS The DSC measurements indicated no differences between commercial materials for mean glass transition (p=0.053), onset melt (p=0.973), or peak melt (p=0.436) temperatures. Likewise, DMA measurements revealed no differences between commercial materials for the mean glass transition (p=0.093), storage modulus (p=0.257), or loss modulus (p=0.172) properties, respectively. The one-sample t-tests revealed that glass transition temperatures were different from intra-oral temperature (p<0.005) for all materials. SIGNIFICANCE Commercialized mouthguard materials are sensitive to repetitive heating and cooling cycles, prolonged thermal treatment, and have glass transitions well below their end-use intra-oral temperature. As such, these materials are functioning as elastomers and not optimal mechanical damping materials. Dental clinicians, healthcare practitioners, or end-users should be aware that these materials are at best problematic with respect to this protective mechanism.