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Thermal dissipation is a critical aspect for the performance and lifetime of electronic devices. In this work, novel composites based on a cycloaliphatic epoxy matrix and BN fillers, obtained by cationic curing of mixtures of 3,4‐epoxy cyclohexylmethyl 3,4‐epoxy cyclohexane carboxylate (ECC) with several amounts of hexagonal boron nitride (BN) were prepared and characterized. As cationic initiator a commercial benzylanilinium salt was used, which by addition of triethanolamine, exhibited an excellent latent character and storage stability. The effect of the formulation composition was studied by calorimetry and rheological measurements. The variation of thermal conductivity, thermal stability, thermal expansion coefficient, and thermomechanical and mechanical properties of the composites with the load of BN filler (ranging from 10 to 40 wt%) was evaluated. An improvement of an 800% (1.04 W/m·K) in thermal conductivity was reached in materials with glass transition temperatures >200°C without any loss in electrical insulation. POLYM. COMPOS., 39:E1760–E1769, 2018. © 2018 Society of Plastics Engineers

A new type of tetraphenylborate salts derived from highly basic and nucleophilic amines, namely 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and triazabicyclodecene (TBD), was applied to the preparation of networked poly(thiourethane)s (PTUs), which showed a vitrimer-like behavior, with higher stress-relaxation rates than PTUs prepared by using dibutyl thin dilaurate (DBTDL) as the catalyst. The use of these salts, which release the amines when heated, instead of the pure amines, allows the formulation to be easily manipulated to prepare any type of samples. The materials prepared from stoichiometric mixtures of hexamethylene diisocyanate (HDI), trithiol (S3) and with a 10% of molar excess of isocyanate or thiol were characterized by FTIR, thermomechanical analysis, thermogravimetry, stress-relaxation tests and tensile tests, thus obtaining a complete thermal and mechanical characterization of the materials. The recycled materials obtained by grinding the original PTUs and hot-pressing the small pieces in the optimized time and temperature conditions were fully characterized by mechanical, thermomechanical and FTIR studies. This allowed us to confirm their recyclability, without appreciable changes in the network structure and performance. From several observations, the dissociative interchange trans-thiocarbamoylation mechanism was evidenced as the main responsible of the topological rearrangements at high temperature, resulting in a vitrimeric-like behavior.

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