Effects of Peroxide Initiator on the Structure and Properties of Ultralow Loss Thermosetting Polyphenylene Oxide-Based Composite

Although thermosetting polyphenylene oxide- (PPO) based composites with excellent dielectric properties have been widely accepted as superior resin matrices of high-performance copper clad laminate (CCL) for 5G network devices, there has been limited information regarding the composition–process–structure–property relationships of the systems. In this work, the effects of peroxide initiator concentration on the structure and dielectric properties of a free radical cured ultralow loss PPO/Triallyl isocyanate (TAIC) composite system were studied. As expected, the glass transition temperature (T(g)) and storage modulus increased with the advancing of crosslinking, whereas the dielectric loss showed an “abnormal” rise with the increase in crosslink density. Extensive studies were carried out by varying the initiator contents and characterizing the structure with spectroscopy, thermal analysis, and positron annihilation lifetime spectrum (PALS) techniques. The results show that the competition of polarity, crosslink density, free volume, and free TAIC are the key factors determining the dielectric properties of the composites.