Comb Polybutadiene with Long Polystyrene Side Chains: A Solution for Tunable Flowability and Enhancing Dielectric Properties in High-Frequency Printed Board Adhesive Films

Liquid high-vinyl polybutadiene (PB) possessed excellent dielectric properties, rendering them suitable candidates for adhesive films of high-frequency printed boards. However, their inherent low molecular weights resulted in chain slippage and overflow during processing, thereby diminishing the performance of the adhesive films. To address this challenge, we synthesized comb PB with long polystyrene side chains via reversible addition-fragmentation chain transfer (RAFT) polymerization, effectively immobilizing the PB backbone and restricting relative chain slippage. Controlling the length and number of "comb teeth" (styrene side chains) efficiently regulated the flowability of comb PB, achieving distinct flow states. Simultaneously, molecular dynamics simulations revealed that the elongated and inflexible polystyrene side chains of comb PB could create minuscule cavities, which impeded close packing of molecules and led to low dielectric constants (2.39/2.01, 1 MHz/10 GHz) and ultralow dielectric losses (0.0071/0.0016, 1 MHz/10 GHz). Furthermore, a series of printed circuit boards were fabricated using a comb PB adhesive film, and the signal loss was significantly reduced to 48.8% (19 GHz) in comparison with a commercial epoxy adhesive. This study demonstrated the potential of comb PB with polystyrene side chains to achieve desirable flow and dielectric properties by introducing tangles, large volume potential resistance, and microporosity compared with block structures.