Random copolymer membrane coated PBO fibers with significantly improved interfacial adhesion for PBO fibers/cyanate ester composites

Poly(p-phenylene-2,6-benzobisoxazole) (PBO) fibers possess excellent dielectric, mechanical properties and heat resistance. However, the surface of PBO fibers is smooth and highly chemical inert, resulting in poor interfacial compatibility to polymer matrix, which severely limits its wider application in high-performance fiber-reinforced resin matrix composites. In this work, random copolymers (P(S-co-BCB-co-MMA)) containing benzocyclobutene in the side-chain were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, which were then utilized to form dense random copolymer membrane on the surface of PBO fibers by thermally cross-linking at 250 °C (PBO@P fibers). Four kinds of synthesized P(S-co-BCB-co-MMA) with different number-average molar mass (M_n) were well controlled and possessed narrow dispersity. When the M_n was 32300, the surface roughness of PBO@P fibers was increased from 11 nm (PBO fibers) to 39 nm. In addition, PBO@P fibers presented the optimal interfacial compatibility with bisphenol A cyanate (BADCy) resins. And the single fiber pull-out strength of PBO@P fibers/BADCy micro-composites was 4.5 MPa, increasing by 45.2% in comparison with that of PBO fibers/BADCy micro-composites (3.1 MPa). Meantime, PBO@P fibers still retained excellent tensile strength (about 5.1 GPa). Overall, this work illustrates a simple and efficient surface functionalization method, which would provide a strong theoretical basis and technical support for controlling the surface structure & chemistry of inert substrates.