Immobilization of polyphosphoesters on poly(ether ether ketone) (PEEK) for facilitating mineral coating

Poly(ether ether ketone) (PEEK) is an alternative material to metals for orthopedic applications. However, the compatibility of PEEK with hard tissues needs to be improved. To address this issue, this study proposes a novel technique for PEEK surface modifications. A polyphosphodiester macromonomer (PEPMA·Na) was synthesized via the demethylation of polyphosphotriester macromonomer obtained via the ring-opening polymerization of cyclic phosphoesters using 2-hydroxypropyl methacrylamide as the initiator. The surface modification of PEEK was performed via photoinduced and self-initiated graft polymerization of PEPMA·Na without using any photoinitiators. The amount of phosphorus due to poly(PEPMA·Na) immobilized on PEEK increased with an increase in the photoirradiation time. The PEEK surface turned hydrophilic due to poly(PEPMA·Na) grafting, with almost similar advancing and receding contact angles, implying that the modified PEEK surface (PEEK-g-poly(PEPMA·Na)) was homogeneous. Specimens were mineral coated by simple static soaking in ×1.5 simulated body fluid (1.5SBF) and by an alternative process that included additional soaking steps in 200 mM CaCl₂ aq. and 200 mM K₂HPO₄ aq. before static soaking in 1.5SBF. Specimens were immersed in 1.5SBF for 28 days in simple static soaking, after which the PEEK-g-poly(PEPMA·Na) surface was completely covered with spherical cauliflower-like mineral deposits that resembled octacalcium phosphate (OCP). Their structural similarities were confirmed via X-ray diffraction (XRD), energy dispersive X-ray spectrometry (EDS), and X-ray fluorescence (XRF) analyses. However, these mineral deposits were not observed on the bare PEEK surface. Due to the additional soaking steps (alternative soaking) undertaken before the static soaking of the specimens in 1.5SBF, the mineral coating on the PEEK-g-poly(PEPMA·Na) was dramatically accelerated and the surface was fully covered with mineral deposits in only one day of soaking. The mineral deposits resulting from both the soaking processes had similar structures. Compared with bare PEEK, osteoblastic MC3T3-E1 cells proliferated more actively on mineral-coated PEEK-g-poly(PEPMA·Na). Thus, the surface immobilization of poly(PEPMA·Na) on a PEEK surface is effective for mineral coating and may be useful to provide hard-tissue compatibility on PEEK.