Grafting polymer brushes by ATRP from functionalized poly(ether ether ketone) microparticles

Abstract

Poly(ether ether ketone) (PEEK) is a semi-crystalline thermoplastic with excellent mechanical and chemical properties. PEEK exhibits a high degree of resistance to thermal, chemical, and bio-degradation. PEEK is used as a biomaterial in the field of orthopedic and dental implants; however, due to its intrinsic hydrophobicity and inert surface, PEEK does not effectively support bone growth. Therefore, new methods to modify PEEK's surface to improve osseointegration are key to next-generation polymer implant materials. Unfortunately, PEEK is a challenging material to both modify and subsequently characterize thus stymieing efforts to improve PEEK osseointegration. In this manuscript, we demonstrate how surface-initiated atom transfer radical polymerization can be used to modify novel PEEK microparticles (PMP). The hard core-soft shell microparticles were synthesized and characterized by dynamic light scattering, attenuated total reflection-infrared, X-ray photoelectron spectroscopy, and transmission electron microscopy, indicating the grafted materials increased solubility and stability in a range of solvents. The discovered surface grafted PMP can be used as compatibilizers for the polymer-tissue interface.

State-of-the-art polyetheretherketone three-dimensional printing and multifunctional modification for dental implants

“… (A) Changes in PEEK chemical bonds after different plasma treatments ( Fu et al, 2021a ). (B) Bending (a) and tensile (b) strength tests of 30 wt% short CF-reinforced PEEK and 60 wt% continuous CF-reinforced PEEK ( Zhou et al, 2022 ).…”

Hydrophilic Poly(meth)acrylates by Controlled Radical Branching Polymerization: Hyperbranching and Fragmentation

“…ATRP of acrylates in water is still considered a challenge due to potential hydrolysis of the C­(sp 3 )–X (secondary halides are more prone to hydrolysis than tertiary), leading to loss of chain-end functionality since the C­(sp 3 )–OH cannot participate in further chain growth. − Second, the high values of equilibrium constant of ATRP in water lead to a high concentration of radicals, which may result in more dead chains. , These challenges shall be even more pronounced during the controlled synthesis of hyperbranched acrylates using inibramers because their incorporation enhances the concentration of radicals. , Recently, we extended the scope EY/Cu photocatalyzed ATRP resulting in well-defined water-soluble linear acrylates under biorelevant conditions − using low-energy green light. , The use of Cu II /Me 6 TREN as deactivator and EY at ppm levels in 1× phosphate-buffered saline (PBS) medium suppressed the dissociation of the [X–Cu II /L] + deactivators and disproportionation of Cu I species to Cu II and Cu 0 thereby maintaining equilibrium throughout ATRP.…”

“… 61 , 62 These challenges shall be even more pronounced during the controlled synthesis of hyperbranched acrylates using inibramers because their incorporation enhances the concentration of radicals. 63 , 64 Recently, we extended the scope EY/Cu photocatalyzed ATRP 65 resulting in well-defined water-soluble linear acrylates under biorelevant conditions 66 − 68 using low-energy green light. 69 , 70 The use of Cu II /Me 6 TREN as deactivator and EY at ppm levels in 1× phosphate-buffered saline (PBS) medium suppressed the dissociation of the [X–Cu II /L] + deactivators and disproportionation of Cu I species to Cu II and Cu 0 thereby maintaining equilibrium throughout ATRP.…”