Amphiphilic silica/fluoropolymer nanoparticles: Synthesis, tem‐responsive and surface properties as protein‐resistance coatings

Abstract

ABSTRACTA series of amphiphilic silica/fluoropolymer nanoparticles of SiO2‐g‐P(PEGMA)‐b‐P(12FMA) were prepared by silica surface‐initiating atom transfer radical polymerization (SI‐ATRP) of poly(ethylene glycol) methyl ether methacrylate (PEGMA) and poly dodecafluoroheptyl methacrylate (P12FMA). Their amphiphilic behavior, lower critical solution temperature (LCST), and surface properties as protein‐resistance coatings were characterized. The introduction of hydrophobic P(12FMA) block leads SiO2‐g‐P(PEGMA)‐b‐P(12FMA) to form individual spherical nanoparticles (∼150 nm in water and ∼170 nm in THF solution) as P(PEGMA)‐b‐P(12FMA) shell grafted on SiO2 core (∼130 nm), to gain obvious lower LCST at 36–52 °C and higher thermostability at 290–320 °C than SiO2‐g‐P(PEGMA) (LCST = 78–90 °C, Td = 220 °C). The water‐casted SiO2‐g‐P(PEGMA)‐b‐P(12FMA) films obtain much rougher surface (125.3–178.4 nm) than THF‐casted films (11.5–16.9 nm) and all SiO2‐g‐P(PEGMA) films (26.8–31.3 nm). Therefore, the water‐casted surfaces exhibit obvious higher water adsorption amount (Δf = −494 ∼ −426 Hz) and harder adsorbed layer (viscoelasticity of ΔD/Δf = −0.28 ∼ −0.36 × 10−6/Hz) than SiO2‐g‐P(PEGMA) films, but present loser adsorbed layer than THF‐casted films (ΔD/Δf = −0.29 ∼ −0.63 × 10−6/Hz). While, the introduction of P(12FMA) segments does not show obviously reduce in the protein‐repelling adsorption of SiO2‐g‐P(PEGMA)‐b‐P(12FMA) films (△f = −15.7 ∼ −22.3 Hz) compared with SiO2‐g‐P(PEGMA) films (△f = −8.3 ∼ −11.3 Hz) and no obvious influence on water adsorption of ancient stone. Therefore, SiO2‐g‐P(PEGMA)‐b‐P(12FMA) is suggested to be used as protein‐resistance coatings. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 381–393