Surface-Initiated Polymerization as an Enabling Tool for Multifunctional (Nano-)Engineered Hybrid Materials

Abstract

Surface-initiated atom transfer radical polymerization (SI-ATRP) has become an indispensable tool for engineering the structure and properties of polymer/inorganic and polymer/organic interfaces. This article describes the progress and challenges that are associated with the application of SI-ATRP to precisely control the molecular characteristics of polymer chains tethered to nanoparticle surfaces and explores the properties and potential applications of the resulting particle brush materials. Even for the conceptually most “simple” particle brush systemsthat is, spherical particles uniformly grafted with amorphous nonpolar polymersthe complex superposition of interactions as well as time- and length-scales related to particle core and tethered chains provides a rich and largely unexplored parameter space for the design of novel functional materials. The application of the particle brush approach to the development of materials for applications ranging from photonic inks and paints to advanced high “k” dielectrics for energy storage and advanced nanocomposite materials with improved optical, mechanical, or transport characteristics is discussed.

Entropy-driven segregation of polymer-grafted nanoparticles under confinement

“…The average radius of SiO 2 core is R 0 = 7.7 ± 2.1 nm, grafted with PS chains with M n,PS = 54 kg/mol at grafting density of 0.57/nm 2 . The PS−g−SiO 2 particles were synthesized by surface-initiated atom transfer radical polymerization using previously published procedures (32). PS solutions (3% by mass in toluene) were premixed with appropriate amounts of PGNPs (mass ratio of AuPS to PS is 30% to 200%) and flowcoated into thin films of thickness h ≈ 80 nm to 140 nm on silicon substrates.…”

Dielectric performance of high permitivity nanocomposites: impact of polystyrene grafting on BaTiO3 and TiO2

“…[11][12][13][14] Recent advances in surface initiated ATRP and Cu-catalyzed "click" chemistry have led to an increasingly diverse group of polymer grafted, hairy nanoparticles (HNPs) that feature high ε r and refractive index core plus a polymer corona with tunable structure. [15][16][17] Solution cast films of these HNPs without an accompanying polymer matrix have recently been characterized for dielectric performance. Tchoul et al reported that hairy PS@TiO 2 matrix free assemblies at 27% v/v inorganic loading have a relative dielectric constant of 6.4, compared to 2.4 for neat PS, while maintaining low dielectric loss similar to PS (tan δ = 0.04 at 1 kHz).…”

Visible Light-Induced Metal Free Surface Initiated Atom Transfer Radical Polymerization of Methyl Methacrylate on SBA-15

“…Significant advances in this area have been achieved by the development of living radical polymerization techniques, especially as nitroxide-mediated polymerization (NMP) [11,12], reversible addition-fragmentation chain transfer polymerization (RAFT) [13], and atom transfer radical polymerization (ATRP) [14]. Among them, surface initiated atom-transfer radical polymerization (SI-ATRP) has been received much of attentions during the past two decades [2,[15][16][17][18]. So far, polymers with controlled structures and functional side groups can be grafted on various surfaces by SI-ATRP, such as antifouling coatings [19], drug delivery [20], stimuli-responsive materials [21], and nanoporous membranes [22].…”