Hairy Nanospheres by Gelation of Reactive Block Copolymer Micelles

Abstract

Summary: A novel way to prepare polymer hair/polysilsesquioxane core hybrid nanospheres is presented based on a self‐assembly and gelation process of a reactive block copolymer, poly(ethylene oxide)‐block‐poly[3‐(trimethoxysilyl)propyl methacrylate] (PEO113‐b‐PTMSPMA206). Nanospheres of uniform size were obtained. Transmission electron microscopy (TEM), dynamic light scattering (DLS), and static light scattering (SLS) were employed to characterize the products.Schematic of the PEO‐b‐PTMSPMA nanospheres formed here, the light gray part represents the PEO hairs, the dark parts are the polysilsesquioxane from the gelation of the PTMSPMA blocks of the self‐assembled sphere.imageSchematic of the PEO‐b‐PTMSPMA nanospheres formed here, the light gray part represents the PEO hairs, the dark parts are the polysilsesquioxane from the gelation of the PTMSPMA blocks of the self‐assembled sphere.

Micellar behavior of well‐defined polystyrene‐based block copolymers with triethoxysilyl reactive groups and their hydrolysis–condensation

“…The alkoxysilyl functionality can be either distributed along the chain in statistical copolymers as in the aforementioned examples12, 13 or be introduced at the end of polymer chains 14. Very recently, well‐defined block copolymer architectures in which one block is composed of MPTMS repeat units have been achieved by controlled radical polymerizations 15–29. For instance, Koh et al15 reported the successful synthesis of multiblock copolymers based on methyl methacrylate (MMA), poly(ethylene) glycol methyl ether methacrylate and MPTMS by atom‐transfer radical polymerization (ATRP).…”

“…For instance, Koh et al15 reported the successful synthesis of multiblock copolymers based on methyl methacrylate (MMA), poly(ethylene) glycol methyl ether methacrylate and MPTMS by atom‐transfer radical polymerization (ATRP). Chen et al16–22 described the synthesis of reactive amphiphilic poly(ethylene oxide)‐ b ‐poly(MPTMS) (PEO‐ b ‐PMPTMS) diblock copolymers by ATRP. Mellon et al23 reported for the first time the reversible addition‐fragmentation chain transfer (RAFT) polymerization of MPTMS and copolymerization of MPTMS with MMA.…”

Hybrid Silicon‐Based Organic/Inorganic Block Copolymers with Sol–Gel Active Moieties: Synthetic Advances, Self‐Assembly and Applications in Biomedicine and Materials Science

“…For the block copolymers PEO 45 ‐ b ‐PTMSPMA x with x= 42 or 59, the self‐assembled structures formed in MeOH/water could be changed by adjusting the water content: spheres, lamellae, rods or vesicles, the latest being obtained at higher water content (>40 wt %) . For PEO 113 ‐ b ‐PTMSPMA 206 with a higher PTMSPMA to PEO ratio of ≈2, micellar nanostructures were formed in MeOH/water . A similar block copolymer based on a silicon‐based monomer with a bulkier group, namely PTESPMA, was studied by the same group .…”

Gelation Inside Block Copolymer Aggregates and Organic/Inorganic Nanohybrids

“…When the PEO segment of PEO‐ b ‐PTMSPMA is longer, PEO 113 ‐ b ‐PTMSPMA x , the aggregation in a methanol/water mixture produces simple spherical micelles exclusively 25. After gelation in the core, nearly monodisperse spherical particles with a polysiloxane core embedded in a PEO corona are obtained, as indicated in Figure 5A.…”