Surface-initiated atom transfer radical polymerization grafting from nanoporous cellulose gels to create hydrophobic nanocomposites

Abstract

Here, we present the preparation of hydrophobic nanoporous cellulose gel-g-poly(glycidyl methacrylate) (NCG-g-PGMA) nanocomposites by surface-initiated atom transfer radical polymerization (SI-ATRP) of glycidyl methacrylate (GMA) monomers and hydrophobic modification with pentadecafluorooctanoyl chloride (C 7 F 15 COCl) on the cellulose nanofibrils of the NCG. The successful grafting of PGMA and hydrophobic modification of C 7 F 15 CO-groups on the NCG was evaluated by Fourier transform infrared (FTIR) spectroscopy. X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirmed that the SI-ATRP and hydrophobic modification did not change the microscopic morphology and structure of the NCG-g-PGMA nanocomposites. Dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) showed remarkable thermomechanical properties and moderate thermal stability. The method has tremendous promise to use NCG as a platform for SI-ATRP and produce new functional NCG-based nanomaterials.

PhotoATRP-Induced Self-Assembly (PhotoATR-PISA) Enables Simplified Synthesis of Responsive Polymer Nanoparticles in One-Pot

“…Unfortunately, none of the PISA samples synthesized provided higher order nanostructures such as vesicles or pure worm-like micelles. Since the polymerization was conducted at ambient temperature, we hypothesized that the glassy nature of the PGMA below T g may cause issues in accessing higher order morphologies . To investigate the validity of this hypothesis, PISA5 and PISA6 were heated to 65 °C post-PISA and the morphological transition was monitored by TEM.…”

“…Since the polymerization was conducted at ambient temperature, we hypothesized that the glassy nature of the PGMA below T g may cause issues in accessing higher order morphologies. 46 To investigate the validity of this hypothesis, PISA5 and PISA6 were heated to 65 °C post-PISA and the morphological transition was monitored by TEM. Interestingly, this thermal annealing allowed the kinetically trapped, asprepared aggregates to transition to worm-like micelles (in gels) and mixtures of beaded worm-like micelles and vesicles for PISA5 and 6, respectively (Figure 4a,b).…”

Surface Fluorination Modification and Anti-Biofouling Study of a pHEMA Hydrogel

“…The characteristic absorption bands at 1200 and 1142 cm –1 could be attributed to stretching vibrations of C–F . The absorption band at 666 cm –1 resulted from the deformation vibration of CF 2 . ,,− Another absorption band at 1780 cm –1 corresponded to the CO of the ester group from F15. − These results confirmed that F15 successfully grafted onto the pHEMA membrane surface.…”

Grafting polymers from cellulose nanocrystals via surface‐initiated atom transfer radical polymerization

“…Surface-initiated ATRP (SI-ATRP) has been widely employed as a very promising and powerful tool to graft polymers from different surfaces. 101,104,[118][119][120][121][122][123][124][125][126] As a "grafting from" method, SI-ATRP allows the grafting of polymer brushes from the surface (flat substrate or nanoparticles) in a controlled manner, with high grafting density. With the assistant of SI-ATRP, a significant amount of amazing hybrid nanomaterials with welldefined polymer brush structures could be precisely prepared for advanced applications.…”

“…Surface‐initiated ATRP (SI‐ATRP) has been widely employed as a very promising and powerful tool to graft polymers from different surfaces 101,104,118–126 . As a “grafting from” method, SI‐ATRP allows the grafting of polymer brushes from the surface (flat substrate or nanoparticles) in a controlled manner, with high grafting density.…”