Cellulose fibers have been successfully grafted with poly(methyl acrylate) using atom transfer radical polymerization, mediated by Me6-TREN and Cu(I)Br at ambient temperature. The initially hydrophilic cellulose was first modified by reacting the hydrozyl groups with 2-bromoisobutyryl bromide whereupon methyl acrylate was grafted from the surface. The resulting polymer-grafted papers were extremely hydrophobic, thetaa = 133 degrees . FT-IR analysis indicates that the amount of grafted polymer can be controlled by adding sacrificial initiator to the polymerizing system. Size exclusion chromatography of the bulk polymer revealed narrow polydispersities and a molecular weight corresponding to the ratio [M]:[I].
Cellulose fibers, in the form of a conventional filter paper, have been modified by reacting the hydroxyl groups on the fiber surface with 2-bromoisobutyryl bromide, followed by grafting using ATRP conditions. The papers were first grafted with methyl acrylate (MA), rendering the paper very hydrophobic as reported in an earlier work. The papers were analyzed by gravimetry, FT-IR, ESCA, and AFM. To verify that the polymerization from the surface was "living", a second layer of another, hydrophilic, polymer, 2-hydroxyethyl methacrylate (HEMA), was grafted upon the PMA layer, creating a block-copolymer graft from the fibers. After the layer of PHEMA had been attached, contact angle measurements were no longer possible, because of the absorbing nature of PHEMA-grafted layer. This indicates that a copolymer had indeed been formed on the surface. FT-IR showed a large increase in carbonyl content after the PHEMA-grafting, which further proves that a layer of PHEMA was attached to the PMA layer. This goes to show that the hydrophilic/hydrophobic behavior of a cellulose surface can be tailored by the use of "living"/controlled radical polymerization methods such as ATRP.
Dendritic polymers are highly branched, globular architectures with multiple representations of functional groups. These nanoscale organic frameworks continue to fascinate researchers worldwide and are today under intensive investigation in application-driven research. A large number of potential application areas have been suggested for dendritic polymers, including theranostics, biosensors, optics, adhesives and coatings. The transition from potential to real applications is strongly dictated by their commercial accessibility, scaffolding ability as well as biocompatibility. A dendritic family that fulfills these requirements is based on the 2,2-bismethylolpropionic acid (bis-MPA) monomer. This critical review is the first of its kind to cover most of the research activities generated on aliphatic polyester dendritic architectures based on bis-MPA. It is apparent that these scaffolds will continue to be in the forefront of cutting-edge research as their structural variations are endless including dendrons, dendrimers, hyperbranched polymers, dendritic-linear hybrids and their hybridization with inorganic surfaces.
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