Grafting from/onto

Acrylonitrile has been grafted onto many polymeric systems. In particular, acrylonitrile grafting has been used to impart hydrophilic behavior to starch (143—145) and polymer fibers (146). Exceptional water absorption capabiUty results from the grafting of acrylonitrile to starch, and the use of 2-acrylamido-2-methylpropanesulfonic acid [15214-89-8] along with acrylonitrile for grafting results in copolymers that can absorb over 5000 times their weight of deionized water (147). 

Grafting reactions alter the physical and mechanical properties of the polymer used as a substrate. Grafting differs from normal chemical modification (e.g., functionalization of polymers) in the possibility of tailoring material properties to a specific end use. For example, cellulose derivatization improves various properties of the original cellulose, but these derivatives cannot compete with many of the petrochemically derived synthetic polymers. Thus, in order to provide a better market position for cellulose derivatives, there is little doubt that further chemical modification is required. Accordingly, grafting of vinyl monomers onto cellulose or cellulose derivatives may improve the intrinsic properties of these polymers. 

By using this technique acrylamide, acrylonitrile, and methyl acrylate were grafted onto cellulose [20]. In this case, oxidative depolymerization of cellulose also occurs and could yield short-lived intermediates [21]. They [21] reported an electron spin resonance spectroscopy study of the affects of different parameters on the rates of formation and decay of free radicals in microcrystalline cellulose and in purified fibrous cotton cellulose. From the results they obtained, they suggested that ceric ions form a chelate with the cellulose molecule, possibly, through the C2 and C3 hydroxyls of the anhy-droglucose unit. Transfer of electrons from the cellulose molecule to Ce(IV) would follow, leading to its reduction... 

Another consequence of the absence of sponataneous transfer and termination reactions is that the polymer chains formed remain living 3), i.e. they carry at the chain end a metal-organic site able to give further reactions. Block copolymer synthesis is probably the major application 12 14), but the preparation of co-functional polymers, some chain extension processes, and the grafting onto reactions arise also directly from the long life time of the active sites. 

The first chiral phases introduced for gas chromatography were either amino acid esters, dipeptide, diamide or carbonyl-bis(amino acid ester) phases [721,724,756-758]. In general, these phases exhitdted poor thermal stability and are infrequently used today. Real interest and progress in chiral separations resulted from the preparation of diamide phases grafted onto a polysiloxane backbone. These phases were thermally stable and could be used to prepare efficient open tubular columns [734,756,758-762]. These phases are prepared from commercially available poly(cyano-propylmethyldimethylsiloxanes) or poly (cyanopropylmethylphenyl-... 

In order to increase the complexity of the peripheral epitopes resulting from the self-assembly process, glycodendrons have been successfully grafted onto various ligands, allowing the formation of dense glycocomplexes. Indeed, in most of the examples, branching of the dendrimers produces a microenvironment that... 

After photopolymerization of a certain monomer for a given time, the polymerization mixture was poured into excess precipitant to isolate the polymer, which was then extracted with a solvent to separate the polymer grafted onto the PSG from the homopolymer. 

The various spectroscopic techniques had revealed that Ti4+ ions in TS-1, Ti-beta and, Ti-MCM-41 are 4-coordinate in the dehydrated state. Tetrapodal Ti(OSi)4 and tripodal Ti(OH)(OSi)3 are the main Ti species. Upon exposure to H20, NH3, H202, or TBHP, they increase their coordination number to 5 or 6. On samples in which the Ti4+ has been grafted onto the silica (referred to as Ti f MCM-41), a dipodal Ti species (Ti(OH)2(OSi)2) may also be present. As a result of interaction with the oxidant ROOH (R = H, alkyl), the formation of 7)1- and p2-peroxo (Ti-O-O-), hydroperoxo (Ti-OOH), and superoxo (Ti02 ) species has been observed experimentally (Section III). A linear correlation between the concentration of the p2-hydroperoxo species and the catalytic activity for propene epoxidation has also been noted from vibration spectroscopy (133). 

Scheme 3. Synthetic routes leading to various rod-coil block copolymers via grafting onto" (16a, 16b, 20) or grafting from" (18) reactions.

Grafting from method, 7 652-653 Grafting onto method, 7 654 Grafting process, 73 537 Grafting through method, 7 653 Graft polymerization. See also Graft copolymerization ABS, 7 419, 421 acrylic ester monomers, 7 386 of methacrylic ester polymers, 76 289-290... 

---