Poly free-radical grafting reactions

Deters (14) vibromilled a blend of cellulose and cellulose triacetate. The acetic acid content of cellulose acetate decreased with grinding time (40 h) while that of the cellulose increased, suggesting the formation of a block or graft copolymer or of an esterification reaction by acetic acid developed by mechanical reaction. Baramboim (/5) dissolved separately in CO polystyrene, poly(methyl methacrylate), and poly(vinyl acetate). After mixing equal volumes of solutions of equivalent polymer concentration, the solvent was evaporated at 50° C under vacuum and the resultant product ball-milled. The examination of the ball-milled products showed the formation of free radicals which copolymerized. 

The results suggests that the copolymer has a graft structure and that the mastication medium involves three kinds of domains. The first is the inner domain of poly(vinyl chloride) which is only slightly penetrated by monomer. Polymerization is initiated by macroradicals created in the PVC domain causing the formation of a true copolymer. Short radical segments arising from transfer reactions migrate into the third external domain which consists practically entirely of pure monomer and there initiate polymerization. The second domain is the surface of the resin particle which is swollen by monomer. The free radicals created by bond rupture appear in this second domain. 

The morphology of the fibrous cellulose graft copolymers depended on the method of initiation of free radical formation, experimental conditions during the copolymerization, chemical modification of the cellulose before reaction, and the type of monomer used (60). Variations in the shape of the fibrous cross section, in layering effects in the fiber, and in the location and distribution of the grafted copolymer in the fiber were observed by electron microscopy (61). Cotton cellulose—poly (acrylonitrile) copolymer was selected to show the possible variations in location and distribution of the grafted copolymer in the fiber. 

The reaction scheme for graft copolyelectrolyte synthesis by free radical copolymerization according to the macromonomer technique is shown in Scheme 15. Besides the aspect of how to control the constitution of the graft copolyelectrolyte, suitable characterization techniques for unequivocal proof of the attained copolymer structure will also be elucidated. The synthesis, characterization and properties of the inversely structured poly(acrylic acid)-g-polystyrene graft copolymers it are covered in another article in this volume [178]. 

The free radical polymerization of styrene initialized by iniferter is influenced by chemical binding of iniferter on the surface of the silica." This reaction is used for grafting the polymer onto the surface of the silica. A similar approach is used when carbon whisker is incorporated during the graft-polymerization of methyl methacrylate. Depending on how the whisker is prepared, surface conversion can be increased up to twelve times compared to a polymerization with no whisker present. The addition of graphite to the poly esterification reaction doubles the molecular weight of the polymer. ... 

Better control of grafting and less homopolymer formation is achievable in ionic reactions than can be obtained in free-radical reactions. Anionic grafting via backbone initiation has been demonstrated (22) with caprolacteim on macromolecular ester sites of styrene/methyl methacrylate copolymers. Cationic grafting of isobutylene onto poly(vinyl chloride) with the aid of aluminum alkyl has been carried out by J. P. Kennedy (23). 

Polymer radicals having free radical centers on the backbone chain (to initiate graft copolymerization) can also be produced by irradiation of a polymer-monomer mixture with ionizing radiation. For example, poly(ethylene-grq/i-styrene) can be produced by the irradiation of a monomer-swollen polymer and the initiation reactions can be represented (Odian, 1991) by... 

Because the free radical initiated graft reaction can also lead to the cross-linking of polyethylene, copolymers of ethylene and with acrylic acid (184,185), glycidyl methacrylate (184,186), methacrylic acid and 10-undecenoic acid (187-189) were synthesized to compatibilize polyethylene/polyamide blends. The poly (ethylene-co-methacrylic acid) ionomers neutralized by sodium (184) and zinc (45,118,190-192) has also used as compatibilizers. High energy irradiation, used to modify the surface of fibers or films at beginning, was also used to compatibilize the polyethylene/polyamide blends (193-196). 

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