Free-Radical Grafting Reactions to Polymers with Double Bonds

Free-Radical Grafting Reactions to Polymers with Double Bonds 

As the concentration of rubber increases, the length of the grafted branches diminishes, while their number remains the same. 

When the concentration of the initiator increases, the length of the branches diminishes, but the number of branches increases. 

Grafting reactions to polybutadiene, however, proceed via chain transferring from the growing chain radical to the backbone [299]. Nevertheless, strong evidence also shows that the initiator radicals can interact directly with polymeric backbones [299, 300]. 

When graft copolymers of polystyrene to natural mbber form, the chain length of the attached branches equals to the chain lengths of the unattached polystyrene homopolymer that forms simultaneously [301]. This led to the following conclusions [303]  

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Discuss free-radical grafting reactions to polymers with double bonds. Give examples and show reactions. 

ESR can equally be used for detection of radicals in masticated rubber their identification in relation to the chemical structure might be approached with specific techniques such as electron nuclear double resonance (ENDOR). ESR studies also contribute to the understanding of the char forming process of various polymers [815], to the study of mechanical fracture, which produces free radicals, grafting reactions, etc. Pedulli et al. [816,817] have determined the bond dissociation enthalpies of a-tocopherol and other phenolic AOs by means of ESR. The determination of the O—H bond dissociation enthalpies of phenolic molecules is of considerable practical interest since this class of chemical compounds includes most of the synthetic and naturally occurring antioxidants which exert their action via an initial hydrogen transfer reaction whose rate constant depends on the strength of the O—H bond. 

When unsaturatcd polymers have hydrogen or halogen atoms in a-position to the double bonds, they are especially sensitive to chain transfer by a free radical attack. Therefore in these cases, the graft copolymerization may involve a combination of two initiation processes which occur simultaneously and compete with each other, one by chain transfer, the other by addition copolymerization. The relative importance of both processes is again dependent on the nature of the polymerizing monomer and of the backbone polymer involved in the reaction. 

Graft Copolymers. In graft copolymerization, a preformed polymer with residual double bonds or active hydrogens is either dispersed or dissolved in the monomer in the absence or presence of a solvent. On this backbone, the monomer is grafted in free-radical reaction. Impact polystyrene is made commercially in three steps first, solid polybutadiene rubber is cut and dispersed as small particles in styrene monomer. Secondly, bulk prepolymerization and thirdly, completion of the polymerization in either bulk or aqueous suspension is made. During the prepolymerization step, styrene starts to polymerize by itself forming droplets of polystyrene with phase separation. When equal phase volumes are attained, phase inversion occurs. The droplets of polystyrene become the continuous phase in which the rubber particles are dispersed. R. L. Kruse has determined the solubility parameter for the phase equilibrium. 

This was followed by casting a film, drying, and raising the temperature to induce crosslinking. For example, the urethane polymer was crosslinked thermally by reaction with triols, while the polyacrylate was essentially crosslinked through sulfur and double bonds by a free-radical process. In this manner, grafting reactions between the two polymers were minimized. 

Grafting a second polymer to the NR molecule in the latex stage is one of the many routes to chemically modified NR. An olefinic monomer with unsaturated double bonds such as methyl methacrylate (MMA), styrene and acrylonitrile are important monomers used for such grafting. " For example, MMA monomer is first converted into an emulsion with some suitable emulsifiers and then mixed with NR latex to copolymerize the monomer in a seeded emulsion polymerization process. It is important to ensure the seed latex particles are saturated with the monomer supplied through diffusion from the emulsified monomer droplets. An oil- or water-soluble initiator can be used to start the reaction. With proper control of the system and reaction conditions, the free radical reaction can be made to propagate within the latex particles as far as possible, so that only grafted NR occurs, without the formation of free homopolymer from the monomer. In this way only chemically modified NR... 

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