Reactivity of monoenic and conjugated diene systems present in unsaturated olefin terpolymers—I. Reactions with t-butoxy radicals (CH3)3 CO•

Atarot, H.; Faucitano, A.; Cesca, S.

doi:10.1016/0014-3057(76)90048-3

Cited by 9 publications

References 7 publications

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Reactions of tert‐butoxy radicals with vinyl monomers

Encina

Rivera

Lissi

1978

J. Polym. Sci. Polym. Chem. Ed.

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Tert‐butoxy radicals generated in the photolysis of di‐tert‐butyl peroxide in benzene at 25°C react with vinyl monomers by double‐bond addition and, in most cases, also by competitive hydrogen abstraction. The rate constant for the double‐bond addition changes by a factor of 17 between isoprene, which shows the highest reactivity, and the methacrylate derivatives, which are the least reactive of the monomers considered. The fraction of tert‐butoxy radicals that react by hydrogen abstraction varies considerably with the monomer structure, ranging from 0.9 (cyclohexyl methacrylate) to less than 0.05 (styrene and conjugated diolefins). In the methacrylate derivatives, most of the hydrogen abstraction takes place, not in the α‐methyl group, but in the alkyl chain.

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Reactions of tert‐butoxy radicals with vinyl monomers

Encina

Rivera

Lissi

1978

J. Polym. Sci. Polym. Chem. Ed.

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Model simulation studies of complex free radical reactions: The graft copolymerization of styrene and acrylonitrile onto ethylene‐propylene‐isopropylidendicyclopentadiene terpolymer

Faucitano

Atarot

Martinotti

et al. 1980

J. Polym. Sci. Polym. Chem. Ed.

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A kinetic analysis without steady approximation of the graft copolymerization of styrene‐acrylonitrile onto ethylene‐ propylene‐isopropylidendicyclopentadiene terpolymer (EP‐IPDCP) is described. Some of the kinetic constants were experimentally determined. The grafting process is interpreted mainly in terms of the attack on EP‐IPDCP by benzoyloxy radicals; phenyl radicals play a minor negative role by enhancing the rate of homopolymerization. A major contribution to the grafting yield is made by the propagation steps in graft polymerization and by crossed termination between grafted and ungrafted chains; of minor importance are the cross terminations between ungrafted growing chains and rubber radicals. The ole played by the solvent (benzene) and by saturated and unsaturated units in the EP‐IPDCP chains is analyzed. Diffusion effects caused by the poor solvent compatibility of grafted and ungrafted chains were taken into account by allowing the termination and propagation rate constants to change in a controlled way during the reaction. The trapping of EP‐IPDCP units caused by the aggregation of polymer particles seems to be indispensable to explain the decreasing trend of the grafting efficiency curve. Other information of interest pertains to the distribution of initiating radicals among the various competing reactions in the process and to the data of concentrations versus reaction time for reactants, products, and free radical intermediates. The results of a sensitivity analysis and the rate constants used in the calculations are given.

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Part 2

Howard¹,

Scaiano²

Landolt-Börnstein - Group II Molecules and Radicals

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Reactivity of monoenic and conjugated diene systems present in unsaturated olefin terpolymers—I. Reactions with t-butoxy radicals (CH3)3 CO•

Cited by 9 publications

References 7 publications

Reactions of tert‐butoxy radicals with vinyl monomers

Reactions of tert‐butoxy radicals with vinyl monomers

Model simulation studies of complex free radical reactions: The graft copolymerization of styrene and acrylonitrile onto ethylene‐propylene‐isopropylidendicyclopentadiene terpolymer

Part 2

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