Electron spin resonance study of free radicals in the radiation grafting of butadiene to poly(vinyl chloride)

Journal Article · Tue Jan 01 04:00:00 EST 1974 · J. Polym. Sci.; (United States)

DOI:https://doi.org/10.1002/pol.1974.180120613· OSTI ID:6811830

Hamanoue, K; Shimizu, M; Higaki, H; Block, I; Silverman, J

The kinetics of the disappearance of propagating butadiene radicals produced in the grafting of butadiene to poly(vinyl chloride) was followed by electron spin resonance measurements. The radical species observed in the temperature range 213-298/sup 0/K is the conjugated allylic radical: --CH/sub 2/--CH==CH--CH/sub 2/ reversible --CH/sub 2/--CH--CH==CH/sub 2/. The reaction conditions were adjusted to provide a highly viscous medium in which the propagation reaction took place. Under these conditions the radicals were stabilized and a precise ESR spectrum was obtained. Arrhenius plots of the second-order decay rate constants yield an activation energy of 5 kcal/mole. This suggests that the bimolecular termination reaction is controlled by the segmental motion of the grafted side chains.

• Research Organization: Univ. of Maryland, College Park
• OSTI ID: 6811830
• Journal Information: J. Polym. Sci.; (United States), Journal Name: J. Polym. Sci.; (United States) Vol. 12; ISSN JPSCA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ACTIVATION ENERGY
BUTADIENE
CHEMICAL RADIATION EFFECTS
CHEMISTRY
CHLORINATED ALIPHATIC HYDROCARBONS
DIENES
ELECTRON SPIN RESONANCE
ENERGY
GRAFT POLYMERS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
MAGNETIC RESONANCE
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC POLYMERS
POLYENES
POLYMERS
POLYVINYLS
PVC
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RESONANCE