THE RADIATION INDUCED cis-trans ISOMERIZATION OF POLYBUTADIENE. I

Journal Article · Sat Apr 19 23:00:00 EST 1958 · Journal of the American Chemical Society (U.S.)

DOI:https://doi.org/10.1021/ja01541a004· OSTI ID:4347626

Golub, M A

The cis double bonds in a high cis-polybutadiene in solution are readily convented into trans double bonds on exposure to gamma -rays in the presence of a suitable sensitizer such as an organic bromide. The isomerization proceeds in the direction of attaining an equllibrium cis/trans ratio of approximately 5/95. This reaction is analogous to the recently reported photosensitized cis-trans isomerization of polybutadiene. In addition, a very much slower ''unsensitized'' radiation induced isomerization of the double bonds was also observed in solution. However, no change in cis/trans ratio could be obtained on gamma -irradiation of the solid polymer. The kinetics of the isomerization of polybutadiene in benzene were studied using allyl bromide, thyl bromide and ethylene bromide as sensitizers, and found to be first order with respect to the cis content in the polymer and somewhat less than half-order in organic bromide. The mechanism is considered to involve pi complexing between the double bonds and free bromine atoms formed in the radiolysis of the bromide. An interesting application of this isomerization is its possible use as a dosimeter in radiation chemistry. (auth)

• Research Organization: B.F. Goodrich Co. Research Center, Brecksville, Ohio
• Sponsoring Organization: USDOE
• NSA Number: NSA-12-009064
• OSTI ID: 4347626
• Journal Information: Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 80; ISSN JACSA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

ALLYL RADICALS
BENZENE
BROMIDES
BUTADIENE
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DECOMPOSITION
ETHYL RADICALS
ETHYLENE
FREE RADICALS
GAMMA RADIATION
ISOMERS
MEASURED VALUES
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
POLYMERS
QUANTITY RATIO
RADIATION DOSES
RADIATION EFFECTS
REACTION KINETICS
SENSITIVITY
SOLIDS
SOLUTIONS
USES