Vulcanization Studies of Elastomers Using Solid-State Carbon-13 NMR

With the use of solid state carbon-13 NMR, changes in the structure of natural rubber and cis-polybutadiene were observed spectroscopically. Cis-trans conversion has been shown to occur in the naturaal rubber by the rearrangement of the allylic free radical. At least four structurally different methyl groups have been detected in the crosslinking of natural rubber by dicumyl peroxide, which indicates that the simple combination of allyic free radical is an oversimplification of the curing process. Quaternary aliphatic carbons have been detected which results from double bond migration. Polybutadiene showed only methine and methylene carbons present in the crosslinked network with a small amount of methyl end-groups. The increase in the line width of the highly crosslinked elastomers was shown to be dominated by the carbon-hydrogen static dipolar interaction. Fourier-transform infrared analysis observed the formation of a molecular complex between dicumyl peroxide and polybutadiene. The formation of trans double bonds was observed in the infrared spectra of polybutadiene. Weak broad bands around 1320 cm−1 were observed in the difference spectrum of cured rubbers and were assigned to carbon-carbon crosslinks. From the structural interpretation of spectra obtained from solid state carbon-13 NMR and Fourier-transform infrared, models are proposed for the crosslinked networks of natural rubber and polybutadiene, obtained from peroxide vulcaniation.