Adsorption of polybutadiene terminated with a very polar functional group (T-PBR) on a silica surface from carbon tetrachloride solution has been investigated by using IR spectroscopy and compared with normal polybutadienes (PBR). Carbon tetrachloride is a good solvent for polybutadiene. The adsorbed amount, A, the surface coverage of the silanol groups, and the bound fraction of a polymer chain p were measured. A marked difference in adsorption behavior between T-PBR and PBR polymers was observed. T-PBR has an A and twice as large as those for PBR, while the p value was approximately the same for both polymers. From the chemical structure of the terminal group we can qualitatively interpret the difference in the adsorption behavior by taking into account the preferential adsorption of the terminal polar functional groups over the double-bond groups in polybutadiene chains onto the silanol groups of silica surface.
From the Part I experiments, n-butyl-EAB shows a strong interaction (chemisorption) with the carbon black surface. The chemical structure of chemisorbed n-butyl-EAB is similar to that of the component, with a peak at 290 nm. The EAB groups of the chain-ends in the modified polymer enhance the adsorption of the polymer onto CB-N, because of a chemisorption by the EAB groups. We estimate that the reaction mechanism of chemisorption is an acid-base reaction and that SBR-EAB has a conformation somewhat rising in the radial direction on the CB-N surfaces. From the Part II experiments, the saturated adsorption of n-butyl-EAB or the chemically-modified polymer prevents the agglomerate-growth of carbon black and enhances the dispersion stability of the carbon black dispersed in a nonpolar solvent such as benzene. From the Part III experiments, the chemically-modified rubber absorbed strongly onto the CB-N surface enhances the dispersion stability of the carbon black in vulcanizates, and, hence, suppresses the transient-structure formation or network formation of carbon-black-carbon-black particles. The reduction in the transient structure decreases the dynamic-shear modulus at low strain amplitude and, hence, decreases the loss modulus maximum G″max, causing the increase of rebound resilience.
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