Semiquantitative Solid-State NMR Study of the Adsorption of Soybean Oils on Silica and Its Significance for Rubber Processing.

Soybean oil (SBO) is a renewable material used as an alternative to conventional petroleum-derived oils in the processing of rubber composites. Upon chemical modifications, such as epoxidation, its performance in the processing of rubber can be significantly improved, as indicated by a considerable reduction of the mixing energy. Although it has been hypothesized that hydrogen bonding between functional groups (e.g., epoxy) of SBOs and silanols present on the silica surface plays a key role, there is still a lack of direct evidence supporting this hypothesis. In this work, it is demonstrated that there is an overall correlation between the epoxy concentration of SBOs and the mixing energy, consistent with the long-held hypothesis. In particular, a correlation between the SBO-silica adsorption affinity and the degree of epoxidation is revealed by a set of surface-selective solid-state nuclear magnetic resonance (ssNMR) experiments. In addition, the surface-selective ssNMR technique demonstrated in this work could also be used to evaluate the adsorption affinity of other oils and/or additives more broadly.

Sensitivity enhancement via multiple contacts in the {1H-29Si}-1H cross polarization experiment: a case study of modified silica nanoparticle surfaces.

{1H-29Si}-1H double cross polarization inverse detection (DCPi) solid-state NMR, has recently been shown to be a powerful tool for studying molecules adsorbed on the silica surface. In this contribution, we develop an improved version (MCPi) which incorporates a block of multiple contact pulses, and quantitatively compare the sensitivities of MCPi and DCPi over a typical range of experimental parameters. The MCPi pulse sequence aims at higher sensitivity and robustness for studying samples with various relaxation characteristics. In the case of dimethyl sulfoxide (DMSO) molecules adsorbed on the silica surface, MCPi performs equally well or up to 2.5 times better than DCPi over a wide range of parameters. The applicability to and performance of MCPi on composite materials was demonstrated using a sample of polymer-silica composite, where significantly higher sensitivity could be achieved at very long total mixing times. The results also showed that both techniques are surface specific in the sense that only the groups close to the surface can be detected.