Looking over liquid silicone rubbers: (1) network topology vs chemical formulations

This study proposes a comprehensive study on liquid silicone rubber (LSR) formulations to unravel which components (among functional polydimethylsiloxane polymers and modified silica fillers) improve the mechanical properties of the final materials. In this first part, various industrial products have been deformulated using conventional chemical analyses. The silica content and their surface chemistry were assessed by TGA. Architecture and molar mass of polymers were deduced from (29)Si NMR and SEC in toluene, respectively. Relative concentrations of hydride and vinyl reactive groups and stoichiometric imbalance (r = nSiH/nSiVi) were quantified by proton NMR. Stoichiometric imbalance is slightly higher than 1.5 for cross-linker with hydride functions well redistributed along the chain, whereas for some formulations, r's as high as 3.7 were implemented. These variations has strong implications on the cross-linking density of the final material, since the remaining hydride groups react together and decrease the molar mass between cross-links. From the comparison between formulations, it was shown that hardness adjustment is mainly performed by playing on two parameters: filler content and molar mass between cross-linking points for hardness ranging from 20 to 30 Shore A. Above this limit, it is necessary to modify the silica surface with reactive groups, such as vinyl functions. Surprisingly, two formulations were shown to use a dual cross-linking catalysis systems, peroxide and platinum, leading to efficient and full cure even at lower temperature (typically 140 °C). Network topologies were estimated from the predicted chemistry of the materials in a final discussion part.