High-Throughput Synthesis and Characterization of Aryl Silicones Using the Piers-Rubinsztajn Reaction

Arylsilicones are widely exploited for their thermal and optical properties. The creation of phenylsilicone elastomers with specific physical properties is typically done by a ‘one off’ formulation and test process. We demonstrate that high‐throughput synthesis methods can be used to rapidly prepare a series of arylsilicone elastomers and then assess the relative impact of different aryl groups on their physical properties. Aromatic groups were incorporated into PDMS elastomers by exploiting the relative reactivity of different functional groups in the Piers‐Rubinsztajn reaction. In order to analyze trends in silicone mechanical properties as a function of increasing aryl concentration – structure/property relationships – libraries of elastomers were both quickly synthesized and characterized using high‐throughput suites starting from low viscosity silicone oils/monomers in 96well plates. Liquid handling parameters were optimized to effectively work with silicones. Incorporating aryl instead of alkyl crosslinkers into the PDMS backbone increased silicone elastomer modulus by ~50 % (at a crosslink density of6%); elastomers prepared with an aromatic crosslinker with 3‐contact points led to much higher moduli vs those with 1‐contact point at the same crosslink density. When located at precise rather than random points on the silicone chains, diphenylsilicones had lower moduli than analogous monophenyl silicones.