Polystyrene--Polydimethylsiloxane as a Potential Silica Substitute for Polysiloxane Reinforcement.

Here we report microphase-separated poly(styrene--dimethylsiloxane) (PS--PDMS) as a reinforcing filler in PDMS thermosets that overcomes the long-standing problem of aging in the processing of silica-reinforced silicone. Surprisingly, PS--PDMS reinforced composites display comparable mechanical performance to silica-modified analogs, even though the modulus of PS is much smaller than that of silica and there is no evidence of percolation with respect to the rigid PS domains. We have found that a few unique characteristics contribute to the reinforcing performance of PS--PDMS. The strong self-assembly behavior promotes batch-to-batch repeatability by having well-dispersed fillers. The structure and size of the fillers depend on the loading and characteristics of both filler and matrix, along with the shear effect. The reinforcing effect of PS--PDMS is mostly brought by the entanglements between the corona layer of the filler and the matrix, rather than the hydrodynamic reinforcement of the PS phase.