Siloxane-Based Reinforcement of Polysiloxanes: from Supramolecular Interactions to Nanoparticles

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Virginia Tech


Polysiloxanes represent a unique class of synthetic polymers, employing a completely inorganic backbone structure comprised of repeating –(Si–O)n– 'siloxane' main chain linkages. This results in an assortment of diverse properties exclusive to the siloxane bond that clearly distinguish them from the –(C–C)n– backbone of purely organic polymers.

Previous work has elucidated a methodology for fabricating flexible and elastic crosslinked poly(dimethyl siloxane) (PDMS) constructs with high Mc through a simultaneous crosslinking and chain-extension methodology. However, these constructs suffer the poor mechanical properties typical of lower molecular weight crosslinked siloxanes (e.g. modulus, tear strength, and strain at break). Filled PDMS networks represent another important class of elastomers in which fillers, namely silica and siloxane-based fillers, impart improved mechanical properties to otherwise weak PDMS networks. This work demonstrates that proper silicon-based reinforcing agent selection (e.g. siloxane-based MQ copolymer nanoparticles) and incorporation provides a synergistic enhancement to mechanical properties, whilst maintaining a low viscosity liquid composition, at high loading content, without the use of co-solvents or heating. Rheological analysis evaluates the viscosity while photorheology and photocalorimetry measurements evaluate rate and extent of curing of the various MQ-loaded formulations, demonstrating theoretical printability up to 40 wt% MQ copolymer nanoparticle incorporation. Dynamic mechanical analysis (DMA) and tensile testing evaluated thermomechanical and mechanical properties of the cured nanocomposites as a function of MQ loading content, demonstrating a 3-fold increase in ultimate stress at 50 wt% MQ copolymer nanoparticle incorporation. VP AM of the 40 wt% MQ-loaded, photo-active PDMS formulation demonstrates facile amenability of photo-active PDMS formulations with high MQ-loading content to 3D printing processes with promising results.

PDMS polyureas represent an important class of elastomers with unique properties derived from the synergy between the nonpolar nature, unusual flexibility, and low glass transition temperature (Tg) afforded by the backbone siloxane linkages (-Si-O)n- of PDMS and the exceptional hydrogen bond ordering and strength evoked by the bidentate hydrogen bonding of urea. The work herein presents an improved melt polycondensation synthetic methodology, which strategically harnesses the spontaneous pyrolytic degradation of urea to afford a series of PDMS polyureas via reactions at high temperatures in the presence of telechelic amine-terminated oligomeric poly(dimethyl siloxane) (PDMS1.6k-NH2) and optional 1,3-bis(3-aminopropyl)tetramethyldisiloxane (BATS) chain extender. This melt polycondensation approach uniquely circumvents the accustomed prerequisite of isocyanate monomer, solvent, and metal catalysts to afford isocyanate-free PDMS polyureas using bio-derived urea with the only reaction byproduct being ammonia, a fundamental raw ingredient for agricultural and industrial products.

As professed above, reinforcement of polysiloxane materials is ascertained via the incorporation of reinforcing fillers or nanoparticles (typically fumed silica) or blocky or segmented development of polymer chains eliciting microphase separation, in order to cajole the elongation potential of polysiloxanes. Herein, a facile approach is detailed towards the synergistic fortification of PDMS-based materials through a collaborative effort between both primary methods of polysiloxane reinforcement. A novel one-pot methodology towards the facile, in situ incorporation of siloxane-based MQ copolymer nanoparticles into segmented PDMS polyureas to afford MQ-loaded thermoplastic and thermoplastic elastomer PDMS polyureas is detailed. The isocyanate-free melt polycondensation achieves visible melt dispersibility of MQ copolymer nanoparticles (good optical clarity) and affords segmented PDMS polyureas while in the presence of MQ nanoparticles, up to 40 wt% MQ, avoiding post-polymerization solvent based mixing, the only other reported alternative. Incorporation of MQ copolymer nanoparticles into segmented PDMS polyureas provides significant enhancements to modulus and ultimate stress properties: results resemble traditional filler effects and are contrary to previous studies and works discussed in Chapter 2 implementing MQ copolymer nanoparticles into chemically-crosslinked PDMS networks. In situ MQ-loaded, isocyanate-free, segmented PDMS polyureas remain compression moldable, affording transparent, free-standing films.



Siloxane, polysiloxane, poly(dimethyl siloxane) (PDMS), MQ copolymer nanoparticle, vat photopolymerization (VP), additive manufacturing (AM), 3D printing (3DP), 1,3-bis(3-aminopropyl)tetramethyldisiloxane (BATS), chain extender, microphase separation