Large, Rapid Swelling of High-cis Polydicyclopentadiene Aerogels Suitable for Solvent-Responsive Actuators

High-cis polydicyclopentadiene (PDCPD) aerogels were synthesized using ring opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) with a relatively air-stable ditungsten catalytic system, Na[W2(μ-Cl)3Cl4(THF)2]·(THF)3 (W2; (W3W)6+, a′2e′4), and norbornadiene (NBD)as a co-initiator. These aerogels are compared in terms of chemical structure and material properties with literature PDCPD aerogels obtained using well-established Ru-based alkylidenes as catalysts. The use of NBD as a co-initiator enhances the degree of crosslinking versus the more frequently used phenylacetylene (PA), yielding materials with a controlled molecular structure that would persist solvent swelling. Indeed, those PDCPD aerogels absorb selected organic solvents (e.g., chloroform, tetrahydrofuran) and swell rapidly, in some cases up to 4 times their original volume within 10 min, thus showing their potential for applications in chemical sensors and solvent-responsive actuators. The advantage of aerogels versus xerogels or dense polymers for these applications is their open porosity, which provides rapid access of the solvent to their interior, thus decreasing the diffusion distance inside the polymer itself, which in turn accelerates the response to the solvents of interest.