Microporous materials are predominantly highly crosslinked network polymers and hence are typically insoluble powders with poor processability. To try and address this we have developed core-shell solvent-dispersible porous polymer particles synthesised by reversible addition-fragmentation chain transfer mediated polymerisation-induced self-assembly (RAFT-mediated PISA) with BET surface areas of up to ~400 m2 g−1.[1] The porous core can be formed from the polymerisation of divinylbenzene and fumaronitrile using a solubilising macromolecular chain transfer agent (macro-CTA) as the outer shell. The particles have been shown to have a dual morphology consisting of smaller spheres of 24–29 nm in diameter aggregated into larger particles of 204–262 nm in diameter. The porous polymer particles were also found to be photoluminescent (emission λmax = 326 nm) when exposed to UV light which could be quenched by the addition of nitroaromatic compounds such as picric acid. Modification of the particles with anthracene functionalities has demonstrated that they can then be used to emit blue light and when used to encapsulate the yellow emitting fluorophore rhodamine B into the core the resulting emsission can be tuned to emit white-light.[2] Functionalized dispersible microporous polymers with divinylbenzene/4-vinylpyridine cores can also be post-synthetically quaternized and used to electrostatically bind the methanol carbonylation catalyst cis-[Rh(CO)2I2]−.[3] Kinetic data for the oxidative addition of iodomethane to immobilized cis-[Rh(CO)2I2]− (the rate-limiting step of the carbonylation cycle) can be measured using in situ using transmission IR spectroscopy. The polymer-supported catalyst was found to be active for carbonylation of MeOH/MeI to give methyl acetate, with an initial rate ca. double that of the homogeneous analogue under the same conditions.

Dispersible microporous polymer particles

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