Our group proposes a novel synthetic pathway, without anionic polymerization, that will allow porous monolithic polymers to be synthesized from commercial poly(ethylene glycol) (PEG) starting materials. Ultimately, we intend to use these materials as scaffolding for metal catalysts as we hypothesize that the rigid structure of the porous monolithic polymer will provide site isolation of the catalytic sites and thereby permit multiple, incompatible catalysts to work in tandem. To access the target porous polymer monoliths, three different polymers are incorporated: polyethylene glycol (PEG), polylactide (PLA), and polystyrene (PS). Starting from commercial PEG, a trithiocarbonate chain transfer agent (CTA) was appended by transesterification to form a mixture of unmodified PEG, PEG with a single CTA appended, and PEG with CTA on both sides. Chain extension with rac-lactide again provides a mixture of materials, though the difference in solubility allows the isolation of the desired PLA-block-PEG-CTA. Chain extension by reversible addition-fragmentation chain transfer polymerization (RAFT) provides access to the linear triblock polymer: PLA-block-PEG-block-PS. To access the desired monolithic material, this RAFT reaction will be modified to include a crosslinker, and the porous material will be made by etching the PLA block. Each synthesized polymer has been characterized by nuclear magnetic resonance spectroscopy and gel permeation chromatography.

Asymmetric PEG functionalization and block polymer synthesis

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