Telechelic polyethylene (PE) is of great utility in the production of triblock copolymers, including those that have been used in membrane applications. One well-controlled route to its synthesis is ring-opening metathesis polymerization (ROMP) of cyclooctene in the presence of a chain-transfer agent (CTA), followed by hydrogenation of the backbone olefins. However, hydroxy-telechelic PE (HTPE) is difficult to access via this strategy due to the instability of ruthenium metathesis catalysis in the presence of readily available allylic alcohols. In this work, we report how the conventional protection/deprotection strategy can be circumvented through implementation of an extended olefin–alcohol CTA. The synthesis of HTPE is further streamlined through the application of a tandem ROMP/hydrogenation approach, which harnesses the Ru catalyst for both metathesis and hydrogenation. This efficiency enables the scalable production of HTPE with alcohol end groups that can be subsequently used as initiating sites for the ring-opening polymerization of lactide to prepare poly(lactide)-PE-poly(lactide) triblock copolymers. Melt processing of the resultant PLA-PE-PLA triblock, followed by etching of the PLA domains, results in well-defined, nanoporous PE materials for potential use in a variety of membrane applications.

Efficient synthesis of hydroxy-telechelic polyethylene for nanoporous membranes

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