Bottlebrush (BB) polymers are a sub-class of branched macromolecules consisting of a central backbone with densely grafted side-chains. Synthetic BB architecture is inspired by a family of proteins known as proteoglycans. Similar to their natural counterparts, synthetic BBs display an interesting combination of high molar mass and low viscosity, thus becoming attractive candidates for applications such as biomimetics, porous membranes, drug delivery, lithographic patterning, and super-soft gels. Methods for achieving synthetic BB architecture have progressed rapidly over last few decades, however definitive structure-property relationships are not well understood due to previous synthetic limitations and overall lack of synthetic variety. BBs derived from flexible polypentenamers provide valuable insight on these structure-property correlations. Polypentenamers contain the same grafting density (<i>n</i><sub>g</sub> = 4) as the more common polynorbornene (PNB) based BBs but are void of rigidifying cyclic tethers in the backbone. The ring opening metathesis polymerization (ROMP) of cyclopentene (CP) derivatives produces a central polypentenamer backbone with initiation sites placed precisely every five carbons from which a vinyl monomer can be grafted via atom transfer radical polymerization (ATRP). This affords flexible polycyclopentene (PCP) BBs with varying graft length, high molar mass, and low dispersity, with great control. The synthetic design and material properties of these more flexible PCP macromolecules will be discussed and compared to PNB BBs.

Structure-property relationships of polypentenamer bottlebrushes

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ACS Fall 2022

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