Elucidating the impact of side chain dispersity on the assembly of bottlebrush polymers at the air‐water interface

Abstract

The synthesis of bottlebrush polymers with discrete side chains, their surface pressure isotherm measurements, and thin film molecular dynamics simulations are reported. Our results show that monolayers of bottlebrushes with discrete side chains achieve higher packing densities and exhibit previously unknown, distinct phase transitions that are unseen in their disperse counterparts. The combination of experimental findings and simulation results show that shape‐defined bottlebrush polymers can advance structure–property relationship studies of branched polymers and the theoretical descriptions of polymer monolayer self‐assembly.

Topologically Precise and Discrete Bottlebrush Polymers: Synthesis, Characterization, and Structure–Property Relationships

“… 24 − 33 Without controlling side-chain dispersity, the permutation of side-chain arrangements in conventional BBPs imposes a significant challenge for understanding their structure–property relationships, 34 especially, at the underexplored regime of low N BB and N SC . 35 , 36 …”

Elucidating the Impact of Structural Parameters on the Glass Transition Temperatures of Bottlebrush Polymers

“…Synthesis of macromonomers and precision bottlebrush polymers Macromonomers were synthesized through a combination of controlled polymerization techniques and chain-end functionalizations. 25,26 Styrene oligomers were first prepared via atom transfer radical polymerization (ATRP) followed by bromine chain end conversion to yield ω-hydroxyl oligo(styrene). As an added advantage to this strategy, traces of non-functional oligomers and other byproducts are easily removed using a plug column to afford synthetically pure OHterminated oligostyrenes, as confirmed through NMR, SEC and TLC analysis (see Supporting Information).…”

“…22,23 Consistent and precise phase separation behaviors were also reported for block copolymers having discrete blocks. 24 The growing importance of suppressing structural heterogeneity for understanding the fundamental properties of brush polymers was also demonstrated in recent reports on precision bottlebrush polymers (PBP, Đside chain = 1.0); 25,26 PBPs display distinct phase transition behavior and high monolayer packing efficiency at the air-water interface.…”

Versatile strategies to tailor the glass transition temperatures of bottlebrush polymers

“…24,25 Consistent and precise phase separation behaviors were also reported for block copolymers having discrete blocks. 26,27 The growing importance of suppressing structural heterogeneity for understanding the fundamental properties of brush polymers was also demonstrated in recent reports on precision bottlebrush polymers (PBP, Đ side chain = 1.0); 28,29 PBPs display distinct phase transition behavior and high monolayer packing efficiency at the air–water interface.…”

“…Macromonomers were synthesized through a combination of controlled polymerization techniques and chain-end functionalizations. 13,22,28,[48][49][50][51][52] Styrene oligomers were first prepared via atom transfer radical polymerization (ATRP) followed by bromine chain end conversion to yield ω-hydroxyl oligo (styrene). As an added advantage to this strategy, traces of nonfunctional oligomers and other byproducts are easily removed using a plug column to afford synthetically pure OH-terminated oligostyrenes, as confirmed through NMR, SEC and TLC analysis (see ESI †).…”