Bottlebrush Block Copolymers at the Interface of Immiscible Liquids: Adsorption and Lateral Packing

Seong, Hong-Gyu; Jin, Zichen; Chen, Zhan; Hu, Mingqiu; Emrick, Todd; Russell, Thomas P.

doi:10.1021/jacs.3c13817

Title: Bottlebrush Block Copolymers at the Interface of Immiscible Liquids: Adsorption and Lateral Packing

Journal Article · 06 May 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c13817 · OSTI ID:2429604

Seong, Hong-Gyu ^[1]; Jin, Zichen ^[1]; Chen, Zhan ^[1];

^[1];

^[2]

University of Massachusetts, Amherst, MA (United States)
University of Massachusetts, Amherst, MA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Amphiphilic bottlebrush block copolymers (BBCPs), having a hydrophilic bottlebrush polymer (BP) linked covalently to a hydrophobic BP, were found to segregate to liquid-liquid interfaces to minimize the free energy of the system. The key parameter influencing the outcome of the experiments is the ratio between the degree of polymerization of the backbone (NBB) and that of the side-chain brushes (NSC). Specifically, a spherical, star-like configuration results when NBB < NSC, while a cylindrical, bottlebrush-like shape is preferred when NBB > NSC. Dynamic interfacial tension (γ) and fluorescence recovery after photobleaching (FRAP) measurements show that the BBCP configuration influences the areal density and in-plane diffusion at the fluid interface. The characteristic relaxation times associated with BBCP adsorption (τA) and reorganization (τR) were determined by fitting time-dependent interfacial tension measurements to a sum of two exponential relaxation functions. Both τA and τR initially increased with NBB up to 92 repeat units, due to the larger hydrodynamic radius in solution and slower in-plane diffusivity, attributed to a shorter cross-sectional diameter of the side-chains near the block junction. This trend reversed at NBB = 190, with shorter τA and τR attributed to increased segregation strength and exposure of the bare water/toluene interface due to tilting and/or wiggling of the backbone chains, respectively. The adsorption energy barrier decreased with higher NBB, due to a reduced BBCP packing density at the fluid interface. In conclusion, this study provides fundamental insights into macromolecular assembly at fluid interfaces, as it pertains to unique bottlebrush block architectures.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); US Army Research Office (ARO)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2429604

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 19 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Adsorption
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Title: Bottlebrush Block Copolymers at the Interface of Immiscible Liquids: Adsorption and Lateral Packing

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