Role of Bottlebrush Additives on the Structure of Block Copolymers in the Bulk and Thin Films

Sunday, Daniel F.; Richter, Lee J.; Flagg, Lucas Q.; Li, Ruipeng; Murphy, Julia G.; Beaucage, Peter A.; Gann, Eliot

doi:10.1021/acs.macromol.4c00637

Role of Bottlebrush Additives on the Structure of Block Copolymers in the Bulk and Thin Films

Journal Article · Tue Jul 09 00:00:00 EDT 2024 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.4c00637· OSTI ID:2440582

^[1]; ^[1]; ^[1]; Li, Ruipeng ^[2]; ^[1]; ^[1]; Gann, Eliot ^[3]

National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Blending block copolymers (BCP) with additives is a useful approach for controlling BCP morphology and properties. In athermal systems, blends of BCPs with polymer additives having very high molecular (M_n) mass generally result in macrophase separation. Bottlebrush polymers, which consist of a linear backbone and grafted side chains, present an interesting alternative where the overall M_n of the system can be very large but the low M_n side chains may drive miscibility with the BCP. Here, in this study, a bottlebrush with a polynorbornene backbone and polystyrene (PS) side chains is blended with PS-b-poly(methyl methacrylate) (PS-b-PMMA) of varying M_n, and the resulting morphologies are examined in both the bulk and thin films. Two different M_n of PS-b-PMMA were used in the bulk study, and the analysis of small-angle X-ray scattering data shows that the blends were miscible and lamellar at all concentrations. This deviates from reference series of both low and high M_n linear polymer additives, which either showed morphological transitions from lamellae to cylinders (low M_n) or were immiscible at all mass fractions studied (high M_n). The relative molecular mass of the side chain (N_SC) and the corresponding component in the BCP (N_A) dictate the distribution of the bottlebrush throughout the BCP, analogous to BCP/linear blends or grafted nanoparticles in a homopolymer matrix. The studies on thin films show a thickness dependence for bottlebrush mass fractions at or above 0.17, a behavior which may be driven by conformational changes of the bottlebrush upon confinement.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2440582

Report Number(s):: BNL--226026-2024-JAAM

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 14 Vol. 57; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Role of Bottlebrush Additives on the Structure of Block Copolymers in the Bulk and Thin Films

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