Modular Approach for the Synthesis of Bottlebrush Diblock Copolymers from Poly(Glycidyl Methacrylate)-block-Poly(Vinyldimethylazlactone) Backbones

Hu, Bin; Carrillo, Jan-Michael; Collins, Liam; Silmore, Kevin S.; Keum, Jong; Bonnesen, Peter V.; Wang, Yangyang; Retterer, Scott; Kumar, Rajeev; Lokitz, Bradley S.

doi:10.1021/acs.macromol.1c01849

Modular Approach for the Synthesis of Bottlebrush Diblock Copolymers from Poly(Glycidyl Methacrylate)-block-Poly(Vinyldimethylazlactone) Backbones

Journal Article · Fri Jan 07 00:00:00 EST 2022 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.1c01849· OSTI ID:1840213

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

A strategy that enables the facile synthesis of bottlebrush block copolymers with flexible backbones was developed. A demonstration of the strategy’s utility was carried out by grafting end-functionalized polymethylmethacrylate (PMMA) and polystyrene (PS) to the dually reactive block copolymer, poly(glycidyl methacrylate)-block-poly(vinyldimethylazlactone) (PGMA-b-PVDMA). Five different bottlebrush diblock copolymers were investigated by size-exclusion chromatography (SEC), 1H NMR, Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray scattering methods, atomic force microscopy (AFM), rheology and computational simulations using molecular dynamics (MD), and self-consistent field theory (SCFT). A relationship between the glass transition temperature and the fraction of chain ends was demonstrated by DSC and highlights the potential of this synthetic method to tailor polymer properties. All five samples were found to be in a disordered phase exhibiting multiscale structures revealed by two broad peaks in small-angle X-ray scattering (SAXS) that can be attributed to graft-to-graft and backbone-to-backbone density correlations using MD simulations. The SCFT-based simulations justify the observation of a disordered phase due to its stabilization by the grafts. Additionally, this modular approach can be easily extended to other grafts, including responsive, conducting, and charged polymers with the prerequisite end groups. The versatility and ease of assembling these functional bottlebrushes constitute a powerful “toolbox” method for the rapid and scalable synthesis of novel bottlebrush block copolymers with desired properties.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1840213

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 2 Vol. 55; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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