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Title: One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile

Journal Article · · ACS Macro Letters

Morphological control plays a central role in soft materials design. Herein, we report the synthesis of a gradient bottlebrush architecture and its role in directing molecular packing in the solid state. Bottlebrush copolymers with gradient interfaces were prepared via one-shot ring-opening metathesis polymerization of exo- and endo-norbornene-capped macromonomers. Kinetic studies revealed a gradient compositional profile separating the two blocks along the backbone. Side-chain symmetric gradient bottlebrush copolymers exhibited a strong tendency to assemble into cylindrical microstructures, in contrast to their block copolymer analogs with sharp interfaces. Furthermore such exquisite architectural control of the interfacial composition affords a delicate handle to direct macromolecular assembly.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1495003
Report Number(s):
BNL-211265-2019-JAAM
Journal Information:
ACS Macro Letters, Vol. 7, Issue 6; ISSN 2161-1653
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 37 works
Citation information provided by
Web of Science

References (42)

Nanoporous Membranes Derived from Block Copolymers: From Drug Delivery to Water Filtration journal June 2010
Block copolymer self-assembly for nanophotonics journal January 2015
Phase Behaviour and Morphologies of Block Copolymers book January 2005
Self-Assembly of Block Copolymers for Photonic-Bandgap Materials journal October 2005
Block copolymer based composition and morphology control in nanostructured hybrid materials for energy conversion and storage: solar cells, batteries, and fuel cells journal January 2011
50th Anniversary Perspective : Block Polymers—Pure Potential journal December 2016
Interfacial Manipulations: Controlling Nanoscale Assembly in Bulk, Thin Film, and Solution Block Copolymer Systems journal February 2013
Microphase Separation in Normal and Inverse Tapered Block Copolymers of Polystyrene and Polyisoprene. 1. Phase State journal January 2001
Phase Behavior of Tapered Diblock Copolymers from Self-Consistent Field Theory journal November 2013
Determination of Interfacial Mixing in Tapered Block Polymer Thin Films: Experimental and Theoretical Investigations journal July 2016
Effect of Tapering on Morphology and Interfacial Behavior of Diblock Copolymers from Molecular Dynamics Simulations journal July 2015
Cylindrical molecular brushes: Synthesis, characterization, and properties journal July 2008
Structure, function, self-assembly, and applications of bottlebrush copolymers journal January 2015
Synthesis of Polystyrene−Polylactide Bottlebrush Block Copolymers and Their Melt Self-Assembly into Large Domain Nanostructures journal March 2009
Synthesis of Comb Block Copolymers by ROMP, ATRP, and ROP and Their Assembly in the Solid State journal January 2006
Efficient Synthesis of Narrowly Dispersed Brush Copolymers and Study of Their Assemblies: The Importance of Side Chain Arrangement journal December 2009
Bottlebrush Block Polymers: Quantitative Theory and Experiments journal October 2015
Nanoscopic Cylindrical Dual Concentric and Lengthwise Block Brush Terpolymers as Covalent Preassembled High-Resolution and High-Sensitivity Negative-Tone Photoresist Materials journal March 2013
Organosoluble polypyrrole nanotubes from core–shell bottlebrush copolymers journal January 2010
Amphiphilic Cylindrical Core−Shell Brushes via a “Grafting From” Process Using ATRP journal September 2001
Cylindrical Core−Shell Brushes Prepared by a Combination of ROP and ATRP journal July 2006
Tandem Synthesis of Core−Shell Brush Copolymers and Their Transformation to Peripherally Cross-Linked and Hollowed Nanostructures journal May 2006
Dynamic Cylindrical Assembly of Triblock Copolymers by a Hierarchical Process of Covalent and Supramolecular Interactions journal February 2011
Graft-through Synthesis and Assembly of Janus Bottlebrush Polymers from A- Branch -B Diblock Macromonomers journal September 2016
Well-Defined Amphiphilic Double-Brush Copolymers and Their Performance as Emulsion Surfactants journal May 2012
Large Pore Size Nanoporous Materials from the Self-Assembly of Asymmetric Bottlebrush Block Copolymers journal March 2011
Tandem RAFT-ATRP Synthesis of Polystyrene–Poly(Methyl Methacrylate) Bottlebrush Block Copolymers and Their Self-Assembly into Cylindrical Nanostructures journal November 2011
Synthesis of Molecular Brushes with Gradient in Grafting Density by Atom Transfer Polymerization journal April 2002
Molecular Brushes with Spontaneous Gradient by Atom Transfer Radical Polymerization journal October 2005
Design, Synthesis, and Self-Assembly of Polymers with Tailored Graft Distributions journal November 2017
Control of Grafting Density and Distribution in Graft Polymers by Living Ring-Opening Metathesis Copolymerization journal March 2017
Synthesis of Dendronized Polymers via Macromonomer Approach by Living ROMP and Their Characterization: From Rod-Like Homopolymers to Block and Gradient Copolymers journal July 2013
Tapered Bottlebrush Polymers: Cone-Shaped Nanostructures by Sequential Addition of Macromonomers journal October 2017
Bottlebrush Polymer Synthesis by Ring-Opening Metathesis Polymerization: The Significance of the Anchor Group journal May 2016
Synthesis and Direct Visualization of Dumbbell-Shaped Molecular Brushes journal December 2011
Comparative Reactivity of E xo - and E ndo -Isomers in the Ru-Initiated Ring-Opening Metathesis Polymerization of Doubly Functionalized Norbornenes with Both Cyano and Ester Groups journal October 2006
ROMP Reactivity of e ndo - and e xo -Dicyclopentadiene journal October 2002
Precision polymers: a kinetic approach for functional poly(norbornenes) journal January 2014
Importance of Macromonomer Quality in the Ring-Opening Metathesis Polymerization of Macromonomers journal August 2015
Interplay between Molecular Packing, Drug Loading, and Core Cross-Linking in Bottlebrush Copolymer Micelles journal February 2017
Self-Assembly of Symmetric Brush Diblock Copolymers journal February 2013
Ordered Nanoporous Polymers from Polystyrene−Polylactide Block Copolymers journal October 2002

Cited By (2)

One-shot preparation of topologically chimeric nanofibers via a gradient supramolecular copolymerization journal October 2019
One-shot preparation of topologically chimeric nanofibers via a gradient supramolecular copolymerization journal October 2019

Figures / Tables (6)