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

Jiang, Liuyin; Nykypanchuk, Dmytro; Ribbe, Alexander E.; Rzayev, Javid

doi:10.1021/acsmacrolett.8b00273

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

Abstract

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.

Authors:

Jiang, Liuyin ^[1];

^[2]; Ribbe, Alexander E. ^[3];

^[1]

Univ. at Buffalo, The State Univ. of New York, Buffalo, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Univ. of Massachusetts, Amherst, MA (United States)

Publication Date:: Tue May 15 00:00:00 EDT 2018

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

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

OSTI Identifier:: 1495003

Report Number(s):: BNL-211265-2019-JAAM
Journal ID: ISSN 2161-1653

Grant/Contract Number:: SC0012704

Resource Type:: Accepted Manuscript

Journal Name:: ACS Macro Letters

Additional Journal Information:: Journal Volume: 7; Journal Issue: 6; Journal ID: ISSN 2161-1653

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; bottlebrush copolymers; self-assembly; gradient copolymers; morphology; norbornene reactivity

Citation Formats


                    Jiang, Liuyin, Nykypanchuk, Dmytro, Ribbe, Alexander E., and Rzayev, Javid. One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile.  United States: N. p., 2018. 
Web.  doi:10.1021/acsmacrolett.8b00273.

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                    Jiang, Liuyin, Nykypanchuk, Dmytro, Ribbe, Alexander E., & Rzayev, Javid. One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile.  United States.  https://doi.org/10.1021/acsmacrolett.8b00273

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                    Jiang, Liuyin, Nykypanchuk, Dmytro, Ribbe, Alexander E., and Rzayev, Javid. Tue .  
"One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile".  United States.  https://doi.org/10.1021/acsmacrolett.8b00273.  https://www.osti.gov/servlets/purl/1495003.

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@article{osti_1495003,

  title        = {One-Shot Synthesis and Melt Self-Assembly of Bottlebrush Copolymers with a Gradient Compositional Profile},

  author       = {Jiang, Liuyin and Nykypanchuk, Dmytro and Ribbe, Alexander E. and Rzayev, Javid},

  abstractNote = {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.},

  doi          = {10.1021/acsmacrolett.8b00273},

  journal      = {ACS Macro Letters},

  number       = 6,

  volume       = 7,

  place        = {United States},

  year         = {Tue May 15 00:00:00 EDT 2018},

  month        = {Tue May 15 00:00:00 EDT 2018}

}

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Journal Article:

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https://doi.org/10.1021/acsmacrolett.8b00273

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Cited by: 37 works

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Figures / Tables:

Figure 1: One-shot synthesis of gradient bottlebrush block copolymers by ring-opening metathesis polymerization.

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Works referencing / citing this record:

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

Kitamoto, Yuichi; Pan, Ziyan; Prabhu, Deepak D.
Nature Communications, Vol. 10, Issue 1
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Kitamoto, Yuichi; Pan, Ziyan; Prabhu, Deepak D.
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Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

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

Abstract

Citation Formats

Figures / Tables:

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

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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

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

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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

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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

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