ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties

Bates, Christopher M.; Chang, Alice B.; Momčilović, Nebojša; Jones, Simon C.; Grubbs, Robert H.

doi:10.1021/acs.macromol.5b00880

Title: ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties

Abstract

The synthesis, self-assembly, conductivity, and rheological properties of ABA triblock brush polymers (BBCPs) with grafted polystyrene (A block, N_PS = 21) and poly(ethylene oxide) (B block, N_PEO = 45) side chains are reported here. Two backbone molecular weights (N_A:N_B:N_A = 11:78:11 and 15:119:15) were investigated with lithium bis(trifluoromethane)sulfonimide (LiTFSI) doping ratios 2 ≤ [EO]:[Li⁺] ≤ 20. Blends with 2 ≤ [EO]:[Li⁺] ≤ 10 suppress PEO crystallization and self-assemble into hexagonally packed cylinders of the minority gPS component. Conductivity is on the order of 10^–3 S/cm at 105 °C with a corresponding elastic modulus ca. 104 Pa. The optimum conductivity occurs at a blend ratio near 10:1 [EO]:[Li⁺], similar to that reported for linear block copolymer analogues.

Authors:

Bates, Christopher M. ^[1]; Chang, Alice B. ^[1]; Momčilović, Nebojša ^[1]; Jones, Simon C. ^[1]; Grubbs, Robert H. ^[1]

California Inst. of Technology (CalTech), Pasadena, CA (United States)

Publication Date:: Tue Jul 07 00:00:00 EDT 2015

Research Org.:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

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

OSTI Identifier:: 1208671

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: 48; Journal Issue: 14; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: ENGLISH

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Hydrocarbons; Crystallization; Homopolymers; Electrical conductivity; Polymers

Citation Formats


                    Bates, Christopher M., Chang, Alice B., Momčilović, Nebojša, Jones, Simon C., and Grubbs, Robert H. ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties.  United States: N. p., 2015. 
Web.  doi:10.1021/acs.macromol.5b00880.

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                    Bates, Christopher M., Chang, Alice B., Momčilović, Nebojša, Jones, Simon C., & Grubbs, Robert H. ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties.  United States.  https://doi.org/10.1021/acs.macromol.5b00880

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                    Bates, Christopher M., Chang, Alice B., Momčilović, Nebojša, Jones, Simon C., and Grubbs, Robert H. Tue .  
"ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties".  United States.  https://doi.org/10.1021/acs.macromol.5b00880.  https://www.osti.gov/servlets/purl/1208671.

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@article{osti_1208671,

  title        = {ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties},

  author       = {Bates, Christopher M. and Chang, Alice B. and Momčilović, Nebojša and Jones, Simon C. and Grubbs, Robert H.},

  abstractNote = {The synthesis, self-assembly, conductivity, and rheological properties of ABA triblock brush polymers (BBCPs) with grafted polystyrene (A block, NPS = 21) and poly(ethylene oxide) (B block, NPEO = 45) side chains are reported here. Two backbone molecular weights (NA:NB:NA = 11:78:11 and 15:119:15) were investigated with lithium bis(trifluoromethane)sulfonimide (LiTFSI) doping ratios 2 ≤ [EO]:[Li+] ≤ 20. Blends with 2 ≤ [EO]:[Li+] ≤ 10 suppress PEO crystallization and self-assemble into hexagonally packed cylinders of the minority gPS component. Conductivity is on the order of 10–3 S/cm at 105 °C with a corresponding elastic modulus ca. 104 Pa. The optimum conductivity occurs at a blend ratio near 10:1 [EO]:[Li+], similar to that reported for linear block copolymer analogues.},

  doi          = {10.1021/acs.macromol.5b00880},

  journal      = {Macromolecules},

  number       = 14,

  volume       = 48,

  place        = {United States},

  year         = {Tue Jul 07 00:00:00 EDT 2015},

  month        = {Tue Jul 07 00:00:00 EDT 2015}

}

Copy to clipboard

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Title: ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties

Abstract

Citation Formats

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Super soft elastomers as ionic conductors journal, August 2004

Amphiphilic polymer gel electrolytes. I. preparation of gels based on poly(ethylene oxide) graft copolymers containing different ionophobic groups: Amphiphilic Polymer Gel Electrolytes. I journal, May 2001

Thermodynamics of Block Copolymers with and without Salt journal, December 2013

Synthesis and Self‐Assembly of Mixed‐Graft Block Copolymers journal, May 2019

Self-assembly of giant bottlebrush block copolymer surfactants from luminescent organic electronic materials journal, January 2019

Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration journal, March 2018

Theoretical prediction of an isotropic to nematic phase transition in bottlebrush homopolymer melts journal, September 2019

Initiating Mechanism of the Anionic Polymerization of Methacrylates with t ‐BuOK and the Synthesis of ABA Type Triblock Copolymers journal, November 2019

Branched 1,2,3-Triazolium-Functionalized Polyacetylene with Enhanced Conductivity journal, November 2016

Effect of side chain and backbone length on lamellar spacing in polystyrene‐block‐poly(dimethyl siloxane) brush block copolymers journal, March 2019

Synthesis, Characterization and Thermal Properties of Poly(ethylene oxide), PEO, Polymacromonomers via Anionic and Ring Opening Metathesis Polymerization journal, April 2017

Synthese und Anwendung von kompartimentierten molekularen Polymerbürsten journal, May 2018

Metathesis cyclopolymerization of substituted 1,6-heptadiyne and dual conductivity of doped polyacetylene bearing branched triazole pendants journal, November 2016

Charging toward improved lithium-ion polymer electrolytes: exploiting synergistic experimental and computational approaches to facilitate materials design journal, January 2019

Brush‐First ROMP of poly(ethylene oxide) macromonomers of varied length: impact of polymer architecture on thermal behavior and Li + conductivity journal, September 2018

Enhanced Ionic and Electronic Conductivity of Polyacetylene with Dendritic 1,2,3-Triazolium-Oligo(ethylene glycol) Pendants journal, April 2018

Synthesis and Applications of Compartmentalised Molecular Polymer Brushes journal, May 2018

Initiating Mechanism of the Anionic Polymerization of Methacrylates with t ‐BuOK and the Synthesis of ABA Type Triblock Copolymers journal, November 2019

Synthesis of triazole-dendronized polyacetylenes by metathesis cyclopolymerization and their conductivity journal, January 2016

Designing polymers for advanced battery chemistries journal, April 2019

A comparative study of thermodynamic, conformational, and structural properties of bottlebrush with star and ring polymer melts journal, July 2018

Grubbs’ and Schrock’s Catalysts, Ring Opening Metathesis Polymerization and Molecular Brushes—Synthesis, Characterization, Properties and Applications journal, February 2019

Influence of residual impurities on ring-opening metathesis polymerization after copper(I)-catalyzed alkyne-azide cycloaddition click reaction journal, January 2019

Chemically inert covalently networked triazole-based solid polymer electrolytes for stable all-solid-state lithium batteries journal, January 2019

Synthesis, Characterization and Thermal Properties of Poly(ethylene oxide), PEO, Polymacromonomers via Anionic and Ring Opening Metathesis Polymerization journal, April 2017

Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes
journal, June 2007

Synthesis and Characterization of Single-Ion Graft Copolymer Electrolytes
journal, January 2005

Connection between Polymer Molecular Weight, Density, Chain Dimensions, and Melt Viscoelastic Properties
journal, August 1994

Effect of Grain Size on the Ionic Conductivity of a Block Copolymer Electrolyte
journal, July 2014

Discontinuous Changes in Ionic Conductivity of a Block Copolymer Electrolyte through an Order–Disorder Transition
journal, January 2012

Charge Transport in Nanostructured PS–PEO–PS Triblock Copolymer Electrolytes
journal, April 2014

Rubbery Graft Copolymer Electrolytes for Solid-State, Thin-Film Lithium Batteries
journal, January 2005

Lithium battery with solid polymer electrolyte based on comb-like copolymers
journal, April 2015

Crystallization and thermal properties of PLLA comb polymer
journal, March 2008

Effect of Ion Distribution on Conductivity of Block Copolymer Electrolytes
journal, March 2009

Linear Rheological Response of a Series of Densely Branched Brush Polymers
journal, September 2011

Effect of side chain length and crosslinking on the ac conductivity of oligo (ethyleneoxide) comb-branch polymer-salt mixtures
journal, October 1990

Polymer Electrolytes
journal, July 2013

Investigating polypropylene-poly(ethylene oxide)-polypropylene triblock copolymers as solid polymer electrolytes for lithium batteries
journal, October 2014

Block copolymer electrolytes for rechargeable lithium batteries
journal, November 2013

Ionic Conductivity of Low Molecular Weight Block Copolymer Electrolytes
journal, January 2013

High-Modulus, High-Conductivity Nanostructured Polymer Electrolyte Membranes via Polymerization-Induced Phase Separation
journal, December 2013

Mixed-Salt Effects on the Ionic Conductivity of Lithium-Doped PEO-Containing Block Copolymers
journal, October 2011

Molecular brushes as super-soft elastomers
journal, September 2006

Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes
journal, July 2009

Mechanisms Underlying Ion Transport in Lamellar Block Copolymer Membranes
journal, March 2012

On the Self-Assembly of Brush Block Copolymers in Thin Films
journal, October 2013

Structure–Conductivity Relationship for Peptoid-Based PEO–Mimetic Polymer Electrolytes
journal, June 2012

All Solid-State Lithium-Polymer Battery Using a Self-Cross-Linking Polymer Electrolyte
journal, January 2003

The effect of different lithium salts on conductivity of comb-like polymer electrolyte with chelating functional group
journal, February 2003

Efficient Synthesis of Narrowly Dispersed Brush Polymers via Living Ring-Opening Metathesis Polymerization of Macromonomers
journal, June 2009

Evolution of Morphology, Modulus, and Conductivity in Polymer Electrolytes Prepared via Polymerization-Induced Phase Separation
journal, February 2015

Star-Shaped Polymer Electrolyte with Microphase Separation Structure for All-Solid-State Lithium Batteries
journal, January 2009

Characteristics of new-type solid polymer electrolyte controlling nano-structure
journal, August 2005

Phase Diagrams and Conductivity Behavior of Poly(ethylene oxide)-Molten Salt Rubbery Electrolytes
journal, December 1994

Polymer Electrolytes for Lithium-Ion Batteries
journal, April 1998

Super soft elastomers as ionic conductors
journal, August 2004

Amphiphilic polymer gel electrolytes. I. preparation of gels based on poly(ethylene oxide) graft copolymers containing different ionophobic groups: Amphiphilic Polymer Gel Electrolytes. I
journal, May 2001

Thermodynamics of Block Copolymers with and without Salt
journal, December 2013

Synthesis and Self‐Assembly of Mixed‐Graft Block Copolymers
journal, May 2019

Self-assembly of giant bottlebrush block copolymer surfactants from luminescent organic electronic materials
journal, January 2019

Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration
journal, March 2018

Theoretical prediction of an isotropic to nematic phase transition in bottlebrush homopolymer melts
journal, September 2019

Initiating Mechanism of the Anionic Polymerization of Methacrylates with t ‐BuOK and the Synthesis of ABA Type Triblock Copolymers
journal, November 2019

Branched 1,2,3-Triazolium-Functionalized Polyacetylene with Enhanced Conductivity
journal, November 2016

Effect of side chain and backbone length on lamellar spacing in polystyrene‐block‐poly(dimethyl siloxane) brush block copolymers
journal, March 2019

Synthesis, Characterization and Thermal Properties of Poly(ethylene oxide), PEO, Polymacromonomers via Anionic and Ring Opening Metathesis Polymerization
journal, April 2017

Synthese und Anwendung von kompartimentierten molekularen Polymerbürsten
journal, May 2018

Metathesis cyclopolymerization of substituted 1,6-heptadiyne and dual conductivity of doped polyacetylene bearing branched triazole pendants
journal, November 2016

Charging toward improved lithium-ion polymer electrolytes: exploiting synergistic experimental and computational approaches to facilitate materials design
journal, January 2019

Brush‐First ROMP of poly(ethylene oxide) macromonomers of varied length: impact of polymer architecture on thermal behavior and Li ⁺ conductivity
journal, September 2018

Enhanced Ionic and Electronic Conductivity of Polyacetylene with Dendritic 1,2,3-Triazolium-Oligo(ethylene glycol) Pendants
journal, April 2018

Synthesis and Applications of Compartmentalised Molecular Polymer Brushes
journal, May 2018

Initiating Mechanism of the Anionic Polymerization of Methacrylates with t ‐BuOK and the Synthesis of ABA Type Triblock Copolymers
journal, November 2019

Synthesis of triazole-dendronized polyacetylenes by metathesis cyclopolymerization and their conductivity
journal, January 2016

Designing polymers for advanced battery chemistries
journal, April 2019

A comparative study of thermodynamic, conformational, and structural properties of bottlebrush with star and ring polymer melts
journal, July 2018

Grubbs’ and Schrock’s Catalysts, Ring Opening Metathesis Polymerization and Molecular Brushes—Synthesis, Characterization, Properties and Applications
journal, February 2019

Influence of residual impurities on ring-opening metathesis polymerization after copper(I)-catalyzed alkyne-azide cycloaddition click reaction
journal, January 2019

Chemically inert covalently networked triazole-based solid polymer electrolytes for stable all-solid-state lithium batteries
journal, January 2019

Synthesis, Characterization and Thermal Properties of Poly(ethylene oxide), PEO, Polymacromonomers via Anionic and Ring Opening Metathesis Polymerization
journal, April 2017