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Title: Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior

Abstract

Block copolymers have been extensively studied due to their ability to spontaneously self‐organize into a wide variety of morphologies that are valuable in energy‐, medical‐, and conservation‐related (nano)technologies. While the phase behavior of bicomponent diblock and triblock copolymers is conventionally governed by temperature and individual block masses, it is demonstrated here that their phase behavior can alternatively be controlled through the use of blocks with random monomer sequencing. Block random copolymers (BRCs), i.e., diblock copolymers wherein one or both blocks are a random copolymer comprised of A and B repeat units, have been synthesized, and their phase behavior, expressed in terms of the order–disorder transition (ODT), has been investigated. The results establish that, depending on the block composition contrast and molecular weight, BRCs can microphase‐separate. We also report that large variation in incompatibility can be generated at relatively constant molecular weight and temperature with these new soft materials. This sequence‐controlled synthetic strategy is extended to thermoplastic elastomeric triblock copolymers differing in chemistry and possessing a random‐copolymer midblock.

Authors:
 [1];  [2];  [1];  [3];  [1];  [4]
+ Show Author Affiliations
  1. Corporate Research and Development The Procter and Gamble Company Cincinnati OH 45224 USA
  2. Department of Materials Science and Engineering North Carolina State University Raleigh NC 27695 USA
  3. Advanced Photon Source Argonne National Laboratory Argonne IL 60439 USA
  4. Department of Materials Science and Engineering North Carolina State University Raleigh NC 27695 USA, Department of Chemical and Biomolecular Engineering North Carolina State University Raleigh NC 27695 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1378300
Grant/Contract Number:  
DE‐AC02‐06CH11357
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Macromolecular Rapid Communications
Additional Journal Information:
Journal Name: Macromolecular Rapid Communications Journal Volume: 38 Journal Issue: 17; Journal ID: ISSN 1022-1336
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Ashraf, Arman R., Ryan, Justin J., Satkowski, Michael M., Lee, Byeongdu, Smith, Steven D., and Spontak, Richard J. Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior. Germany: N. p., 2017. Web. doi:10.1002/marc.201700207.
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Ashraf, Arman R., Ryan, Justin J., Satkowski, Michael M., Lee, Byeongdu, Smith, Steven D., & Spontak, Richard J. Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior. Germany. https://doi.org/10.1002/marc.201700207
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Ashraf, Arman R., Ryan, Justin J., Satkowski, Michael M., Lee, Byeongdu, Smith, Steven D., and Spontak, Richard J. Thu . "Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior". Germany. https://doi.org/10.1002/marc.201700207.
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@article{osti_1378300,
title = {Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior},
author = {Ashraf, Arman R. and Ryan, Justin J. and Satkowski, Michael M. and Lee, Byeongdu and Smith, Steven D. and Spontak, Richard J.},
abstractNote = {Block copolymers have been extensively studied due to their ability to spontaneously self‐organize into a wide variety of morphologies that are valuable in energy‐, medical‐, and conservation‐related (nano)technologies. While the phase behavior of bicomponent diblock and triblock copolymers is conventionally governed by temperature and individual block masses, it is demonstrated here that their phase behavior can alternatively be controlled through the use of blocks with random monomer sequencing. Block random copolymers (BRCs), i.e., diblock copolymers wherein one or both blocks are a random copolymer comprised of A and B repeat units, have been synthesized, and their phase behavior, expressed in terms of the order–disorder transition (ODT), has been investigated. The results establish that, depending on the block composition contrast and molecular weight, BRCs can microphase‐separate. We also report that large variation in incompatibility can be generated at relatively constant molecular weight and temperature with these new soft materials. This sequence‐controlled synthetic strategy is extended to thermoplastic elastomeric triblock copolymers differing in chemistry and possessing a random‐copolymer midblock.},
doi = {10.1002/marc.201700207},
journal = {Macromolecular Rapid Communications},
number = 17,
volume = 38,
place = {Germany},
year = {Thu Jun 29 00:00:00 EDT 2017},
month = {Thu Jun 29 00:00:00 EDT 2017}
}
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Journal Article:
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Accepted Manuscript (Publisher)
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https://doi.org/10.1002/marc.201700207
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Works referenced in this record:

Synthesis, Structure, and Properties of Alternating and Random Poly(styrene- b -butadiene) Multiblock Copolymers
journal, May 2013

  • Lee, Intaek; Bates, Frank S.
  • Macromolecules, Vol. 46, Issue 11
  • DOI: 10.1021/ma400479b

Interfacial Modification as a Route to Novel Bilayered Morphologies in Binary Block Copolymer/Homopolymer Blends
journal, July 1998

  • Laurer, Jonathan H.; Smith, Steven D.; Samseth, Jon
  • Macromolecules, Vol. 31, Issue 15
  • DOI: 10.1021/ma980200j

Fluctuation effects in the theory of microphase separation in block copolymers
journal, July 1987

  • Fredrickson, Glenn H.; Helfand, Eugene
  • The Journal of Chemical Physics, Vol. 87, Issue 1
  • DOI: 10.1063/1.453566

The soliton mechanism of phase separation of polydisperse multiblock copolymers
journal, January 2016

  • Ivanova, A. N.; Kuchanov, S. I.; Shaginyan, Sh. A.
  • Polymer Science Series A, Vol. 58, Issue 1
  • DOI: 10.1134/S0965545X1601003X

Phase Behavior of Gradient Copolymers
journal, July 2008

  • Jiang, Run; Jin, Qinghua; Li, Baohui
  • Macromolecules, Vol. 41, Issue 14
  • DOI: 10.1021/ma8002517

Microstructures of polybutadienes prepared by anionic polymerization in polar solvents. Ion-pair and solvent effects
journal, March 1984

  • Bywater, S.; Firat, Y.; Black, P. E.
  • Journal of Polymer Science: Polymer Chemistry Edition, Vol. 22, Issue 3
  • DOI: 10.1002/pol.1984.170220316

Multiblock Polymers: Panacea or Pandora's Box?
journal, April 2012

Random Block Copolymers: Structure, Dynamics, and Mechanical Properties in the Bulk and at Selective Substrates
journal, December 2012

  • Steinmüller, Birger; Müller, Marcus; Hambrecht, Keith R.
  • Macromolecules, Vol. 45, Issue 24
  • DOI: 10.1021/ma302151z

Pathways to Macroscale Order in Nanostructured Block Copolymers
journal, August 1997

Microstructural Analysis of a Cubic Bicontinuous Morphology in a Neat SIS Triblock Copolymer
journal, June 1997

  • Laurer, Jonathan H.; Hajduk, Damian A.; Fung, Jennifer C.
  • Macromolecules, Vol. 30, Issue 13
  • DOI: 10.1021/ma970449l

Ternary Phase Behavior of a Triblock Copolymer in the Presence of an Endblock-Selective Homopolymer and a Midblock-Selective Oil
journal, July 2012

  • Krishnan, Arjun S.; Smith, Steven D.; Spontak, Richard J.
  • Macromolecules, Vol. 45, Issue 15
  • DOI: 10.1021/ma300417u

Segmental dynamics in lamellar phases of tapered copolymers
journal, January 2016

  • Sethuraman, Vaidyanathan; Ganesan, Venkat
  • Soft Matter, Vol. 12, Issue 37
  • DOI: 10.1039/C6SM01516F

The Full Phase Behavior for Block Copolymers in Solvents of Varying Selectivity
journal, June 2002

  • Lodge, Timothy P.; Pudil, Bryant; Hanley, Kenneth J.
  • Macromolecules, Vol. 35, Issue 12
  • DOI: 10.1021/ma0200975

Structure, viscoelasticity, and interfacial dynamics of a model polymeric bicontinuous microemulsion
journal, January 2016

  • Hickey, Robert J.; Gillard, Timothy M.; Irwin, Matthew T.
  • Soft Matter, Vol. 12, Issue 1
  • DOI: 10.1039/C5SM02009C

Supramolecular Materials via Block Copolymer Self-Assembly
journal, August 2001

Phase behavior in copolymer blends: poly(2,6-dimethyl-1,4-phenylene oxide) and halogen-substituted styrene copolymers
journal, December 1983

  • Ten Brinke, Gerrit; Karasz, Frank E.; MacKnight, William J.
  • Macromolecules, Vol. 16, Issue 12
  • DOI: 10.1021/ma00246a006

The Gyroid: A New Equilibrium Morphology in Weakly Segregated Diblock Copolymers
journal, July 1994

  • Hajduk, Damian A.; Harper, Paul E.; Gruner, Sol M.
  • Macromolecules, Vol. 27, Issue 15
  • DOI: 10.1021/ma00093a006

Failure of the dilution approximation in block copolymer solutions
journal, November 1995

  • Lodge, T. P.; Pan, C.; Jin, X.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 33, Issue 16
  • DOI: 10.1002/polb.1995.090331614

Polymer-Polymer Phase Behavior
journal, February 1991

Functional Supramolecular Polymers for Biomedical Applications
journal, November 2014

  • Dong, Ruijiao; Zhou, Yongfeng; Huang, Xiaohua
  • Advanced Materials, Vol. 27, Issue 3
  • DOI: 10.1002/adma.201402975

Discovery of a Frank-Kasper   Phase in Sphere-Forming Block Copolymer Melts
journal, October 2010

Physical Microfabrication of Shape-Memory Polymer Systems via Bicomponent Fiber Spinning
journal, October 2016

  • Tallury, Syamal S.; Pourdeyhimi, Behnam; Pasquinelli, Melissa A.
  • Macromolecular Rapid Communications, Vol. 37, Issue 22
  • DOI: 10.1002/marc.201600235

Boosting the Performance of Organic Optoelectronic Devices Using Multiple-Patterned Plasmonic Nanostructures
journal, May 2016

Tapered Block Copolymers Containing Ethylene and a Functionalized Comonomer
journal, May 2006

  • Diamanti, Steve J.; Khanna, Vikram; Hotta, Atsushi
  • Macromolecules, Vol. 39, Issue 9
  • DOI: 10.1021/ma052456c

Microphase separation in multiblock copolymer melts
journal, December 1989

  • Mayes, Anne M.; Olvera de la Cruz, Monica
  • The Journal of Chemical Physics, Vol. 91, Issue 11
  • DOI: 10.1063/1.457290

Block Copolymers—Designer Soft Materials
journal, February 1999

  • Bates, Frank S.; Fredrickson, Glenn H.
  • Physics Today, Vol. 52, Issue 2
  • DOI: 10.1063/1.882522

σ Phase Formed in Conformationally Asymmetric AB-Type Block Copolymers
journal, August 2014

  • Xie, Nan; Li, Weihua; Qiu, Feng
  • ACS Macro Letters, Vol. 3, Issue 9
  • DOI: 10.1021/mz500445v

Monodisperse cylindrical micelles by crystallization-driven living self-assembly
journal, May 2010

  • Gilroy, Joe B.; Gädt, Torben; Whittell, George R.
  • Nature Chemistry, Vol. 2, Issue 7
  • DOI: 10.1038/nchem.664

Morphology and transport properties of midblock-sulfonated triblock copolymers
journal, January 2010

  • Moore, Hunter D.; Saito, Tomonori; Hickner, Michael A.
  • Journal of Materials Chemistry, Vol. 20, Issue 30
  • DOI: 10.1039/c0jm00068j

Block Copolymers with a Twist
journal, December 2009

  • Ho, Rong-Ming; Chiang, Yeo-Wan; Chen, Chun-Ku
  • Journal of the American Chemical Society, Vol. 131, Issue 51
  • DOI: 10.1021/ja9083804

Sequence-Controlled Polymers
journal, August 2013

A Solvent-Vapor Approach toward the Control of Block Ionomer Morphologies
journal, April 2016

Microfibres and macroscopic films from the coordination-driven hierarchical self-assembly of cylindrical micelles
journal, August 2016

  • Lunn, David J.; Gould, Oliver E. C.; Whittell, George R.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12371

Phase Behavior of Block Copolymer/Homopolymer Blends
journal, August 1995

Architecturally Complex Polymers with Controlled Heterogeneity
journal, August 2011

Aperiodic Copolymers
journal, September 2014

Effects of Blockiness and Polydispersity on the Phase Behavior of Random Block Copolymers
journal, August 2016

  • Vanderwoude, Gordon; Shi, An-Chang
  • Macromolecular Theory and Simulations, Vol. 26, Issue 1
  • DOI: 10.1002/mats.201600044

Concentration fluctuation effects on disorder–order transitions in block copolymer melts
journal, September 1991

  • Mayes, A. M.; de la Cruz, M. Olvera
  • The Journal of Chemical Physics, Vol. 95, Issue 6
  • DOI: 10.1063/1.461736

Block copolymer self-organization vs. interfacial modification in bilayered thin-film laminates
journal, January 2011

  • Gozen, Arif O.; Zhou, Jiajia; Roskov, Kristen E.
  • Soft Matter, Vol. 7, Issue 7
  • DOI: 10.1039/c0sm01169j

Manipulating ordering transitions in interfacially modified block copolymers
journal, January 2009

  • Singh, Nripen; Tureau, Maëva S.; Epps, III, Thomas H.
  • Soft Matter, Vol. 5, Issue 23
  • DOI: 10.1039/b908739g

Enhancement of mechanical properties of triblock copolymers by random copolymer middle blocks
journal, June 2007

Hierarchical Manipulation of Block Copolymer Patterns on 3D Topographic Substrates: Beyond Graphoepitaxy
journal, June 2016

  • Park, Sungjune; Cheng, Xiao; Böker, Alexander
  • Advanced Materials, Vol. 28, Issue 32
  • DOI: 10.1002/adma.201601098

Regular Mixing Thermodynamics of Hydrogenated Styrene–Isoprene Block–Random Copolymers
journal, April 2013

  • Beckingham, Bryan S.; Register, Richard A.
  • Macromolecules, Vol. 46, Issue 8
  • DOI: 10.1021/ma4002512

Membranes with artificial free-volume for biofuel production
journal, June 2015

  • Petzetakis, Nikos; Doherty, Cara M.; Thornton, Aaron W.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8529

Blockiness and Sequence Polydispersity Effects on the Phase Behavior and Interfacial Properties of Gradient Copolymers
journal, July 2012

  • Ganesan, Venkat; Kumar, N. Arun; Pryamitsyn, Victor
  • Macromolecules, Vol. 45, Issue 15
  • DOI: 10.1021/ma301136y

Complex Phase Behavior of a Disordered “Random” Diblock Copolymer in the Presence of a Parent Homopolymer
journal, April 1997

  • Laurer, Jonathan H.; Ashraf, Arman; Smith, Steven D.
  • Langmuir, Vol. 13, Issue 8
  • DOI: 10.1021/la960807y

Communication: Molecular-level insights into asymmetric triblock copolymers: Network and phase development
journal, September 2014

  • Tallury, Syamal S.; Mineart, Kenneth P.; Woloszczuk, Sebastian
  • The Journal of Chemical Physics, Vol. 141, Issue 12
  • DOI: 10.1063/1.4896612

Universal Phenomenology of Symmetric Diblock Copolymers near the Order–Disorder Transition
journal, January 2015

  • Medapuram, Pavani; Glaser, Jens; Morse, David C.
  • Macromolecules, Vol. 48, Issue 3
  • DOI: 10.1021/ma5017264

Dual modes of self-assembly in superstrongly segregated bicomponent triblock copolymer melts
journal, January 2015

  • Woloszczuk, Sebastian; Mineart, Kenneth P.; Spontak, Richard J.
  • Physical Review E, Vol. 91, Issue 1
  • DOI: 10.1103/PhysRevE.91.010601

Phase Behavior of Triblock Copolymers Varying in Molecular Asymmetry
journal, October 2005

A General Approach to Sequence-Controlled Polymers Using Macrocyclic Ring Opening Metathesis Polymerization
journal, June 2015

  • Gutekunst, Will R.; Hawker, Craig J.
  • Journal of the American Chemical Society, Vol. 137, Issue 25
  • DOI: 10.1021/jacs.5b04940
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