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Title: Association of a multifunctional ionic block copolymer in a selective solvent

Abstract

The self-assembly of multiblock copolymers in solutions is controlled by a delicate balance between inherent phase segregation due to incompatibility of the blocks and the interaction of the individual blocks with the solvent. The current study elucidates the association of pentablock copolymers in a mixture of selective solvents which are good for the hydrophobic segments and poor for the hydrophilic blocks using small angle neutron scattering (SANS). The pentablock consists of a center block of randomly sulfonated polystyrene, designed for transport, tethered to poly-ethylene-r-propylene and end-capped by poly-t-butyl styrene, for mechanical stability. We find that the pentablock forms ellipsoidal core-shell micelles with the sulfonated polystyrene in the core and Gaussian decaying chains of swollen poly-ethylene-r-propylene and poly-t-butyl styrene tertiary in the corona. With increasing solution concentration, the size of the micelle, the thickness of the corona, and the aggregation number increase, while the solvent fraction in the core decreases. As a result, in dilute solution the micelle increases in size as the temperature is increased, however, temperature effects dissipate with increasing solution concentration.

Authors:
 [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [2];  [3]; ORCiD logo [4];  [1]
  1. Clemson Univ., Clemson, SC (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Kraton Polymers US LLC, Houston, TX (United States)
  4. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1332952
Alternate Identifier(s):
OSTI ID: 1332014
Report Number(s):
SAND-2016-11506J
Journal ID: ISSN 0021-9606; JCPSA6; 649110; TRN: US1700124
Grant/Contract Number:  
AC04-94AL85000; FG02-08ER46528; SC007908
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 18; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; micelles; solvents; block copolymers; aggregation; polymer structure

Citation Formats

Etampawala, Thusitha N., Aryal, Dipak, Osti, Naresh C., He, Lilin, Heller, William T., Willis, Carl L., Grest, Gary S., and Perahia, Dvora. Association of a multifunctional ionic block copolymer in a selective solvent. United States: N. p., 2016. Web. doi:10.1063/1.4967291.
Etampawala, Thusitha N., Aryal, Dipak, Osti, Naresh C., He, Lilin, Heller, William T., Willis, Carl L., Grest, Gary S., & Perahia, Dvora. Association of a multifunctional ionic block copolymer in a selective solvent. United States. https://doi.org/10.1063/1.4967291
Etampawala, Thusitha N., Aryal, Dipak, Osti, Naresh C., He, Lilin, Heller, William T., Willis, Carl L., Grest, Gary S., and Perahia, Dvora. Mon . "Association of a multifunctional ionic block copolymer in a selective solvent". United States. https://doi.org/10.1063/1.4967291. https://www.osti.gov/servlets/purl/1332952.
@article{osti_1332952,
title = {Association of a multifunctional ionic block copolymer in a selective solvent},
author = {Etampawala, Thusitha N. and Aryal, Dipak and Osti, Naresh C. and He, Lilin and Heller, William T. and Willis, Carl L. and Grest, Gary S. and Perahia, Dvora},
abstractNote = {The self-assembly of multiblock copolymers in solutions is controlled by a delicate balance between inherent phase segregation due to incompatibility of the blocks and the interaction of the individual blocks with the solvent. The current study elucidates the association of pentablock copolymers in a mixture of selective solvents which are good for the hydrophobic segments and poor for the hydrophilic blocks using small angle neutron scattering (SANS). The pentablock consists of a center block of randomly sulfonated polystyrene, designed for transport, tethered to poly-ethylene-r-propylene and end-capped by poly-t-butyl styrene, for mechanical stability. We find that the pentablock forms ellipsoidal core-shell micelles with the sulfonated polystyrene in the core and Gaussian decaying chains of swollen poly-ethylene-r-propylene and poly-t-butyl styrene tertiary in the corona. With increasing solution concentration, the size of the micelle, the thickness of the corona, and the aggregation number increase, while the solvent fraction in the core decreases. As a result, in dilute solution the micelle increases in size as the temperature is increased, however, temperature effects dissipate with increasing solution concentration.},
doi = {10.1063/1.4967291},
url = {https://www.osti.gov/biblio/1332952}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 18,
volume = 145,
place = {United States},
year = {2016},
month = {11}
}

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Works referenced in this record:

Form factors of block copolymer micelles with spherical, ellipsoidal and cylindrical cores
journal, June 2000


Predicting the solution morphology of a sulfonated pentablock copolymer in binary solvent mixtures
journal, September 2015


Molecular architecture and rheological characterization of novel intramolecularly crosslinked polystyrene nanoparticles
journal, January 2006


Amphiphilic Block Copolymer Films: Phase Transition, Stabilization, and Nanoscale Templates
journal, February 2009


The 40 m general purpose small-angle neutron scattering instrument at Oak Ridge National Laboratory
journal, August 2012


Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996


Effect of the Soluble Block Size on Spherical Diblock Copolymer Micelles
journal, September 2008


Solvent controlled ion association in structured copolymers: Molecular dynamics simulations in dilute solutions
journal, September 2015


Characterization of a sulfonated pentablock copolymer for desalination applications
journal, November 2010


Association and Structure of Thermosensitive Comblike Block Copolymers in Aqueous Solutions
journal, July 2008


Caractérisation de la structure des membranes ionomères (NAFION ® ) par diffusion de rayons X aux petits angles
journal, July 2002


Block Ionomer Micelles in Solution. 1. Characterization of Ionic Cores by Small-Angle X-ray Scattering
journal, August 1994


Micellar Morphology in Bulk Styrene-Core Ionic Diblock Copolymers
journal, August 1994


Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Phase Behavior of Polyelectrolyte Block Copolymers in Mixed Solvents
journal, March 2008


Scattering Form Factor of Block Copolymer Micelles
journal, January 1996


Mechanisms of micellization and rheology of PEO–PPO–PEO triblock copolymers with various architectures
journal, December 2008


Phase Behavior of a Single Structured Ionomer Chain in Solution: Phase Behavior of a Single Structured Ionomer Chain …
journal, August 2014


A−B Diblock Copolymer Micelles:  Effects of Soluble-Block Length and Component Compatibility
journal, September 2007


Effect of Macromolecular Architecture on the Morphology of Polystyrene–Polyisoprene Block Copolymers
journal, February 2013


The extended Q -range small-angle neutron scattering diffractometer at the SNS
journal, July 2010


Temperature-dependent micellar structures in poly(styrene-b-isoprene) diblock copolymer solutions near the critical micelle temperature
journal, January 2004


Optimized intermolecular potential functions for liquid hydrocarbons
journal, October 1984


Influence of the Degree of Sulfonation on the Structure and Dynamics of Sulfonated Polystyrene Copolymers
journal, December 2010


Micellar Morphology in Sulfonated Pentablock Copolymer Solutions
journal, December 2010


Water purification by membranes: The role of polymer science
journal, June 2010


Scattering from block copolymer micelles
journal, August 2002


Self-assembly of a semi-fluorinated diblock copolymer in a selective solvent
journal, January 2012


Block and graft copolymer micelles in solution
journal, October 1976


Quantifying the “Neutrality” of Good Solvents for Block Copolymers:  Poly(styrene- b -isoprene) in Toluene, Benzene, and THF
journal, December 1998