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Title: Poly(methyl methacrylate)-block-poly(n-butyl methacrylate) Diblock Copolymer Micelles in an Ionic Liquid: Scaling of Core and Corona Size with Core Block Length

Abstract

Here, the structure of poly(methyl methacrylate)-block-poly(n-butyl methacrylate) (PMMA-b-PnBMA) micelles in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]), a selective solvent for the PMMA block, has been studied using dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). A series of seven PMMA-b-PnBMA diblock copolymers were prepared by reversible addition–fragmentation chain-transfer (RAFT) polymerization, in which the degree of polymerization of the PMMA block was kept constant while the PnBMA block length was varied. All the polymers formed spherical micelles at ambient temperature in dilute solution; their hydrodynamic radius (Rh) and core radius (Rc) were obtained by DLS and SAXS, respectively. It was found that Rc and the degree of polymerization of the core block, NB, followed a power law relationship in which Rc ~ NB0.71±0.01. The corona thickness (Lcorona), given by the difference of Rh and Rc, does not show any apparent dependence on NB. These results were compared to scaling theory, and were found to be only in partial agreement with the star model proposed by Halperin et al. However, the mean-field calculations of micellar dimensions by Nagarajan and Ganesh were in excellent agreement with the data. This comprehensive experimental study provides precise quantification of the Rc and Lcoronamore » dependence on core block lengths, due to the use of seven different block copolymers with identical corona block lengths.« less

Authors:
 [1];  [1]
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  1. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Science Foundation (NSF); E. I. DuPont de Nemours & Co.; Dow Chemical Company; State of Illinois; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1256360
Grant/Contract Number:  
DMR-1206459; DMR-9304725; IBHE HECA NWU 96; W-31-109-Eng-38
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 49; Journal Issue: 9; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Dynamic light scattering; X-ray scattering; Micelles; Copolymers; Solvents

Citation Formats

Ma, Yuanchi, and Lodge, Timothy P. Poly(methyl methacrylate)-block-poly(n-butyl methacrylate) Diblock Copolymer Micelles in an Ionic Liquid: Scaling of Core and Corona Size with Core Block Length. United States: N. p., 2016. Web. doi:10.1021/acs.macromol.6b00315.
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Ma, Yuanchi, & Lodge, Timothy P. Poly(methyl methacrylate)-block-poly(n-butyl methacrylate) Diblock Copolymer Micelles in an Ionic Liquid: Scaling of Core and Corona Size with Core Block Length. United States. https://doi.org/10.1021/acs.macromol.6b00315
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Ma, Yuanchi, and Lodge, Timothy P. Fri . "Poly(methyl methacrylate)-block-poly(n-butyl methacrylate) Diblock Copolymer Micelles in an Ionic Liquid: Scaling of Core and Corona Size with Core Block Length". United States. https://doi.org/10.1021/acs.macromol.6b00315. https://www.osti.gov/servlets/purl/1256360.
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@article{osti_1256360,
title = {Poly(methyl methacrylate)-block-poly(n-butyl methacrylate) Diblock Copolymer Micelles in an Ionic Liquid: Scaling of Core and Corona Size with Core Block Length},
author = {Ma, Yuanchi and Lodge, Timothy P.},
abstractNote = {Here, the structure of poly(methyl methacrylate)-block-poly(n-butyl methacrylate) (PMMA-b-PnBMA) micelles in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]), a selective solvent for the PMMA block, has been studied using dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). A series of seven PMMA-b-PnBMA diblock copolymers were prepared by reversible addition–fragmentation chain-transfer (RAFT) polymerization, in which the degree of polymerization of the PMMA block was kept constant while the PnBMA block length was varied. All the polymers formed spherical micelles at ambient temperature in dilute solution; their hydrodynamic radius (Rh) and core radius (Rc) were obtained by DLS and SAXS, respectively. It was found that Rc and the degree of polymerization of the core block, NB, followed a power law relationship in which Rc ~ NB0.71±0.01. The corona thickness (Lcorona), given by the difference of Rh and Rc, does not show any apparent dependence on NB. These results were compared to scaling theory, and were found to be only in partial agreement with the star model proposed by Halperin et al. However, the mean-field calculations of micellar dimensions by Nagarajan and Ganesh were in excellent agreement with the data. This comprehensive experimental study provides precise quantification of the Rc and Lcorona dependence on core block lengths, due to the use of seven different block copolymers with identical corona block lengths.},
doi = {10.1021/acs.macromol.6b00315},
journal = {Macromolecules},
number = 9,
volume = 49,
place = {United States},
year = {Fri Apr 29 00:00:00 EDT 2016},
month = {Fri Apr 29 00:00:00 EDT 2016}
}
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Works referenced in this record:

Block copolymers of styrene andn-alkyl methacrylates with long alkyl groups. Micellization behavior in selective solvents
journal, January 2004

  • Pitsikalis, Marinos; Siakali-Kioulafa, Ekaterini; Hadjichristidis, Nikos
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 42, Issue 17
  • DOI: 10.1002/pola.20258

Analysis of Macromolecular Polydispersity in Intensity Correlation Spectroscopy: The Method of Cumulants
journal, December 1972

  • Koppel, Dennis E.
  • The Journal of Chemical Physics, Vol. 57, Issue 11
  • DOI: 10.1063/1.1678153

Star shaped polymers : a model for the conformation and its concentration dependence
journal, January 1982

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

  • LaRue, Isaac; Adam, Mireille; Zhulina, Ekaterina B.
  • Macromolecules, Vol. 41, Issue 17
  • DOI: 10.1021/ma800403r

Self-Diffusion and Tracer Diffusion in Sphere-Forming Block Copolymers
journal, September 2003

  • Cavicchi, Kevin A.; Lodge, Timothy P.
  • Macromolecules, Vol. 36, Issue 19
  • DOI: 10.1021/ma0346815

Structural Properties of Weakly Segregated PS−PB Block Copolymer Micelles in n -Alkanes: Solvent Entropy Effects
journal, April 2009

  • Lund, Reidar; Willner, Lutz; Lindner, Peter
  • Macromolecules, Vol. 42, Issue 7
  • DOI: 10.1021/ma8021629

Polymeric micelles: a star model
journal, November 1987

Regularized Positive Exponential Sum (REPES) Program - A Way of Inverting Laplace Transform Data Obtained by Dynamic Light Scattering
journal, January 1995

  • Jakeš, Jaromír
  • Collection of Czechoslovak Chemical Communications, Vol. 60, Issue 11
  • DOI: 10.1135/cccc19951781

Block copolymer self‐assembly in selective solvents: Spherical micelles with segregated cores
journal, May 1989

  • Nagarajan, R.; Ganesh, K.
  • The Journal of Chemical Physics, Vol. 90, Issue 10
  • DOI: 10.1063/1.456390

Determination of the Micelle Architecture of Polystyrene/Poly(4-vinylpyridine) Block Copolymers in Dilute Solution
journal, June 1994

  • Antonietti, Markus; Heinz, Steffi; Schmidt, Manfred
  • Macromolecules, Vol. 27, Issue 12, p. 3276-3281
  • DOI: 10.1021/ma00090a021

Remarkable Effect of Molecular Architecture on Chain Exchange in Triblock Copolymer Micelles
journal, April 2015

Disorder-order transitions in soft sphere polymer micelles
journal, September 1993

Molecular Exchange in PEO−PB Micelles in Water
journal, January 2003

  • Won, You-Yeon; Davis, H. Ted; Bates, Frank S.
  • Macromolecules, Vol. 36, Issue 3
  • DOI: 10.1021/ma021439+

Styrene/butadiene block copolymer micelles in heptane
journal, January 1985

  • Bluhm, T. L.; Whitmore, M. D.
  • Canadian Journal of Chemistry, Vol. 63, Issue 1
  • DOI: 10.1139/v85-041

Theory of Block Polymer Micelles: Recent Advances and Current Challenges
journal, May 2012

  • Zhulina, E. B.; Borisov, O. V.
  • Macromolecules, Vol. 45, Issue 11
  • DOI: 10.1021/ma300195n

Theory of unsymmetric polymer–polymer interfaces
journal, February 1975

  • Helfand, Eugene; Sapse, Anne Marie
  • The Journal of Chemical Physics, Vol. 62, Issue 4
  • DOI: 10.1063/1.430632

Conformations of block-copolymer molecules in selective solvents (micellar structures
journal, January 1985

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

  • Bang, Joona; Viswanathan, Karthik; Lodge, Timothy P.
  • The Journal of Chemical Physics, Vol. 121, Issue 22
  • DOI: 10.1063/1.1812753

Surfactant or block copolymer micelles? Structural properties of a series of well-defined n -alkyl–PEO micelles in water studied by SANS
journal, January 2014

  • Zinn, Thomas; Willner, Lutz; Lund, Reidar
  • Soft Matter, Vol. 10, Issue 28
  • DOI: 10.1039/C4SM00625A

Static properties of polystyrene in poly(methyl methacrylate)–benzene semidilute solution
journal, January 1985

  • Numasawa, N.; Hamada, T.; Nose, T.
  • Journal of Polymer Science: Polymer Letters Edition, Vol. 23, Issue 1
  • DOI: 10.1002/pol.1985.130230101

Theory of critical micelle concentration for solutions of block copolymers
journal, October 1983

  • Leibler, Ludwik; Orland, Henri; Wheeler, John C.
  • The Journal of Chemical Physics, Vol. 79, Issue 7
  • DOI: 10.1063/1.446209

Micellization of block copolymers
journal, July 2003

A small-angle neutron scattering investigation of the structure of highly swollen block copolymer micelles
journal, November 2002

  • Castelletto, V.; Hamley, I. W.; Pedersen, J. S.
  • The Journal of Chemical Physics, Vol. 117, Issue 17
  • DOI: 10.1063/1.1509747

Hydrodynamic studies on micellar solutions of styrene–butadiene block copolymers in selective solvents
journal, October 1985

  • Oranli, Levent; Bahadur, Pratap; Riess, Gérard
  • Canadian Journal of Chemistry, Vol. 63, Issue 10
  • DOI: 10.1139/v85-447

Star and Cylindrical Micelles of Polystyrene- block -poly(2-cinnamoylethyl methacrylate) in Cyclopentane
journal, May 1997

  • Tao, Jian; Stewart, Sean; Liu, Guojun
  • Macromolecules, Vol. 30, Issue 9
  • DOI: 10.1021/ma9612788

A Small-Angle Neutron and X-ray Contrast Variation Scattering Study of the Structure of Block Copolymer Micelles:  Corona Shape and Excluded Volume Interactions
journal, January 2003

  • Pedersen, Jan Skov; Svaneborg, Carsten; Almdal, Kristoffer
  • Macromolecules, Vol. 36, Issue 2
  • DOI: 10.1021/ma0204913

Chain Exchange in Binary Copolymer Micelles at Equilibrium: Confirmation of the Independent Chain Hypothesis
journal, April 2013

  • Lu, J.; Bates, F. S.; Lodge, T. P.
  • ACS Macro Letters, Vol. 2, Issue 5
  • DOI: 10.1021/mz400167x

Micellar behaviour of styrene—isoprene block copolymers in selective solvents
journal, December 1985

Micellization of polystyrene-poly(ethylene oxide) block copolymers in water. 5. A test of the star and mean-field models
journal, March 1992

  • Xu, Renliang; Winnik, Mitchell A.; Riess, Gerard
  • Macromolecules, Vol. 25, Issue 2
  • DOI: 10.1021/ma00028a025

Adsorption at the solid—solution interface and micelle formation in water of the poly(oxyethylene—styrene—oxyethylene) triblock copolymer
journal, August 1993

  • Jada, A.; Siffert, B.; Riess, G.
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 75
  • DOI: 10.1016/0927-7757(93)80431-D

Hydrophobic, Highly Conductive Ambient-Temperature Molten Salts †
journal, January 1996

  • Bonhôte, Pierre; Dias, Ana-Paula; Papageorgiou, Nicholas
  • Inorganic Chemistry, Vol. 35, Issue 5
  • DOI: 10.1021/ic951325x

Theory of the kinetics of micellar equilibria and quantitative interpretation of chemical relaxation studies of micellar solutions of ionic surfactants
journal, April 1976

  • Aniansson, E. A. G.; Wall, S. N.; Almgren, M.
  • The Journal of Physical Chemistry, Vol. 80, Issue 9
  • DOI: 10.1021/j100550a001

Structure and Dynamics of Concentrated Solutions of Asymmetric Block Copolymers in Slightly Selective Solvents
journal, January 1996

  • Lodge, T. P.; Xu, X.; Ryu, C. Y.
  • Macromolecules, Vol. 29, Issue 18
  • DOI: 10.1021/ma9604404

Small-Angle Neutron Scattering Analysis of the Structure and Interaction of Triblock Copolymer Micelles in Aqueous Solution
journal, April 1998

  • Liu, Yingchun; Chen, Sow-Hsin; Huang, John S.
  • Macromolecules, Vol. 31, Issue 7
  • DOI: 10.1021/ma971253o

Path-Dependent Morphology and Relaxation Kinetics of Highly Amphiphilic Diblock Copolymer Micelles in Ionic Liquids
journal, February 2010

  • Meli, Luciana; Santiago, Jessica M.; Lodge, Timothy P.
  • Macromolecules, Vol. 43, Issue 4
  • DOI: 10.1021/ma902366c

Structure−Property Study of Diblock Copolymer Micelles:  Core and Corona Radius with Varying Composition and Degree of Polymerization
journal, November 2005

  • Guerrero-Sanchez, Carlos; Wouters, Daan; Fustin, Charles-André
  • Macromolecules, Vol. 38, Issue 24
  • DOI: 10.1021/ma051544u

Block Copolymers of Styrene and Stearyl Methacrylate. Synthesis and Micellization Properties in Selective Solvents
journal, July 2000

  • Pitsikalis, Marinos; Siakali-Kioulafa, Ekaterini; Hadjichristidis, Nikos
  • Macromolecules, Vol. 33, Issue 15
  • DOI: 10.1021/ma0002646

Block Copolymer Micelles in Dilute Solution
journal, January 1978

  • Kotaka, Tadao; Tanaka, Takeshi; Hattori, Mitsuhiro
  • Macromolecules, Vol. 11, Issue 1
  • DOI: 10.1021/ma60061a025

Solubilization in spherical block copolymer micelles: Scaling analysis based on star model
journal, May 1993

  • Nagarajan, R.; Ganesh, K.
  • The Journal of Chemical Physics, Vol. 98, Issue 9
  • DOI: 10.1063/1.464708

Poly(styrene-b-isoprene) micelles. Effect of molecular weight on micelle size
journal, January 1986

Light-scattering study of the association behavior of styrene-ethylene oxide block copolymers in aqueous solution
journal, January 1991

  • Xu, Renliang; Winnik, Mitchell A.; Hallett, F. R.
  • Macromolecules, Vol. 24, Issue 1
  • DOI: 10.1021/ma00001a014

Interfacial properties of immiscible homopolymer blends in the presence of block copolymers
journal, March 1982

Diblock Copolymer Micelles in a Dilute Solution
journal, June 2005

  • Zhulina, Ekaterina B.; Adam, Mireile; LaRue, Isaac
  • Macromolecules, Vol. 38, Issue 12
  • DOI: 10.1021/ma048102n

Logarithmic Chain-Exchange Kinetics of Diblock Copolymer Micelles
journal, February 2006

Molecular Exchange in Ordered Diblock Copolymer Micelles
journal, May 2011

  • Choi, Soo-Hyung; Bates, Frank S.; Lodge, Timothy P.
  • Macromolecules, Vol. 44, Issue 9
  • DOI: 10.1021/ma102788v

Formation of Block Copolymer Micelles in Solution:  A Monte Carlo Study of Chain Length Dependence
journal, March 2001

  • Milchev, Andrey; Bhattacharya, Aniket; Binder, Kurt
  • Macromolecules, Vol. 34, Issue 6
  • DOI: 10.1021/ma000645j

A Monte Carlo simulation for the micellization of ABA- and BAB-type triblock copolymers in a selective solvent. II. Effects of the block composition
journal, November 2002

  • Kim, Seung Hyun; Jo, Won Ho
  • The Journal of Chemical Physics, Vol. 117, Issue 18
  • DOI: 10.1063/1.1512646

Micelle formation and polyisobutylene solubilization by polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene block copolymers
journal, May 1995

  • Quintana, José R.; Salazar, Ramiro A.; Katime, Issa
  • Macromolecular Chemistry and Physics, Vol. 196, Issue 5
  • DOI: 10.1002/macp.1995.021960519

Micellization of strongly segregated block copolymers
journal, June 1996

  • Förster, Stephan; Zisenis, Mathias; Wenz, Eckhard
  • The Journal of Chemical Physics, Vol. 104, Issue 24
  • DOI: 10.1063/1.471723

Structures of PEP–PEO Block Copolymer Micelles: Effects of Changing Solvent and PEO Length and Comparison to a Thermodynamic Model
journal, December 2011

  • Jensen, Grethe Vestergaard; Shi, Qing; Deen, G. Roshan
  • Macromolecules, Vol. 45, Issue 1
  • DOI: 10.1021/ma2016369

Structure of Poly(styrene- b -ethylene- alt -propylene) Diblock Copolymer Micelles in Squalane †
journal, October 2009

  • Choi, Soo-Hyung; Bates, Frank S.; Lodge, Timothy P.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 42
  • DOI: 10.1021/jp8111149

Lower Critical Solution Temperature Phase Behavior of Poly( n -butyl methacrylate) in Ionic Liquid Mixtures
journal, November 2013

  • Hoarfrost, Megan L.; He, Yanpu; Lodge, Timothy P.
  • Macromolecules, Vol. 46, Issue 23
  • DOI: 10.1021/ma401450w

Theory of block copolymer micelles in solution
journal, September 1983

Micelle Morphology and Mechanical Response of Triblock Gels
journal, November 2009

  • Seitz, Michelle E.; Burghardt, Wesley R.; Shull, Kenneth R.
  • Macromolecules, Vol. 42, Issue 22
  • DOI: 10.1021/ma901448x

Tethered chains in polymer microstructures
book, January 2006

  • Halperin, A.; Tirrell, M.; Lodge, T. P.
  • Macromolecules: Synthesis, Order and Advanced Properties
  • DOI: 10.1007/BFb0051635

Structure of polystyrene-block-poly(ethylene oxide) diblock copolymer micelles in water
journal, November 1996

  • Jada, Amane; Hurtrez, Guy; Siffert, Bernard
  • Macromolecular Chemistry and Physics, Vol. 197, Issue 11
  • DOI: 10.1002/macp.1996.021971117
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