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

Ma, Yuanchi; Lodge, Timothy P.

doi:10.1021/acs.macromol.6b00315

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

Journal Article · Fri Apr 29 00:00:00 EDT 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b00315· OSTI ID:1256360

Ma, Yuanchi ^[1]; Lodge, Timothy P. ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)

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 (R_h) and core radius (R_c) were obtained by DLS and SAXS, respectively. It was found that R_c and the degree of polymerization of the core block, NB, followed a power law relationship in which R_c ~ NB^0.71±0.01. The corona thickness (L_corona), given by the difference of Rh and R_c, 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 R_c and L_corona dependence on core block lengths, due to the use of seven different block copolymers with identical corona block lengths.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: 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)

Grant/Contract Number:: DMR-1206459; DMR-9304725; IBHE HECA NWU 96; W-31-109-Eng-38

OSTI ID:: 1256360

Journal Information:: Macromolecules, Vol. 49, Issue 9; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

Citation Metrics:

Cited by: 21 works

Citation information provided by
Web of Science

References (59)

Block copolymers of styrene andn-alkyl methacrylates with long alkyl groups. Micellization behavior in selective solvents Pitsikalis, Marinos; Siakali-Kioulafa, Ekaterini; Hadjichristidis, Nikos Journal of Polymer Science Part A: Polymer Chemistry, Vol. 42, Issue 17 https://doi.org/10.1002/pola.20258	journal	January 2004
Analysis of Macromolecular Polydispersity in Intensity Correlation Spectroscopy: The Method of Cumulants Koppel, Dennis E. The Journal of Chemical Physics, Vol. 57, Issue 11 https://doi.org/10.1063/1.1678153	journal	December 1972
Star shaped polymers : a model for the conformation and its concentration dependence Daoud, M.; Cotton, J. P. Journal de Physique, Vol. 43, Issue 3 https://doi.org/10.1051/jphys:01982004303053100	journal	January 1982
Effect of the Soluble Block Size on Spherical Diblock Copolymer Micelles LaRue, Isaac; Adam, Mireille; Zhulina, Ekaterina B. Macromolecules, Vol. 41, Issue 17 https://doi.org/10.1021/ma800403r	journal	September 2008
Self-Diffusion and Tracer Diffusion in Sphere-Forming Block Copolymers Cavicchi, Kevin A.; Lodge, Timothy P. Macromolecules, Vol. 36, Issue 19 https://doi.org/10.1021/ma0346815	journal	September 2003
Structural Properties of Weakly Segregated PS−PB Block Copolymer Micelles in n -Alkanes: Solvent Entropy Effects Lund, Reidar; Willner, Lutz; Lindner, Peter Macromolecules, Vol. 42, Issue 7 https://doi.org/10.1021/ma8021629	journal	April 2009
Polymeric micelles: a star model Halperin, A. Macromolecules, Vol. 20, Issue 11 https://doi.org/10.1021/ma00177a051	journal	November 1987
Regularized Positive Exponential Sum (REPES) Program - A Way of Inverting Laplace Transform Data Obtained by Dynamic Light Scattering Jakeš, Jaromír Collection of Czechoslovak Chemical Communications, Vol. 60, Issue 11 https://doi.org/10.1135/cccc19951781	journal	January 1995
Block copolymer self‐assembly in selective solvents: Spherical micelles with segregated cores Nagarajan, R.; Ganesh, K. The Journal of Chemical Physics, Vol. 90, Issue 10 https://doi.org/10.1063/1.456390	journal	May 1989
Determination of the Micelle Architecture of Polystyrene/Poly(4-vinylpyridine) Block Copolymers in Dilute Solution Antonietti, Markus; Heinz, Steffi; Schmidt, Manfred Macromolecules, Vol. 27, Issue 12, p. 3276-3281 https://doi.org/10.1021/ma00090a021	journal	June 1994
Remarkable Effect of Molecular Architecture on Chain Exchange in Triblock Copolymer Micelles Lu, Jie; Bates, Frank S.; Lodge, Timothy P. Macromolecules, Vol. 48, Issue 8 https://doi.org/10.1021/acs.macromol.5b00294	journal	April 2015
Disorder-order transitions in soft sphere polymer micelles McConnell, Glen A.; Gast, Alice P.; Huang, John S. Physical Review Letters, Vol. 71, Issue 13 https://doi.org/10.1103/PhysRevLett.71.2102	journal	September 1993
Molecular Exchange in PEO−PB Micelles in Water Won, You-Yeon; Davis, H. Ted; Bates, Frank S. Macromolecules, Vol. 36, Issue 3 https://doi.org/10.1021/ma021439+	journal	January 2003
Styrene/butadiene block copolymer micelles in heptane Bluhm, T. L.; Whitmore, M. D. Canadian Journal of Chemistry, Vol. 63, Issue 1 https://doi.org/10.1139/v85-041	journal	January 1985
Theory of Block Polymer Micelles: Recent Advances and Current Challenges Zhulina, E. B.; Borisov, O. V. Macromolecules, Vol. 45, Issue 11 https://doi.org/10.1021/ma300195n	journal	May 2012
Theory of unsymmetric polymer–polymer interfaces Helfand, Eugene; Sapse, Anne Marie The Journal of Chemical Physics, Vol. 62, Issue 4 https://doi.org/10.1063/1.430632	journal	February 1975
Investigation of Polystyrene-Poly(ethylene oxide) Block Copolymer Micelle Formation in Organic and Aqueous Solutions by Nonradiative Energy Transfer Experiments Calderara, F.; Hruska, Z.; Hurtrez, G. Macromolecules, Vol. 27, Issue 5 https://doi.org/10.1021/ma00083a020	journal	September 1994
Conformations of block-copolymer molecules in selective solvents (micellar structures Zhulina, Ye. B.; Birshtein, T. M. Polymer Science U.S.S.R., Vol. 27, Issue 3 https://doi.org/10.1016/0032-3950(85)90238-2	journal	January 1985
Temperature-dependent micellar structures in poly(styrene-b-isoprene) diblock copolymer solutions near the critical micelle temperature Bang, Joona; Viswanathan, Karthik; Lodge, Timothy P. The Journal of Chemical Physics, Vol. 121, Issue 22 https://doi.org/10.1063/1.1812753	journal	January 2004
Refractometric determination of second-order transition temperatures in polymers. II. Some acrylic, vinyl halide, and styrene polymers Wiley, Richard H.; Brauer, G. M. Journal of Polymer Science, Vol. 3, Issue 3 https://doi.org/10.1002/pol.1948.120030321	journal	June 1948
Surfactant or block copolymer micelles? Structural properties of a series of well-defined n -alkyl–PEO micelles in water studied by SANS Zinn, Thomas; Willner, Lutz; Lund, Reidar Soft Matter, Vol. 10, Issue 28 https://doi.org/10.1039/C4SM00625A	journal	January 2014
Static properties of polystyrene in poly(methyl methacrylate)–benzene semidilute solution Numasawa, N.; Hamada, T.; Nose, T. Journal of Polymer Science: Polymer Letters Edition, Vol. 23, Issue 1 https://doi.org/10.1002/pol.1985.130230101	journal	January 1985
Theory of critical micelle concentration for solutions of block copolymers Leibler, Ludwik; Orland, Henri; Wheeler, John C. The Journal of Chemical Physics, Vol. 79, Issue 7 https://doi.org/10.1063/1.446209	journal	October 1983
Micellization of block copolymers Riess, G. Progress in Polymer Science, Vol. 28, Issue 7 https://doi.org/10.1016/S0079-6700(03)00015-7	journal	July 2003
A small-angle neutron scattering investigation of the structure of highly swollen block copolymer micelles Castelletto, V.; Hamley, I. W.; Pedersen, J. S. The Journal of Chemical Physics, Vol. 117, Issue 17 https://doi.org/10.1063/1.1509747	journal	November 2002
Hydrodynamic studies on micellar solutions of styrene–butadiene block copolymers in selective solvents Oranli, Levent; Bahadur, Pratap; Riess, Gérard Canadian Journal of Chemistry, Vol. 63, Issue 10 https://doi.org/10.1139/v85-447	journal	October 1985
Star and Cylindrical Micelles of Polystyrene- block -poly(2-cinnamoylethyl methacrylate) in Cyclopentane Tao, Jian; Stewart, Sean; Liu, Guojun Macromolecules, Vol. 30, Issue 9 https://doi.org/10.1021/ma9612788	journal	May 1997
A Small-Angle Neutron and X-ray Contrast Variation Scattering Study of the Structure of Block Copolymer Micelles: Corona Shape and Excluded Volume Interactions Pedersen, Jan Skov; Svaneborg, Carsten; Almdal, Kristoffer Macromolecules, Vol. 36, Issue 2 https://doi.org/10.1021/ma0204913	journal	January 2003
Chain Exchange in Binary Copolymer Micelles at Equilibrium: Confirmation of the Independent Chain Hypothesis Lu, J.; Bates, F. S.; Lodge, T. P. ACS Macro Letters, Vol. 2, Issue 5 https://doi.org/10.1021/mz400167x	journal	April 2013
Micellar behaviour of styrene—isoprene block copolymers in selective solvents Bahadur, P.; Sastry, N. V.; Marti, S. Colloids and Surfaces, Vol. 16, Issue 3-4 https://doi.org/10.1016/0166-6622(85)80263-8	journal	December 1985
Micellization of polystyrene-poly(ethylene oxide) block copolymers in water. 5. A test of the star and mean-field models Xu, Renliang; Winnik, Mitchell A.; Riess, Gerard Macromolecules, Vol. 25, Issue 2 https://doi.org/10.1021/ma00028a025	journal	March 1992
Adsorption at the solid—solution interface and micelle formation in water of the poly(oxyethylene—styrene—oxyethylene) triblock copolymer Jada, A.; Siffert, B.; Riess, G. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 75 https://doi.org/10.1016/0927-7757(93)80431-D	journal	August 1993
Hydrophobic, Highly Conductive Ambient-Temperature Molten Salts ^† Bonhôte, Pierre; Dias, Ana-Paula; Papageorgiou, Nicholas Inorganic Chemistry, Vol. 35, Issue 5 https://doi.org/10.1021/ic951325x	journal	January 1996
Theory of the kinetics of micellar equilibria and quantitative interpretation of chemical relaxation studies of micellar solutions of ionic surfactants Aniansson, E. A. G.; Wall, S. N.; Almgren, M. The Journal of Physical Chemistry, Vol. 80, Issue 9 https://doi.org/10.1021/j100550a001	journal	April 1976
Structure and Dynamics of Concentrated Solutions of Asymmetric Block Copolymers in Slightly Selective Solvents Lodge, T. P.; Xu, X.; Ryu, C. Y. Macromolecules, Vol. 29, Issue 18 https://doi.org/10.1021/ma9604404	journal	January 1996
Small-Angle Neutron Scattering Analysis of the Structure and Interaction of Triblock Copolymer Micelles in Aqueous Solution Liu, Yingchun; Chen, Sow-Hsin; Huang, John S. Macromolecules, Vol. 31, Issue 7 https://doi.org/10.1021/ma971253o	journal	April 1998
Path-Dependent Morphology and Relaxation Kinetics of Highly Amphiphilic Diblock Copolymer Micelles in Ionic Liquids Meli, Luciana; Santiago, Jessica M.; Lodge, Timothy P. Macromolecules, Vol. 43, Issue 4 https://doi.org/10.1021/ma902366c	journal	February 2010
Structure−Property Study of Diblock Copolymer Micelles: Core and Corona Radius with Varying Composition and Degree of Polymerization Guerrero-Sanchez, Carlos; Wouters, Daan; Fustin, Charles-André Macromolecules, Vol. 38, Issue 24 https://doi.org/10.1021/ma051544u	journal	November 2005
Block Copolymers of Styrene and Stearyl Methacrylate. Synthesis and Micellization Properties in Selective Solvents Pitsikalis, Marinos; Siakali-Kioulafa, Ekaterini; Hadjichristidis, Nikos Macromolecules, Vol. 33, Issue 15 https://doi.org/10.1021/ma0002646	journal	July 2000
Block Copolymer Micelles in Dilute Solution Kotaka, Tadao; Tanaka, Takeshi; Hattori, Mitsuhiro Macromolecules, Vol. 11, Issue 1 https://doi.org/10.1021/ma60061a025	journal	January 1978
Solubilization in spherical block copolymer micelles: Scaling analysis based on star model Nagarajan, R.; Ganesh, K. The Journal of Chemical Physics, Vol. 98, Issue 9 https://doi.org/10.1063/1.464708	journal	May 1993
Poly(styrene-b-isoprene) micelles. Effect of molecular weight on micelle size Bluhm, T. L.; Malhotra, S. L. European Polymer Journal, Vol. 22, Issue 3 https://doi.org/10.1016/0014-3057(86)90096-0	journal	January 1986
Light-scattering study of the association behavior of styrene-ethylene oxide block copolymers in aqueous solution Xu, Renliang; Winnik, Mitchell A.; Hallett, F. R. Macromolecules, Vol. 24, Issue 1 https://doi.org/10.1021/ma00001a014	journal	January 1991
Interfacial properties of immiscible homopolymer blends in the presence of block copolymers Noolandi, J.; Hong, K. M. Macromolecules, Vol. 15, Issue 2 https://doi.org/10.1021/ma00230a054	journal	March 1982
Diblock Copolymer Micelles in a Dilute Solution Zhulina, Ekaterina B.; Adam, Mireile; LaRue, Isaac Macromolecules, Vol. 38, Issue 12 https://doi.org/10.1021/ma048102n	journal	June 2005
Logarithmic Chain-Exchange Kinetics of Diblock Copolymer Micelles Lund, Reidar; Willner, Lutz; Stellbrink, Jörg Physical Review Letters, Vol. 96, Issue 6 https://doi.org/10.1103/PhysRevLett.96.068302	journal	February 2006
Molecular Exchange in Ordered Diblock Copolymer Micelles Choi, Soo-Hyung; Bates, Frank S.; Lodge, Timothy P. Macromolecules, Vol. 44, Issue 9 https://doi.org/10.1021/ma102788v	journal	May 2011
Formation of Block Copolymer Micelles in Solution: A Monte Carlo Study of Chain Length Dependence Milchev, Andrey; Bhattacharya, Aniket; Binder, Kurt Macromolecules, Vol. 34, Issue 6 https://doi.org/10.1021/ma000645j	journal	March 2001
A Monte Carlo simulation for the micellization of ABA- and BAB-type triblock copolymers in a selective solvent. II. Effects of the block composition Kim, Seung Hyun; Jo, Won Ho The Journal of Chemical Physics, Vol. 117, Issue 18 https://doi.org/10.1063/1.1512646	journal	November 2002
Scaling theory of supermolecular structures in block copolymer-solvent systems: 1. Model of micellar structures Birshtein, T. M.; Zhulina, E. B. Polymer, Vol. 30, Issue 1 https://doi.org/10.1016/0032-3861(89)90399-6	journal	January 1989
Micelle formation and polyisobutylene solubilization by polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene block copolymers Quintana, José R.; Salazar, Ramiro A.; Katime, Issa Macromolecular Chemistry and Physics, Vol. 196, Issue 5 https://doi.org/10.1002/macp.1995.021960519	journal	May 1995
Micellization of strongly segregated block copolymers Förster, Stephan; Zisenis, Mathias; Wenz, Eckhard The Journal of Chemical Physics, Vol. 104, Issue 24 https://doi.org/10.1063/1.471723	journal	June 1996
Structures of PEP–PEO Block Copolymer Micelles: Effects of Changing Solvent and PEO Length and Comparison to a Thermodynamic Model Jensen, Grethe Vestergaard; Shi, Qing; Deen, G. Roshan Macromolecules, Vol. 45, Issue 1 https://doi.org/10.1021/ma2016369	journal	December 2011
Structure of Poly(styrene- b -ethylene- alt -propylene) Diblock Copolymer Micelles in Squalane ^† Choi, Soo-Hyung; Bates, Frank S.; Lodge, Timothy P. The Journal of Physical Chemistry B, Vol. 113, Issue 42 https://doi.org/10.1021/jp8111149	journal	October 2009
Lower Critical Solution Temperature Phase Behavior of Poly( n -butyl methacrylate) in Ionic Liquid Mixtures Hoarfrost, Megan L.; He, Yanpu; Lodge, Timothy P. Macromolecules, Vol. 46, Issue 23 https://doi.org/10.1021/ma401450w	journal	November 2013
Theory of block copolymer micelles in solution Noolandi, Jaan; Hong, Kin Ming Macromolecules, Vol. 16, Issue 9 https://doi.org/10.1021/ma00243a007	journal	September 1983
Micelle Morphology and Mechanical Response of Triblock Gels Seitz, Michelle E.; Burghardt, Wesley R.; Shull, Kenneth R. Macromolecules, Vol. 42, Issue 22 https://doi.org/10.1021/ma901448x	journal	November 2009
Tethered chains in polymer microstructures Halperin, A.; Tirrell, M.; Lodge, T. P. Macromolecules: Synthesis, Order and Advanced Properties https://doi.org/10.1007/BFb0051635	book	January 2006
Structure of polystyrene-block-poly(ethylene oxide) diblock copolymer micelles in water Jada, Amane; Hurtrez, Guy; Siffert, Bernard Macromolecular Chemistry and Physics, Vol. 197, Issue 11 https://doi.org/10.1002/macp.1996.021971117	journal	November 1996

Cited By (2)

Broadband dielectric spectroscopy of micelles and microemulsions formed in a hydrophilic ionic liquid: the relaxation mechanism and interior parameters Lian, Yiwei; Zhao, Kongshuang New Journal of Chemistry, Vol. 42, Issue 4 https://doi.org/10.1039/c7nj04813k	journal	January 2018
Self-Assembly of Block and Graft Copolymers in Organic Solvents: An Overview of Recent Advances Atanase, Leonard; Riess, Gerard Polymers, Vol. 10, Issue 1 https://doi.org/10.3390/polym10010062	journal	January 2018

Similar Records

Exchange Kinetics for a Single Block Copolymer in Micelles of Two Different Sizes

Journal Article · Tue Mar 13 00:00:00 EDT 2018 · Macromolecules · OSTI ID:1256360

Zhao, Dan; Ma, Yuanchi; Lodge, Timothy P.

Unexpected Conformational Behavior of Poly(poly(ethylene glycol) methacrylate)-Poly(propylene carbonate)-Poly(poly(ethylene glycol) methacrylate) (PPEGMA-PPC-PPEGMA) Amphiphilic Block Copolymers in Micellar Solution and at the Air-Water Interface

Journal Article · Wed Apr 15 00:00:00 EDT 2020 · Journal of Colloid and Interface Science · OSTI ID:1256360

Lee, Jaewon; Pan, Jingyi; Chun, Jaehun; +1 more

Fluorine-Containing ABC Linear Triblock Terpolymers: Synthesis and Self-assembly in Solution

Journal Article · Sat Jan 01 00:00:00 EST 2011 · Journal of Polymer Science, Part A: Polymer Chemistry · OSTI ID:1256360

He, Lihong; Hinestrosa Salazar, Juan P; Pickel, Joseph M; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Dynamic light scattering
X-ray scattering
Micelles
Copolymers
Solvents

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

Citation Formats

References (59)

Cited By (2)

Similar Records

Related Subjects