Temperature-dependent self-assembly and rheological behavior of a thermoreversible pmma-P n BA-PMMA triblock copolymer gel

Zabet, Mahla; Mishra, Satish; Boy, Ramiz; Walters, Keisha B.; Naskar, Amit K.; Kundu, Santanu

doi:10.1002/polb.24336

Title: Temperature-dependent self-assembly and rheological behavior of a thermoreversible pmma-P n BA-PMMA triblock copolymer gel

Journal Article · Sat Mar 25 00:00:00 EDT 2017 · Journal of Polymer Science. Part B, Polymer Physics

DOI:https://doi.org/10.1002/polb.24336· OSTI ID:1368270

Zabet, Mahla ^[1]; Mishra, Satish ^[1]; Boy, Ramiz ^[2]; Walters, Keisha B. ^[3]; Naskar, Amit K. ^[2]; Kundu, Santanu ^[1]

Dave C. Swalm School of Chemical Engineering, Mississippi State University, MS State Mississippi 39762
Oak Ridge National Laboratory, Materials Science and Technology Division, Oak Ridge Tennessee 37831
School of Chemical, Biological and Materials Engineering, University of Oklahoma, Norman Oklahoma 73019

Self-assembly and mechanical properties of triblock copolymers in a mid-block selective solvent are of interest in many applications. Herein, we report physical assembly of an ABA triblock copolymer, [PMMA–PnBA–PMMA] in two different mid-block selective solvents, n-butanol and 2-ethyl-1-hexanol. Gel formation resulting from end-block associations and the corresponding changes in mechanical properties have been investigated over a temperature range of -80 °C to 60 °C, from near the solvent melting points to above the gelation temperature. Shear-rheometry, thermal analysis, and small-angle neutron scattering data reveal formation and transition of structure in these systems from a liquid state to a gel state to a percolated cluster network with decrease in temperature. The aggregated PMMA end-blocks display a glass transition temperature. Our results provide new understanding into the structural changes of a self-assembled triblock copolymer gel over a large length scale and wide temperature range.

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

Sponsoring Organization:: National Science Foundation (NSF)

OSTI ID:: 1368270

Journal Information:: Journal of Polymer Science. Part B, Polymer Physics, Vol. 55, Issue 11; ISSN 0887-6266

Publisher:: Wiley

Country of Publication:: United States

Language:: ENGLISH

References (66)

Formation of macroporous self-assembled hydrogels through cryogelation of Fmoc–Phe–Phe Berillo, Dmitriy; Mattiasson, Bo; Galaev, Igor Yu. Journal of Colloid and Interface Science, Vol. 368, Issue 1 https://doi.org/10.1016/j.jcis.2011.11.006	journal	February 2012
Supramolecular gels formed from multi-component low molecular weight species Buerkle, Lauren E.; Rowan, Stuart J. Chemical Society Reviews, Vol. 41, Issue 18 https://doi.org/10.1039/c2cs35106d	journal	January 2012
C ₃ -Symmetrical Supramolecular Architectures: Fibers and Organic Gels from Discotic Trisamides and Trisureas van Gorp, Judith J.; Vekemans, Jef A. J. M.; Meijer, E. W. Journal of the American Chemical Society, Vol. 124, Issue 49 https://doi.org/10.1021/ja020984n	journal	December 2002
Microtubule Formation Using Two-Component Gel System Lee, Ho Yong; Nam, Seong Ryong; Hong, Jong-In Journal of the American Chemical Society, Vol. 129, Issue 5 https://doi.org/10.1021/ja0676197	journal	February 2007
Solvent-regulated ordering in block copolymers Alexandridis, Paschalis; Spontak, Richard J. Current Opinion in Colloid & Interface Science, Vol. 4, Issue 2 https://doi.org/10.1016/S1359-0294(99)00022-9	journal	April 1999
Micellar Ordering in Concentrated Solutions of Di- and Triblock Copolymers in a Slightly Selective Solvent Hamley, I. W.; Fairclough, J. P. A.; Ryan, A. J. Macromolecules, Vol. 31, Issue 4 https://doi.org/10.1021/ma970831y	journal	February 1998
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
Origins of Mechanical Strength and Elasticity in Thermally Reversible, Acrylic Triblock Copolymer Gels Drzal, Peter L.; Shull, Kenneth R. Macromolecules, Vol. 36, Issue 6 https://doi.org/10.1021/ma021255v	journal	March 2003
Strain Stiffening in Synthetic and Biopolymer Networks Erk, Kendra A.; Henderson, Kevin J.; Shull, Kenneth R. Biomacromolecules, Vol. 11, Issue 5 https://doi.org/10.1021/bm100136y	journal	May 2010
Time-Resolved Small-Angle X-ray Scattering Study of the Kinetics of Disorder−Order Transition in a Triblock Copolymer in a Selective Solvent for the Middle Block Nie, Huifen; Bansil, Rama; Ludwig, Karl Macromolecules, Vol. 36, Issue 21 https://doi.org/10.1021/ma034357+	journal	September 2003
Structural studies of aqueous solutions of PEO - PPO - PEO triblock copolymers, their micellar aggregates and mesophases; a small-angle neutron scattering study Mortensen, Kell Journal of Physics: Condensed Matter, Vol. 8, Issue 25A https://doi.org/10.1088/0953-8984/8/25A/008	journal	June 1996
Triblock Copolymer Self-Assembly in Ionic Liquids: Effect of PEO Block Length on the Self-Assembly of PEO–PPO–PEO in Ethylammonium Nitrate López-Barrón, Carlos R.; Li, Dongcui; Wagner, Norman J. Macromolecules, Vol. 47, Issue 21 https://doi.org/10.1021/ma501238w	journal	October 2014
Structure and ordering kinetics of micelles in triblock copolymer solutions in selective solvents Bansil, R.; Nie, H.; Li, Y. Macromolecular Symposia, Vol. 190, Issue 1 https://doi.org/10.1002/masy.200290012	journal	November 2002
Physical Gelation in a Triblock Copolymer Solution: In Situ Study of Stress−Strain Behavior and Structural Development Kleppinger, R.; van Es, M.; Mischenko, N. Macromolecules, Vol. 31, Issue 17 https://doi.org/10.1021/ma9801164	journal	August 1998
Self-Assembly and Stress Relaxation in Acrylic Triblock Copolymer Gels Seitz, Michelle E.; Burghardt, Wesley R.; Faber, K. T. Macromolecules, Vol. 40, Issue 4 https://doi.org/10.1021/ma061993+	journal	January 2007
Small-Angle X-ray and Neutron Scattering from Bulk and Oriented Triblock Copolymer Gels Mischenko, N.; Reynders, K.; Koch, M. H. J. Macromolecules, Vol. 28, Issue 6 https://doi.org/10.1021/ma00110a045	journal	November 1995
Properties of electroresponsive poly(vinyl alcohol)/poly(acrylic acid) IPN hydrogels under an electric stimulus Kim, So Yeon; Shin, Heung Soo; Lee, Young Moo Journal of Applied Polymer Science, Vol. 73, Issue 9 https://doi.org/10.1002/(SICI)1097-4628(19990829)73:9<1675::AID-APP8>3.0.CO;2-9	journal	August 1999
Electric field sensitive neutral polymer gels Filipcsei, G.; Fehér, J.; Zrı́nyi, M. Journal of Molecular Structure, Vol. 554, Issue 1 https://doi.org/10.1016/S0022-2860(00)00564-0	journal	October 2000
Concentration Dependence of Loop Fraction in Styrene−Isoprene−Styrene Triblock Copolymer Solutions and Corresponding Changes in Equilibrium Elasticity Watanabe, Hiroshi; Sato, Tomohiro; Osaki, Kunihiro Macromolecules, Vol. 33, Issue 7 https://doi.org/10.1021/ma991979f	journal	April 2000
Morphology and Rheology of SIS and SEPS Triblock Copolymers in the Presence of a Midblock-Selective Solvent Laurer, J. H.; Khan, S. A.; Spontak, R. J. Langmuir, Vol. 15, Issue 23 https://doi.org/10.1021/la981441n	journal	November 1999
Thermoplastic elastomer gels. II. Effects of composition and temperature on morphology and gel rheology Laurer, J. H.; Mulling, J. F.; Khan, S. A. Journal of Polymer Science Part B: Polymer Physics, Vol. 36, Issue 14 https://doi.org/10.1002/(SICI)1099-0488(199810)36:14<2513::AID-POLB5>3.0.CO;2-T	journal	October 1998
Structural Studies of Thermoplastic Triblock Copolymer Gels Mischenko, N.; Reynders, K.; Mortensen, K. Macromolecules, Vol. 27, Issue 8 https://doi.org/10.1021/ma00086a061	journal	April 1994
Rheological and Dielectric Behavior of a Styrene−Isoprene−Styrene Triblock Copolymer in Selective Solvents. 2. Contribution of Loop-Type Middle Blocks to Elasticity and Plasticity Watanabe, Hiroshi; Sato, Tomohiro; Osaki, Kunihiro Macromolecules, Vol. 30, Issue 19 https://doi.org/10.1021/ma9617577	journal	September 1997
Three-dimensional crystallographic determination of the body-centered-cubic morphologies of shear-aligned block copolymer systems Mortensen, Kell Journal of Polymer Science Part B: Polymer Physics, Vol. 42, Issue 17 https://doi.org/10.1002/polb.20166	journal	July 2004
Ordering Phenomena in ABA Triblock Copolymer Gels Reynders, K.; Mischenko, N.; Kleppinger, R. Journal of Applied Crystallography, Vol. 30, Issue 5 https://doi.org/10.1107/S0021889897001520	journal	October 1997
A High-Temperature Cubic Morphology in Triblock Copolymer Gels Kleppinger, R.; Reynders, K.; Mischenko, N. Macromolecules, Vol. 30, Issue 22 https://doi.org/10.1021/ma9703968	journal	November 1997
Phase behavior and viscoelastic properties of entangled block copolymer gels Vega, Daniel A.; Sebastian, John M.; Loo, Yueh-Lin Journal of Polymer Science Part B: Polymer Physics, Vol. 39, Issue 18 https://doi.org/10.1002/polb.1192	journal	January 2001
Long-range order in physical networks of gel-forming triblock copolymer solutions Kleppinger, R.; Mischenko, N.; Reynaers, H. L. Journal of Polymer Science Part B: Polymer Physics, Vol. 37, Issue 15 https://doi.org/10.1002/(SICI)1099-0488(19990801)37:15<1833::AID-POLB7>3.0.CO;2-7	journal	August 1999
Rate-Dependent Stiffening and Strain Localization in Physically Associating Solutions Erk, Kendra A.; Shull, Kenneth R. Macromolecules, Vol. 44, Issue 4 https://doi.org/10.1021/ma102156p	journal	February 2011
Rheological Properties of Aqueous Micellar Gels of a Thermo- and pH-Sensitive ABA Triblock Copolymer O’Lenick, Thomas G.; Jin, Naixiong; Woodcock, Jeremiah W. The Journal of Physical Chemistry B, Vol. 115, Issue 12 https://doi.org/10.1021/jp2001332	journal	March 2011
Synthesis of Biocompatible, Stimuli-Responsive, Physical Gels Based on ABA Triblock Copolymers Ma, Yinghua; Tang, Yiqing; Billingham, Norman C. Biomacromolecules, Vol. 4, Issue 4 https://doi.org/10.1021/bm034118u	journal	July 2003
Thermoreversible Physical Gelation of Block Copolymers in a Selective Solvent Sato, Tomohiro; Watanabe, Hiroshi; Osaki, Kunihiro Macromolecules, Vol. 33, Issue 5 https://doi.org/10.1021/ma991602+	journal	February 2000
Aggregation of Telechelic Triblock Copolymers: From Animals to Flowers Lairez, D.; Adam, M.; Carton, J. -P. Macromolecules, Vol. 30, Issue 22 https://doi.org/10.1021/ma970666m	journal	November 1997
Association and physical gelation of ABA triblock copolymer in selective solvent Inomata, Katsuhiro; Nakanishi, Daisuke; Banno, Ai Polymer, Vol. 44, Issue 18 https://doi.org/10.1016/S0032-3861(03)00534-2	journal	August 2003
Triblock copolymer based thermoreversible gels. 1: Self-association of sPMMA end-blocks in o-xylene and viscoelasticity of the gels Yu, Jian Ming; Jérôme, Robert; Teyssié, Philippe Polymer, Vol. 38, Issue 2 https://doi.org/10.1016/S0032-3861(96)00496-X	journal	January 1997
Thermoreversible Ion Gels with Tunable Melting Temperatures from Triblock and Pentablock Copolymers He, Yiyong; Lodge, Timothy P. Macromolecules, Vol. 41, Issue 1 https://doi.org/10.1021/ma702014z	journal	January 2008
Thermoplastic elastomer gels. I. Effects of composition and processing on morphology and gel behavior Laurer, Jonathan H.; Mulling, James F.; Khan, Saad A. Journal of Polymer Science Part B: Polymer Physics, Vol. 36, Issue 13 https://doi.org/10.1002/(SICI)1099-0488(19980930)36:13<2379::AID-POLB13>3.0.CO;2-0	journal	September 1998
Modeling viscoelastic properties of triblock copolymers: A DPD simulation study Sliozberg, Yelena R.; Andzelm, Jan W.; Brennan, John K. Journal of Polymer Science Part B: Polymer Physics, Vol. 48, Issue 1 https://doi.org/10.1002/polb.21839	journal	January 2010
Complex Micelles from Self-Assembly of ABA Triblock Copolymers in B-Selective Solvents Kong, Weixin; Li, Baohui; Jin, Qinghua Langmuir, Vol. 26, Issue 6 https://doi.org/10.1021/la903292f	journal	March 2010
Self-Consistent Field Theory of Gelation in Triblock Copolymer Solutions Bras, Rafael E.; Shull, Kenneth R. Macromolecules, Vol. 42, Issue 21 https://doi.org/10.1021/ma9013687	journal	November 2009
Phase behavior of SEBS triblock copolymer gels Chantawansri, Tanya L.; Duncan, Andrew J.; Ilavsky, Jan Journal of Polymer Science Part B: Polymer Physics, Vol. 49, Issue 20 https://doi.org/10.1002/polb.22335	journal	August 2011
Computational Study of the Structure and Rheological Properties of Self-Associating Polymer Networks Wilson, Mark; Rabinovitch, Avinoam; Baljon, Arlette R. C. Macromolecules, Vol. 48, Issue 17 https://doi.org/10.1021/acs.macromol.5b00885	journal	August 2015
Shear banding in simulated telechelic polymers Billen, Joris; Wilson, Mark; Baljon, Arlette R. C. Chemical Physics, Vol. 446 https://doi.org/10.1016/j.chemphys.2014.11.001	journal	January 2015
Reduction and analysis of SANS and USANS data using IGOR Pro Kline, Steven R. Journal of Applied Crystallography, Vol. 39, Issue 6, p. 895-900 https://doi.org/10.1107/S0021889806035059	journal	November 2006
Studies on poly(ethyl acrylate) in θ solvents Llopis, J.; Albert, A.; Usobiaga, P. European Polymer Journal, Vol. 3, Issue 2 https://doi.org/10.1016/0014-3057(67)90070-5	journal	May 1967
Supramolecular dendritic liquid quasicrystals Zeng, Xiangbing; Ungar, Goran; Liu, Yongsong Nature, Vol. 428, Issue 6979 https://doi.org/10.1038/nature02368	journal	March 2004
Halogen Bonding: A New Interaction for Liquid Crystal Formation Nguyen, H. Loc; Horton, Peter N.; Hursthouse, Michael B. Journal of the American Chemical Society, Vol. 126, Issue 1 https://doi.org/10.1021/ja036994l	journal	January 2004
Viscoelastic phase separation Tanaka, Hajime Journal of Physics: Condensed Matter, Vol. 12, Issue 15 https://doi.org/10.1088/0953-8984/12/15/201	journal	March 2000
Quantitative Structure−Property Relationship (QSPR) Correlation of Glass Transition Temperatures of High Molecular Weight Polymers Katritzky, Alan R.; Sild, Sulev; Lobanov, Victor Journal of Chemical Information and Computer Sciences, Vol. 38, Issue 2 https://doi.org/10.1021/ci9700687	journal	March 1998
Thermally Responsive Amphiphilic Conetworks and Gels Based on Poly( N -isopropylacrylamide) and Polyisobutylene Kali, Gergely; Vavra, Szilvia; László, Krisztina Macromolecules, Vol. 46, Issue 13 https://doi.org/10.1021/ma400535r	journal	June 2013
A Comparison of Ethanol and Butanol as Oxygenates Using a Direct-Injection, Spark-Ignition Engine Wallner, Thomas; Miers, Scott A.; McConnell, Steve Journal of Engineering for Gas Turbines and Power, Vol. 131, Issue 3 https://doi.org/10.1115/1.3043810	journal	February 2009
Vibrational and structural properties of amorphous n-butanol: A complementary Raman spectroscopy and X-ray diffraction study Hédoux, Alain; Guinet, Yannick; Paccou, L. The Journal of Chemical Physics, Vol. 138, Issue 21 https://doi.org/10.1063/1.4808159	journal	June 2013
The kinetics of isothermal cold crystallization and tensile properties of poly(ethylene terephthalate) Wellen, R. M. R.; Rabello, M. S. Journal of Materials Science, Vol. 40, Issue 23 https://doi.org/10.1007/s10853-005-3173-3	journal	September 2005
Physical aging of polymers Hutchinson, John M. Progress in Polymer Science, Vol. 20, Issue 4 https://doi.org/10.1016/0079-6700(94)00001-I	journal	January 1995
Microstructure and Physical Properties of a pH-Responsive Gel Based on a Novel Biocompatible ABA-Type Triblock Copolymer Castelletto, Valeria; Hamley, Ian W.; Ma, Yinghua Langmuir, Vol. 20, Issue 10 https://doi.org/10.1021/la049859a	journal	May 2004
Structural Development and Adhesion of Acrylic ABA Triblock Copolymer Gels Flanigan, Cynthia M.; Crosby, Alfred J.; Shull, Kenneth R. Macromolecules, Vol. 32, Issue 21 https://doi.org/10.1021/ma990873h	journal	October 1999
Viscoelastic properties of branched polyacrylate melts: Viscoelasticity of branched PA melts Ahmad, Nasir M.; Lovell, Peter A.; Underwood, Sylvia M. Polymer International, Vol. 50, Issue 6 https://doi.org/10.1002/pi.672	journal	June 2001
Microphase structure of block ionomers. 1. Study of molded styrene-4-vinylpyridinium ABA blocks by SAXS and SANS Gouin, Jean Pierre; Williams, Claudine E.; Eisenberg, Adi Macromolecules, Vol. 22, Issue 12 https://doi.org/10.1021/ma00202a032	journal	December 1989
A new Guinier–Porod model Hammouda, Boualem Journal of Applied Crystallography, Vol. 43, Issue 4 https://doi.org/10.1107/S0021889810015773	journal	May 2010
Surface and mass fractals in vapor-phase aggregates Hurd, Alan J.; Schaefer, Dale W.; Martin, James E. Physical Review A, Vol. 35, Issue 5 https://doi.org/10.1103/PhysRevA.35.2361	journal	March 1987
Insight into Clustering in Poly(ethylene oxide) Solutions Hammouda, Boualem; Ho, Derek L.; Kline, Steve Macromolecules, Vol. 37, Issue 18 https://doi.org/10.1021/ma049623d	journal	September 2004
Structural Properties of Pure Simple Alcohols from Ethanol, Propanol, Butanol, Pentanol, to Hexanol: Comparing Monte Carlo Simulations with Experimental SAXS Data Tomšič, Matija; Jamnik, Andrej; Fritz-Popovski, Gerhard The Journal of Physical Chemistry B, Vol. 111, Issue 7 https://doi.org/10.1021/jp066139z	journal	February 2007
Molecular mapping of poly(methyl methacrylate) super-helix stereocomplexes Christofferson, Andrew Joseph; Yiapanis, George; Ren, Jing Ming Chemical Science, Vol. 6, Issue 2 https://doi.org/10.1039/C4SC02971B	journal	January 2015
X-ray scattering measurements of order in non-crystalline polymers Windle, A. H. Pure and Applied Chemistry, Vol. 57, Issue 11 https://doi.org/10.1351/pac198557111627	journal	January 1985
Fracture-Healing Kinetics of Thermoreversible Physical Gels Quantified by Shear Rheophysical Experiments Thornell, Travis L.; Helfrecht, Benjamin A.; Mullen, Scott A. ACS Macro Letters, Vol. 3, Issue 10 https://doi.org/10.1021/mz500524d	journal	October 2014
In situ neutron scattering study of structural transitions in fibrin networks under shear deformation Weigandt, Katie M.; Porcar, Lionel; Pozzo, Danilo C. Soft Matter, Vol. 7, Issue 21, p. 9992-10000 https://doi.org/10.1039/c1sm06176c	journal	January 2011

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