Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid

Abstract

Here, we utilized small-angle neutron scattering (SANS) to quantitatively characterize the LCST-type phase behavior of the poly(benzyl methacrylate) (PBnMA) derivative poly(2-phenylethyl methacrylate) (PPhEtMA) in the deuterated ionic liquid (IL) d8-1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (d8-[C2mIm+][TFSA-]). The SANS curves showed a discontinuous change from those characteristics of dispersed polymer chains to those of large aggregates of PPhEtMA chains suspended in the IL solution, indicating that phase separation occurs discontinuously at Tc. We also evaluated the enthalpic and entropic contributions to the effective interaction parameter χeff of PPhEtMA in [C2mIm+][TFSA-] and compared them with those of PBnMA. The absolute value of the enthalpic contribution observed for PPhEtMA was smaller than that for PBnMA. This difference in the enthalpic term can be attributed to the unfavorable interaction between the IL and the alkyl group in the side chain of PPhEtMA. In addition, the temperature dependence of χeff was smaller than the previously reported value for a thermo-responsive polymer in an aqueous system. Finally, it was found out that the strong dependence of Tc on the chemical structure in IL systems originated from the relatively smaller temperature dependence of χeff.

Authors:
 [1];  [2];  [3];  [4];  [5];  [4];  [1]
+ Show Author Affiliations
  1. Univ. of Tokyo (Japan). Inst. for Solid State Physics
  2. Yamaguchi Univ., Ube (Japan)
  3. National Inst. for Materials Science (NIMS), Tsukuba (Japan). Polymer Materials Unit
  4. Yokohama National Univ., Hodogaya-ku (Japan)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). High Flux Isotope Reactor (HFIR)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1327601
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 18; Journal Issue: 27; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Hirosawa, Kazu, Fujii, Kenta, Ueki, Takeshi, Kitazawa, Yuzo, Littrell, Kenneth C., Watanabe, Masayoshi, and Shibayama, Mitsuhiro. SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid. United States: N. p., 2016. Web. doi:10.1039/C6CP02254E.
Copy to clipboard
Hirosawa, Kazu, Fujii, Kenta, Ueki, Takeshi, Kitazawa, Yuzo, Littrell, Kenneth C., Watanabe, Masayoshi, & Shibayama, Mitsuhiro. SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid. United States. https://doi.org/10.1039/C6CP02254E
Copy to clipboard
Hirosawa, Kazu, Fujii, Kenta, Ueki, Takeshi, Kitazawa, Yuzo, Littrell, Kenneth C., Watanabe, Masayoshi, and Shibayama, Mitsuhiro. Fri . "SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid". United States. https://doi.org/10.1039/C6CP02254E. https://www.osti.gov/servlets/purl/1327601.
Copy to clipboard
@article{osti_1327601,
title = {SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid},
author = {Hirosawa, Kazu and Fujii, Kenta and Ueki, Takeshi and Kitazawa, Yuzo and Littrell, Kenneth C. and Watanabe, Masayoshi and Shibayama, Mitsuhiro},
abstractNote = {Here, we utilized small-angle neutron scattering (SANS) to quantitatively characterize the LCST-type phase behavior of the poly(benzyl methacrylate) (PBnMA) derivative poly(2-phenylethyl methacrylate) (PPhEtMA) in the deuterated ionic liquid (IL) d8-1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (d8-[C2mIm+][TFSA-]). The SANS curves showed a discontinuous change from those characteristics of dispersed polymer chains to those of large aggregates of PPhEtMA chains suspended in the IL solution, indicating that phase separation occurs discontinuously at Tc. We also evaluated the enthalpic and entropic contributions to the effective interaction parameter χeff of PPhEtMA in [C2mIm+][TFSA-] and compared them with those of PBnMA. The absolute value of the enthalpic contribution observed for PPhEtMA was smaller than that for PBnMA. This difference in the enthalpic term can be attributed to the unfavorable interaction between the IL and the alkyl group in the side chain of PPhEtMA. In addition, the temperature dependence of χeff was smaller than the previously reported value for a thermo-responsive polymer in an aqueous system. Finally, it was found out that the strong dependence of Tc on the chemical structure in IL systems originated from the relatively smaller temperature dependence of χeff.},
doi = {10.1039/C6CP02254E},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 27,
volume = 18,
place = {United States},
year = {Fri Jun 17 00:00:00 EDT 2016},
month = {Fri Jun 17 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C6CP02254E
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Lower Critical Solution Temperature Phase Behavior of Linear Polymers in Imidazolium-Based Ionic Liquids: Effects of Structural Modifications
journal, March 2009

  • Kodama, Koichi; Nanashima, Hideyuki; Ueki, Takeshi
  • Langmuir, Vol. 25, Issue 6
  • DOI: 10.1021/la803945n

Structural aspects of the LCST phase behavior of poly(benzyl methacrylate) in room-temperature ionic liquid
journal, March 2011

Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis
journal, August 1999

  • Welton, Thomas
  • Chemical Reviews, Vol. 99, Issue 8, p. 2071-2084
  • DOI: 10.1021/cr980032t

Lithium Secondary Batteries Using Modified-Imidazolium Room-Temperature Ionic Liquid
journal, June 2006

  • Seki, Shiro; Kobayashi, Yo; Miyashiro, Hajime
  • The Journal of Physical Chemistry B, Vol. 110, Issue 21
  • DOI: 10.1021/jp0620872

Unusual Li + Ion Solvation Structure in Bis(fluorosulfonyl)amide Based Ionic Liquid
journal, September 2013

  • Fujii, Kenta; Hamano, Hiroshi; Doi, Hiroyuki
  • The Journal of Physical Chemistry C, Vol. 117, Issue 38
  • DOI: 10.1021/jp4053264

Room temperature ionic liquids as novel media for ‘clean’ liquid–liquid extraction
journal, January 1998

  • Huddleston, Jonathan G.; Willauer, Heather D.; Swatloski, Richard P.
  • Chem. Commun., Issue 16
  • DOI: 10.1039/A803999B

Ionic liquids: solvent properties and organic reactivity
journal, January 2005

  • Chiappe, Cinzia; Pieraccini, Daniela
  • Journal of Physical Organic Chemistry, Vol. 18, Issue 4
  • DOI: 10.1002/poc.863

Lipase-Catalyzed Reactions in Ionic Liquids
journal, December 2000

  • Madeira Lau, R.; Van Rantwijk, F.; Seddon, K. R.
  • Organic Letters, Vol. 2, Issue 26
  • DOI: 10.1021/ol006732d

Dissolution of Cellose with Ionic Liquids
journal, May 2002

  • Swatloski, Richard P.; Spear, Scott K.; Holbrey, John D.
  • Journal of the American Chemical Society, Vol. 124, Issue 18, p. 4974-4975
  • DOI: 10.1021/ja025790m

Biocatalysis in Ionic Liquids
journal, June 2007

  • van Rantwijk, Fred; Sheldon, Roger A.
  • Chemical Reviews, Vol. 107, Issue 6, p. 2757-2785
  • DOI: 10.1021/cr050946x

Water-in-ionic liquid microemulsions as a new medium for enzymatic reactions
journal, January 2008

  • Moniruzzaman, Muhammad; Kamiya, Noriho; Nakashima, Kazunori
  • Green Chemistry, Vol. 10, Issue 5
  • DOI: 10.1039/b802501k

Ionic liquid–polymer gel catalytic membrane
journal, January 1997

  • Carlin, Richard T.; Fuller, Joan
  • Chemical Communications, Issue 15
  • DOI: 10.1039/a702195j

Gas separations using non-hexafluorophosphate [PF6]− anion supported ionic liquid membranes
journal, July 2004

Ionic liquids as electrolytes
journal, August 2006

Solubilization of polymers by ionic liquids
journal, January 2006

  • Winterton, Neil
  • Journal of Materials Chemistry, Vol. 16, Issue 44
  • DOI: 10.1039/b610143g

Advanced applications of ionic liquids in polymer science
journal, May 2009

Polymers in Ionic Liquids: Dawn of Neoteric Solvents and Innovative Materials
journal, January 2012

  • Ueki, Takeshi; Watanabe, Masayoshi
  • Bulletin of the Chemical Society of Japan, Vol. 85, Issue 1
  • DOI: 10.1246/bcsj.20110225

LCST-type liquid–liquid phase separation behaviour of poly(ethylene oxide) derivatives in an ionic liquid
journal, January 2008

  • Tsuda, Ryohei; Kodama, Koichi; Ueki, Takeshi
  • Chemical Communications, Issue 40
  • DOI: 10.1039/b810127b

Thermosensitive Self-Assembly of Diblock Copolymers with Lower Critical Micellization Temperatures in an Ionic Liquid
journal, August 2009

  • Tamura, Saki; Ueki, Takeshi; Ueno, Kazuhide
  • Macromolecules, Vol. 42, Issue 16
  • DOI: 10.1021/ma900922d

Photoisomerization-Induced Tunable LCST Phase Separation of Azobenzene-Containing Polymers in an Ionic Liquid
journal, August 2009

  • Ueki, Takeshi; Yamaguchi, Ayuko; Ito, Naoki
  • Langmuir, Vol. 25, Issue 16
  • DOI: 10.1021/la901159r

Doubly Thermosensitive Self-Assembly of Diblock Copolymers in Ionic Liquids
journal, February 2009

  • Ueki, Takeshi; Watanabe, Masayoshi; Lodge, Timothy P.
  • Macromolecules, Vol. 42, Issue 4
  • DOI: 10.1021/ma802443b

Lower Critical Solution Temperature (LCST) Phase Behavior of Poly(ethylene oxide) in Ionic Liquids
journal, June 2010

  • Lee, Hau-Nan; Lodge, Timothy P.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 13
  • DOI: 10.1021/jz100617t

Poly( n -butyl methacrylate) in Ionic Liquids with Tunable Lower Critical Solution Temperatures (LCST)
journal, March 2011

  • Lee, Hau-Nan; Lodge, Timothy P.
  • The Journal of Physical Chemistry B, Vol. 115, Issue 9
  • DOI: 10.1021/jp1106058

Polymer Actuators Using Ion-Gel Electrolytes Prepared by Self-Assembly of ABA-Triblock Copolymers
journal, December 2011

  • Imaizumi, Satoru; Kokubo, Hisashi; Watanabe, Masayoshi
  • Macromolecules, Vol. 45, Issue 1
  • DOI: 10.1021/ma2022138

Specific Solvation of Benzyl Methacrylate in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)amide Ionic Liquid
journal, January 2013

  • Matsugami, Masaru; Fujii, Kenta; Ueki, Takeshi
  • Analytical Sciences, Vol. 29, Issue 3
  • DOI: 10.2116/analsci.29.311

Thermodynamic study on phase transitions of poly(benzyl methacrylate) in ionic liquid solvents
journal, September 2009

  • Ueki, Takeshi; Arai, Asako Ayusawa; Kodama, Koichi
  • Pure and Applied Chemistry, Vol. 81, Issue 10
  • DOI: 10.1351/PAC-CON-08-09-04

Unusual Lower Critical Solution Temperature Phase Behavior of Poly(ethylene oxide) in Ionic Liquids
journal, April 2012

  • Lee, Hau-Nan; Newell, Nakisha; Bai, Zhifeng
  • Macromolecules, Vol. 45, Issue 8
  • DOI: 10.1021/ma300335p

Structural Study on the UCST-Type Phase Separation of Poly( N -isopropylacrylamide) in Ionic Liquid
journal, January 2013

  • Asai, Hanako; Fujii, Kenta; Ueki, Takeshi
  • Macromolecules, Vol. 46, Issue 3
  • DOI: 10.1021/ma3020273

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

Origins of Unusual Phase Behavior in Polymer/Ionic Liquid Solutions
journal, July 2013

  • White, Ronald P.; Lipson, Jane E. G.
  • Macromolecules, Vol. 46, Issue 14
  • DOI: 10.1021/ma400710z

Tuning of Sol–Gel Transition Temperatures for Thermoreversible Ion Gels
journal, February 2014

  • Kitazawa, Yuzo; Ueki, Takeshi; Imaizumi, Satoru
  • Chemistry Letters, Vol. 43, Issue 2
  • DOI: 10.1246/cl.130929

Experimental evidences for molecular origin of low- Q peak in neutron/x-ray scattering of 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ionic liquids
journal, December 2011

  • Fujii, Kenta; Kanzaki, Ryo; Takamuku, Toshiyuki
  • The Journal of Chemical Physics, Vol. 135, Issue 24
  • DOI: 10.1063/1.3672097

High-performance ion gel with tetra-PEG network
journal, January 2012

  • Fujii, Kenta; Asai, Hanako; Ueki, Takeshi
  • Soft Matter, Vol. 8, Issue 6
  • DOI: 10.1039/C2SM07119C

Cross-Linked Polymer−Ionic Liquid Composite Materials
journal, June 2003

  • Snedden, Peter; Cooper, Andrew I.; Scott, Keith
  • Macromolecules, Vol. 36, Issue 12
  • DOI: 10.1021/ma021710n

Self-Assembly of Block Copolymer Micelles in an Ionic Liquid
journal, March 2006

  • He, Yiyong; Li, Zhibo; Simone, Peter
  • Journal of the American Chemical Society, Vol. 128, Issue 8
  • DOI: 10.1021/ja058091t

A constrained regularization method for inverting data represented by linear algebraic or integral equations
journal, September 1982

Physicochemical Properties and Structures of Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in Imidazolium Cation
journal, April 2005

  • Tokuda, Hiroyuki; Hayamizu, Kikuko; Ishii, Kunikazu
  • The Journal of Physical Chemistry B, Vol. 109, Issue 13
  • DOI: 10.1021/jp044626d

Difference in Lower Critical Solution Temperature Behavior between Random Copolymers and a Homopolymer Having Solvatophilic and Solvatophobic Structures in an Ionic Liquid †
journal, May 2007

  • Ueki, Takeshi; Karino, Takeshi; Kobayashi, Yosuke
  • The Journal of Physical Chemistry B, Vol. 111, Issue 18
  • DOI: 10.1021/jp0670900

Small angle neutron scattering study on poly(N‐isopropyl acrylamide) gels near their volume‐phase transition temperature
journal, November 1992

  • Shibayama, Mitsuhiro; Tanaka, Toyoichi; Han, Charles C.
  • The Journal of Chemical Physics, Vol. 97, Issue 9
  • DOI: 10.1063/1.463636

Deuterium isotope effect on swelling process in aqueous polymer gels
journal, March 1999

Deuterium Isotope Effect on Volume Phase Transition of Polymer Gel:  Temperature Dependence
journal, November 1999

  • Shirota, Hideaki; Kuwabara, Nozomi; Ohkawa, Kazuya
  • The Journal of Physical Chemistry B, Vol. 103, Issue 47
  • DOI: 10.1021/jp992401a

Some Thermodynamic Properties of Polymer-Solvent Systems. Comparison between Deuterated and Undeuterated Systems
journal, March 1975

Deuteration effects on the miscibility and phase separation kinetics of polymer blends
journal, November 1986

  • Yang, Hsinjin; Shibayama, Mitsuhiro; Stein, Richard S.
  • Macromolecules, Vol. 19, Issue 6
  • DOI: 10.1021/ma00160a032

Liquid‐liquid phase separation in multicomponent polymer systems, 21. Deuterium isotope effect in polymer compatibility
journal, February 1984

  • Atkin, Elizabeth L.; Kleintjens, Ludo A.; Koningsveld, Ronald
  • Die Makromolekulare Chemie, Vol. 185, Issue 2, p. 377-387
  • DOI: 10.1002/macp.1984.021850214

Thermal Properties of Copolymer Gels Containing N -Isopropylacrylamide
journal, January 1996

  • Shibayama, Mitsuhiro; Mizutani, Shin-ya; Nomura, Shunji
  • Macromolecules, Vol. 29, Issue 6
  • DOI: 10.1021/ma951390q

Structural Analysis of High Performance Ion-Gel Comprising Tetra-PEG Network
journal, April 2012

  • Asai, Hanako; Fujii, Kenta; Ueki, Takeshi
  • Macromolecules, Vol. 45, Issue 9
  • DOI: 10.1021/ma300244u

Scattering from a polymer solution at an arbitrary concentration
journal, August 1984

Small-angle X-ray scattering studies of semidilute polystyrene-cyclohexane solutions
journal, October 1996

  • Xie, Yonglin; Ludwig, Karl F.; Bansil, Rama
  • Physica A: Statistical Mechanics and its Applications, Vol. 232, Issue 1-2
  • DOI: 10.1016/0378-4371(96)00218-X

SANS from Poly(ethylene oxide)/Water Systems
journal, October 2002

  • Hammouda, B.; Ho, D.; Kline, S.
  • Macromolecules, Vol. 35, Issue 22
  • DOI: 10.1021/ma011657n

Counterion-Correlation-Induced Attraction and Necklace Formation in Polyelectrolyte Solutions:  Theory and Simulations
journal, March 2006

  • Liao, Qi; Dobrynin, Andrey V.; Rubinstein, Michael
  • Macromolecules, Vol. 39, Issue 5
  • DOI: 10.1021/ma052086s

Pearl-Necklace-Like Chain Conformation of Hydrophobic Polyelectrolyte:  a SANS Study of Partially Sulfonated Polystyrene in Water †
journal, September 2007

  • Spiteri, M. N.; Williams, C. E.; Boué, F.
  • Macromolecules, Vol. 40, Issue 18
  • DOI: 10.1021/ma060896d

Persistence length of cellulose tricarbanilate by small-angle neutron scattering
journal, May 1976

Small-Angle Neutron Scattering Investigation of Pressure Influence on the Structure of Weakly Charged Poly( N -isopropylacrylamide) Solutions and Gels
journal, November 2004

  • Nasimova, Irina; Karino, Takeshi; Okabe, Satoshi
  • Macromolecules, Vol. 37, Issue 23
  • DOI: 10.1021/ma049058e

Comparison of Inter- and Intramolecular Correlations of Polystyrene in Poor and ϑ Solvents via Small-Angle Neutron Scattering
journal, November 1998

  • Melnichenko, Yuri B.; Wignall, George D.; Van Hook, W. Alexander
  • Macromolecules, Vol. 31, Issue 23
  • DOI: 10.1021/ma9812480

Theory of the Phase Transition between Helix and Random Coil in Polypeptide Chains
journal, August 1959

  • Zimm, B. H.; Bragg, J. K.
  • The Journal of Chemical Physics, Vol. 31, Issue 2
  • DOI: 10.1063/1.1730390

Cooperative Hydration, Chain Collapse, and Flat LCST Behavior in Aqueous Poly( N -isopropylacrylamide) Solutions
journal, May 2005

  • Okada, Yukinori; Tanaka, Fumihiko
  • Macromolecules, Vol. 38, Issue 10
  • DOI: 10.1021/ma0502497

SANS and DLS Study of Tacticity Effects on Hydrophobicity and Phase Separation of Poly( N -isopropylacrylamide)
journal, July 2013

  • Nishi, Kengo; Hiroi, Takashi; Hashimoto, Kei
  • Macromolecules, Vol. 46, Issue 15
  • DOI: 10.1021/ma401349v

Phase Equilibria in Polymer—Solvent Systems 1,2
journal, October 1952

  • Shultz, A. R.; Flory, P. J.
  • Journal of the American Chemical Society, Vol. 74, Issue 19
  • DOI: 10.1021/ja01139a010
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Design and synthesis study of the thermo-sensitive copolymer carrier of penicillin G acylase
    journal, April 2018

    • Li, Ke; Chen, Zhen Bin; Liu, Dong Lei
    • Polymers for Advanced Technologies, Vol. 29, Issue 7
    • DOI: 10.1002/pat.4299

    Design and synthesis study of the thermo-sensitive poly (N-vinylpyrrolidone-b- N, N-diethylacrylamide)
    journal, January 2018

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: