Proton-Conducting Sulfonated Aromatic Ionomers and Membranes by Chemical Modifications and ...

76 Pages·2017·6.6 MB·English

by  Elin Persson

Proton-Conducting Sulfonated Aromatic Ionomers and Membranes by Chemical
Modifications and Polycondensations
Persson Jutemar, Elin
2010
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Citation for published version (APA):
Persson Jutemar, E. (2010). Proton-Conducting Sulfonated Aromatic Ionomers and Membranes by Chemical
Modifications and Polycondensations. [Doctoral Thesis (compilation), Centre for Analysis and Synthesis].
Total number of authors:
1
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LUND UNIVERSITY
PO Box 117
221 00 Lund
[phone]
Proton-conducting sulfonated
aromatic ionomers and membranes by
chemical modifications and
polycondensations

Elin Persson Jutemar
Division of Polymer & Materials Chemistry

Thesis
2010

Thesis submitted for the degree of Doctor of Philosophy in
Engineering, to be defended in public at the Center for
Chemistry and Chemical Engineering, Lecture Hall K:C, on
December 15, at 10.00, as approved by the Faculty of
Engineering, Lund University
Opponent: Professor Howard M. Colquhoun
Department of Chemistry, University of Reading, United
Kingdom
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PROTON-CONDUCTING SULFONATED AROMATIC
IONOMERS AND MEMBRANES BY CHEMICAL
MODIFICATIONS AND POLYCONDENSATIONS
ELIN PERSSON JUTEMAR
2010
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© Elin Persson Jutemar, 2010
Doctoral thesis
Division of Polymer & Materials Chemistry
Lund University
P.O. Box 124, SE-22100 Lund, Sweden
All rights reserved
ISBN 978-91-7422-255-5
Printed by MediaTryck AB, Lund
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LIST OF PAPERS
This thesis is the result of studies presented in the following papers, referred to in
the text by their respective Roman numerals.
I. Sulfonated poly(arylene ether sulfone) ionomers containing di- and
tetrasulfonated arylene sulfone segments
Elin Persson Jutemar, Shogo Takamuku, and Patric Jannasch
Manuscript accepted for publication in Polymer Chemistry
DOI:10.1039/c0py00290a.
II. Locating sulfonic acid groups on various side chains to poly(arylene
ether sulfone)s: Effects on the ionic clustering and properties of
proton-exchange membranes
Elin Persson Jutemar and Patric Jannasch
Journal of Membrane Science 2010, 351, 87-95.
III. Facile Synthesis and Polymerization of 2,6-Difluoro-2’-
sulfobenzophenone for Aromatic Proton Conducting Ionomers with
Pendant Sulfobenzoyl Groups
Elin Persson Jutemar, Shogo Takamuku, and Patric Jannasch
Macromolecular Rapid Communications 2010, 31, 1348-1353.
IV. Influence of the Polymer Backbone Structure on the Properties of
Aromatic Ionomers with Pendant Sulfobenzoyl Side Chains for Use as
Proton-Exchange Membranes
Elin Persson Jutemar and Patric Jannasch
Manuscript submitted to ACS Applied Materials & Interfaces
V. Copoly(Arylene Ether Nitriles) and Copoly(Arylene Ether Sulfone)
Ionomers with Pendant Sulfobenzoyl Groups for Proton Conducting
Fuel Cell Membranes
Elin Persson Jutemar and Patric Jannasch
Manuscript accepted for publication in Journal of Polymer Science, Part A:
Polymer Chemistry

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ADDITIONAL PAPER NOT INCLUDED IN THE THESIS
Pore Size Distribution and Water Uptake in Hydrocarbon and
Perfluorinated Proton-Exchange Membranes as Studied by NMR
Cryoporometry
S. von Kraemer, A. I. Sagidullin, G. Lindberg, I. Furó, E. Persson, and P.
Jannasch
Fuel Cells 2008, 08, 262-269.

MY CONTRIBUTION TO THE PAPERS
Paper I: I took an active part in the planning of the study. I performed all the
experimental work except for the polymerizations. I wrote the paper.
Paper II: I took an active part in the planning of the study. I performed all the
experimental work and wrote the paper.
Paper III: I took an active part in the planning of the study. I performed all the
experimental work except for the polymerizations. I wrote the paper.
Paper IV: I took an active part in the planning of the study. I performed all the
experimental work and wrote the paper.
Paper V: I took an active part in the planning of the study. I performed all the
experimental work and wrote the paper.

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ABBREVIATIONS
BCPSB 4,4’-Bis[(4-chlorophenyl)sulfonyl]-1,1’-biphenyl
DCDPS Dichlorodiphenyl sulfone
DFSBP 2,6-Difluoro-2’-sulfobenzophenone lithium salt
DL Degree of lithiation
DMAc N,N-Dimethylacetamide
DMFC Direct methanol fuel cell
DMSO Dimethylsulfoxide
EIS Electrochemical impedance spectroscopy
EW Equivalent weight
FTIR Fourier transform infrared spectroscopy
IEC Ion-exchange capacity
n-BuLi n-Butyllithium
NMP N-Methyl pyrrolidone
NMR Nuclear magnetic resonance spectroscopy
PAE Poly(arylene ether)
PAEES Poly(arylene ether ether sulfide)
PAEN Poly(arylene ether nitrile)
PAES Poly(arylene ether sulfone)
PAS Poly(arylene sulfide)
PEEK Poly(ether ether ketone)
PEMFC Polymer electrolyte membrane fuel cell or
Proton-exchange membrane fuel cell
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PSU Polysulfone
RH Relative humidity
SAXS Small angle X-ray scattering
SBACA 2-Sulfobenzoic acid cyclic anhydride
SBFBB 1,4-Bis(3-sodium sulfonate-4-fluorobenzoyl) benzene
SDCDPS Disodium 3,3-disulfonate-4,4’-dichlorodiphenyl sulfone
SDFBP Disodium 3,3-disulfonate-4,4’-difluorobenzophenone
sPEEK Sulfonated poly(ether ether ketone)
T Degradation temperature
d
T Glass transition temperature
g
THF Tetrahydrofuran

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CONTENTS
Scope of the work .......................................................................... - 1 -
Introduction ................................................................................. - 3 -
2.1 Proton-exchange membrane fuel cells ............................................. - 3 -
2.2 Proton-conducting polymer membranes ......................................... - 5 -
Polymer synthesis and chemical modification ................................ - 15 -
3.1 Characteristics of polysulfones ...................................................... - 15 -
3.2 Direct sulfonation of polysulfones ................................................ - 16 -
3.3 Lithiation of polysulfones ............................................................. - 17 -
3.4 Nucleophilic aromatic substitution reactions ................................ - 19 -
3.5 Random copolymerization ........................................................... - 21 -
Special characterization techniques ............................................... - 25 -
4.1 Small angle X-ray scattering (SAXS) ............................................. - 25 -
4.2 Proton conductivity measurements ............................................... - 26 -
Thesis work ................................................................................. - 29 -
5.1 Polysulfones carrying highly sulfonated segments (Paper I) ........... - 33 -
5.2 Polysulfones carrying sulfonated aromatic side chains (Paper II) ... - 38 -
5.3 Aromatic homopolymers and copolymers with pendant
sulfonated side chains prepared by polycondensation reactions
(Papers III-V) ..................................................................................... - 42 -
Summary and outlook ................................................................. - 51 -
Populärvetenskaplig sammanfattning ............................................ - 53 -
Acknowledgements ...................................................................... - 55 -
References ................................................................................... - 57 -

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