Raul Hernandez Thesis

Clemson University
TigerPrints
All Theses Theses
4-22-2008
PERFLUOROCYCLOBUTYL ARYL ETHER
POLYMERS FOR PROTON EXCHANGE
MEMBRANES
Raul Hernandez
Clemson University, raulh@clemson.edu
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Recommended Citation
Hernandez, Raul, "PERFLUOROCYCLOBUTYL ARYL ETHER POLYMERS FOR PROTON EXCHANGE MEMBRANES"
(2008). All Theses. Paper 315.

PERFLUOROCYCLOBUTYL ARYL ETHER POLYMERS FOR PROTON
EXCHANGE MEMBRANES
_____________________________
A Thesis
Presented to
the Graduate School of
Clemson University
___________________________________
In Partial Fulfillment
of the Requirements for the Degree
Master of Science
Chemistry
___________________________________
by
Raul S. Hernandez
May 2008
___________________________________
Accepted by:
Dr. Dennis W. Smith, Jr., Committee Chair
Dr. Stephen Creager
Dr Darryl DesMarteau
Dr. Earl Wagener

ii
ABSTRACT
Over the last decades Nafion® has emerged as the polymer of choice for the fabrication
of Proton Exchange Membranes (PEM)s, due to its excellent proton conductivity and
long-term stability. However, high temperatures and low relative humidity decrease fuel
cell efficiency, due to the highly hydrated conditions required for proton conductivity. To
overcome these issues, different types of sulfonated polymers have been proposed as
promising substitutes for Nafion ®, these include; Polysulfones Perfluorocyclobutyl
(PFCB) aryl ether polymers among others.
Chapter 2 of this thesis describes the synthesis of a new class of sulfonated polysulfones
containing the perfluorocyclobutyl (PFCB) unit. These polymers have been prepared by
the polycondensation of a unique bis-phenol (Bisphenol –T) with
dichlorodiphenylsulfone (DCDPS) and sulfonated dichlorodiphenylsulfone (SDCDPS)
under nucleophilic substitution conditions.
Three different molar ratios of Bisphenol –T: DCDPS: SDCDPS were used: 1:1:0, 1:0:1
and 1:0.68:0.32, (P1, P2 and P3, respectively). The degree of incorporation of the
sulfonated repeat unit into the copolymers was determined by 1
H NMR. The resulting
polymers show solubility in polar organic solvents such as DMAc and DMSO. The
incorporation of SDCDPS into the backbone of the polymer decreased the mechanical
strength of the membranes. Solution casting of the unsulfonated polymer P1 yielded

iii
tough, flexible films with a glass transition temperature of 138 o
C. and catastrophic
weight loss in N2 at 350-450 o
C. Sulfonation of polymers P2 and P3 resulted in lower
molecular weight brittle films and lower stability and mechanical properties.
Chapter 3 describes the incorporation of zirconia into PFCB aryl ether polymers. The
complex surface of zirconia aerogel was modified by complexation with p-
trifluorovinyloxy phenyl phosphoric acid. PFCB polymers with different Ionic Exchange
Capacity values were obtained by sulfonation with ClSO3H (P4, P5, P6). Sulfonated
PFCB polymers showed a reproducible increase in the Ionic Exchange Capacity (IEC)
after the addition of 10 wt % modified zirconia, whereas unmodified zirconia resulted in
lower IEC membranes. Polymers P4 and P5 improved their thermo-oxidative stability.
The use of modified zirconia proved to be a simple yet valuable tool towards the
fabrication of more efficient PEMs.

iv
DEDICATION
I dedicate this thesis to my family; Mom, Dad, Cristina and Adriana to whom I thank for
their support and help even though the distance.

v
ACKNOWLEDGEMENTS
I thank God for putting in my way the people that in one way or another contributed to
the culmination of this thesis. Without their participation this work would not have been
possible.
Especial thanks to Dr. Dennis Smith for his unconditional support and belief in me. To
the US Department of Energy for financial support. To Dr Arno Rettenbacher for his help
and leadership in the zirconia aerogel project. To Dr Amit Sankhe for his help and
guidance on the PAES project and the IEC measurements.
To the committee members for this MS thesis which include; Dr. Earl Wagener, Dr.
Stephen Creager, and Darryl DesMarteau for their insightful comments and guidance.
To Dr Chris Topping and Rahula Jaiasinghe at Tetramer Technologies LLC for their
helpful advice and suggestions and also for the donation of starting materials.To Clemson
University and the Chemistry Department Faculty and Staff.
Especial thanks to Scott Iacono, Steve Budy and Nikki Fox and all present and past
members in Dr. Smith’s group which include Dr Suresh Iyer, Dr. Jack Jin, Dr. Clark
Ligon, Dr. Mark Perpall, Andy Neilson, Dahlia Haynes, Madan Banda, Dakarai Brown,
Sriram Yagneswaran, Ken Tackett and Wenjin Deng.

vi
To all my Colombian friends at Clemson for their companion and making me feel close
to home. And finally, I would like to thank Dr. Luis and Lourdes Echegoyen, because I
knew about Clemson University through them.

vii
TABLE OF CONTENTS
Page
TITLE PAGE ................................................................................................................... i
ABSTRACT.................................................................................................................... ii
DEDICATION ............................................................................................................... iv
ACKNOWLEDGEMENTS .............................................................................................v
LIST OF TABLES ......................................................................................................... ix
LIST OF FIGURES..........................................................................................................x
LIST OF SCHEMES.................................................................................................... xiii
CHAPTER
1. INTRODUCTION...........................................................................................1
1.1 Proton Exchange Membranes.............................................................1
1.2 Nafion®..............................................................................................3
1.3 Other Perfluorosulfonic Acids ...........................................................5
1.4 Poly(Arylene Ether Sulfones) ............................................................6
1.5 Other Hydrocarbon Alternatives........................................................7
1.6 Perfluorocyclobutyl Aryl Ether Polymers..........................................9
1.7 Inorganic Fillers as Reinforcing Materials.......................................12
2. POLYSULFONES CONTAINING THE PFCB ARYL
ETHER LINKAGE ..................................................................................14
2.1 Introduction......................................................................................14
2.2 Results and Discussion.....................................................................15
2.3 Conclusions......................................................................................25
3. ZIRCONIA DOPED PFCB ARYL ETHER POLYMERS ..........................26
3.1 Introduction......................................................................................26
3.2 Results and Discussion.....................................................................27
3.3 Conclusions......................................................................................45

viii
Table of Contents (Continued)
Page
4. EXPERIMENTAL ........................................................................................46
4.1 Instruments.......................................................................................46
4.2 Materials...........................................................................................47
4.3 Procedures ........................................................................................47
APPENDICES................................................................................................................56
A: Crystal data for compound (4) ...................................................................57
B: Crystal data for compound (7)....................................................................62
C: Crystal data for compound (9)....................................................................67
D: Selected Spectra .......................................................................................76
REFERENCES...............................................................................................................91

ix
LIST OF TABLES
Table Page
1. Comparative table of fluoropolymers vs hydrocarbon polymers...........................4
2. Commercially available PFSA ionomers for fuel cell applications.......................5
3. Physical characteristics of Nafion and Nafion/zirconium hydrogen
phosphate composite membranes......................................................................12
4. Selected properties of polymers P1-P3................................................................23
5. IEC values of doped PFCB polymers ..................................................................43

x
LIST OF FIGURES
Figure Page
1. Design of a fuel cell ...............................................................................................2
2. Molecular structure of Nafion®
..............................................................................3
3. Structure of Udel®
: a PAES synthesized from Bis-A and DCDPS........................6
4. BAM®
ionomer ......................................................................................................7
5. Sulfonated PBI .......................................................................................................8
6. Polymer electrolyte developed by Honda ..............................................................8
7. Monomer developed by Fujitsu Limited..............................................................11
8. Sulfonated Fluorovinylene Aromatic Ether Polymer...........................................11
9. X-ray crystal structure of Bisphenol-T.................................................................14
10. FTIR spectra of polymers P1, P2 and P3...........................................................18
11. 1H NMR spectra of polymers P1-P3.................................................................20
12. DSC analysis of polymers P1 (10 o
C/min, under N2) ........................................21
13. TGA of polymer P1, P2 and P3 under N2 at 10 o
C/min ....................................22
14. Free standing film formed from polymer P1 .....................................................23
15. Parr reactor.........................................................................................................28
16. X-ray crystal structure of p-trifluorovinyloxy phenyl phosphonic acid.............29
17. Surface chemistry of zirconia.............................................................................30
18. Adsorpion of aryl phosphonic acid on the surface of zirconia...........................31
19. TGA of surface modified zirconia .....................................................................32
20. FTIR of zirconia, FTVE-PA and modified zirconia ..........................................33

xi
List of Figures (Continued)
Figure Page
21. X-ray crystal structure of sulfolane bisphenol structure 7 .................................34
22. X-ray crystal structure of 4,4’-di-(2-bromotetrafluoroethoxy)-3,3’-
Biphenyldisulfonyl chloride...........................................................................36
23. Previously attempted TFVE monomer ..............................................................37
24. 19
F NMR spectrum of crude reaction mixture....................................................38
25. Previously reported organic salts .......................................................................39
26. Proposed organozic intermediate .......................................................................40
27. IEC of sulfonated BPVE polymers ....................................................................41
28. Adsorption modes for arylphosphonic acids......................................................42
29. TGA analysis of P4, P4 10% mod ZrO2 and BPVE..........................................44
30. TGA analysis of P5, P5 10% mod ZrO2 and BPVE..........................................44
31. 1
H NMR of SDCDPS.........................................................................................76
32. 19
F NMR of P1...................................................................................................77
33. 1
H NMR of P2....................................................................................................78
34. 1
H NMR of P3....................................................................................................79
35. 1
H NMR of sulfolane structure in DMSO-d6 ....................................................80
36.13
C NMR of sulfolane structure in DMSO-d6 .....................................................81
37. 31
P NMR of p-trifluorovinyloxyphenyl phosphonic acid...................................82
38. 19
F NMR of p-trifluorovinyloxyphenyl phosphonic acid...................................83

xii
List of Figures (Continued) Page
39. 1
H NMR of 9 ......................................................................................................84
40. 19
F NMR of 9......................................................................................................85
41. 1
H NMR of 10 ....................................................................................................86
42. 19
F NMR of 10....................................................................................................87
43. H1
NMR of P4....................................................................................................88
44. 1
H NMR of P5....................................................................................................89
45. 1
H NMR of P6....................................................................................................90

xiii
LIST OF SCHEMES
Scheme Page
1. Half cell reaction taking place in a fuel cell...........................................................1
2. Synthesis of sulfonyl fluoride vinyl ether ..............................................................4
3. Preparation of PFCB aryl ether polymers ..............................................................9
4. Synthesis of polymer P1, P2 and P3....................................................................15
5. Nucleophilic Aromatic Substitution.....................................................................16
6. Decomposition of Potassium Carbonate ..............................................................16
7. Proposed route towards zirconia doped sulfonated PFCB
aryl ether polymers...........................................................................................26
8. Formation of ZrO2 aerogel ...................................................................................28
9. Synthesis of p-trifluorovinyloxy phenyl phosphonic acid (4)..............................28
10. Surface modification of zirconia........................................................................31
11. Direct sulfonation of BPVE ...............................................................................33
12. Previuosly reported synthesis of 7 .....................................................................34
13. Synthesis of bromo-presursor 10........................................................................35
14. Attempted elimination of 10 ..............................................................................37

CHAPTER 1
INTRODUCTION
1.1 Proton Exchange Membranes
Fuel cells are electrochemical devices that use the oxidation of hydrogen and, in some
cases, methanol to produce power (Scheme 1). Although fuel cells have been known
since 1839,1
it was not until the last decade that they began to be recognized as potential
substitutes for traditional gasoline-powered technologies. It is expected that fuel cells will
help reduce foreign oil dependency and air pollution in the next few years.2
Hydrogen Fuel Cell Direct Methanol Fuel Cell
H2 2 H+
+ 2e-
4H+
+ 4e-
+ O2 2 H2O
CH3OH + H2O CO2 + 6H+
+ 6e-
3
/2 O2 + 6H+
+ 6e-
3H2O
H2 + 1
/2 O2 H2O CH3OH + 3
/2 O2 CO2 + 2H2O
Scheme 1. Half cell reactions taking place in a fuel cell.
The design of a fuel cell consists primarily of a cathode, an anode and a proton exchange
membrane (PEM). On the anode side, hydrogen gas is converted to protons and electrons.
Protons pass through the membrane and react with oxygen and electrons on the cathode
side. Electrons flow from the anode to the cathode through an external circuit containing
a motor or other electric load which consumes the power generated by the cell.1
(Figure 1)

2
Figure 1. Design of a fuel cell.
Since the introduction of fuel cells, several materials have been proposed for the
fabrication of PEMs.3
Common themes critical to all high performance proton exchange
membranes include: high protonic conductivity, low electronic conductivity, low
permeability to fuel and oxidant, low water transport through diffusion and electro-
osmosis, oxidative and hydrolytic stability, good mechanical properties in both the dry
and hydrated states, cost, and capability for fabrication into membrane electrode
assemblies (MEAs).4
The light weight and quick start-up times of PEM fuel cells make them good candidates
for automotive applications, for which the U.S. Department of Energy has currently
established a guideline of 120 °C and 50% relative humidity as target operating
conditions and a goal of 0.1 S/cm for the protonic conductivity of the membrane.3

3
1.2 Nafion®
One of the most successful polymers used for PEMs is Nafion®, (Figure 2) which is a
Perfluorosulfonic acid (PFSA) copolymer. In addition to the classical properties of
fluorinated polymers (Table 1), Nafion®
has excellent proton conductivity (~ 1.0 S/cm2
)
and good thermal and mechanical stability. Nevertheless, proton conductivity of Nafion®
decreases at high temperature and low relative humidities. These limitations, in addition
to its high price, have made difficult its extensive implementation in automotive fuel cell
technologies.3
Figure 2. Molecular structure of Nafion®
.
The synthesis of Nafion is a multiple step process that involves the copolymerization of
tetrafluoroethylene with a proprietary monomer. The later compound can be preapared
from fluorinated β-sultones which upon reaction with triethylamine yields the
corresponding acyl fluoride. This product is reacted with hexafluoropropylene oxide
(HFPO) to produce the corresponding sulfonyl fluoride adduct (Scheme 2). Pyrolytic
decarboxilation of the later product genereates the coresponding sulfonyl fluoride vinyl
ether.
CFCF2 CF2CF2
OCF2CFOCF2CF2SO3H
CF3
mn

4
Scheme 2. Synthesis of sulfonyl fluoride vinyl ether.
Table 1. Comparative table of fluoropolymers vs hydrocarbon polymers.
Hydrocarbon Polymers Fluoropolymers
Poor Thermo-oxidative stability Good thermo-oxidative stability
High reactivity towards radicals Low reactivity towards radicals
Low cost High cost

5
1.3 Other Perfluorosulfonic Acids
Other PFSAs have been developed at Solvay-Solexis, Dow, 3M and other companies
(Table 2). These polymers have similar structures. The major difference is the side chain
length and the absence of the CF3 group, which gives them a higher degree of
crystallinity, higher glass transition temperature (Tg),5
lower fuel crossover and
improving the mechanical properties.6
“Short-side chain” (SSC) ionomers have also
shown a significant improvement in fuel cell performance. Arcella et. al. compared the
power output of a six-cell stack using Dow and Nafion membranes. Dow membranes had
a power output four times higher than that of Nafion membranes.5
Table 2. Commercially available PFSA ionomers for fuel cell applications.
Commercial Name Manufacturer Chemical Structure
Nafion® 117 DuPont
Hyflon® ION E83 Solvay
Solexis
3M PEM 3M

6
1.4 Poly(Arylene Ether Sulfones)
Other polymers that are currently under study for PEM fuel cell applications include
poly(arylene ether ether ketones), poly(phenylene sulfides) and poly(arylene ether
sulfones), due to their facile synthesis, low cost and excellent mechanical and thermal
stability.7
McGrath et. al. have worked intensively in the development of PEMs made of
Poly(arylene ether sulfones) (PAES) (Figure 3). PAES can be synthesized from the
polycondensation of bisphenols and dihalides. This procedure allows for precise control
of sulfonation in the final polymer. Ueda et al. copolymerized 3,3'-disulfonated-4,4'-
dichlorodiphenyl sulfone (SDCDPS) and Bisphenol A (BPA) to generate copolymers
with up to 30 % of the disulfonated monomer by simply controlling the ratio of
sulfonated to non-sulfonated dihalide, as opposed to the post-sulfonation method, where
the target degree of sulfonation is not easily controlled and side reactions occur.8,9
Figure 3. Structure of Udel®
: a PAES synthesized from Bis-A and DCDPS.

7
1.5 Other Hydrocarbon Alternatives
Alternative polymers for fuel cell membranes include polystyrene, polyarylene ether
ether ketone, polybenzimidazole and polyphosphazene.7
All these polymer can be
prepared from readily available monomers and their synthesis is pretty straight forward.
Ballard Advance Material Corporation introduced a of series sulfonated copolymers of
trifluorostyrene and substituted trifluorostyrene monomers (Figure 4) to achieve
processable materials and to reach the requirements for fuel cell operation in terms of
lifetime and performance.10
Figure 4. BAM®
ionomer
Another polymer that has received has received great attention is polybenzimidazole (PBI)
(Figure 5) due to its ability to achieve high proton conductivity at elevated temperatures
and low relative humidity. The proton transport mechanism for PBI does not require
humidification, making them very attractive for high operating temperature fuel cells.11

8
Figure 5. Sulfonated PBI
Recently Honda developed an inexpensive polymer electrolyte that exhibits excellent
efficiency of generating electric power.12
The aforementioned polymer consists of a
sulfonated polyarylene containing no fluorine in its molecular structure (Figure 6), thus
making it attractive from the synthetic and economic point of view.
O
O
O
n m
O
O
SO3H
n/m = 70/30
Figure 6. Polymer electrolyte developed by Honda.

9
1.6 Perfluorocyclobutyl Aryl Ether Polymers
Perfluorocyclobutyl (PFCB) aryl ether polymers have also been proposed for potential
use in PEMs.13,14,15,16
PFCB aryl ether polymers are a unique class of partially fluorinated
polymers, prepared from the thermal [2+2] cycloaddition of aryl trifluorovinyl ether
(TFVE) monomers in bulk or solution without initiator (Scheme 3).17,18
PFCB aryl ether polymers can alternatively be synthesized from the polycondensation of
monomers containing the PFCB ring (1) with a suitable reagent (Scheme 3).19
These
monomers exist as a mixture of cis and trans stereoisomers which can be separated by
selective recrystallization.20
O O ArAr
F F
FF
F F
O O Ar
F F
FF
F F n
160 o
CO
Ar
O
F
F
F
F
FF
O O ArAr
F F
FF
F F
OHHO Ar XX+
A
B
1
Scheme 3. Preparation of PFCB aryl ether polymers. A: thermal [2+2] cycloaddition. B:
polycondesation of monomers containing the PFCB ring.

10
PFCB aryl ether polymers retain many classical properties of fluoropolymers such as low
surface energy, thermal and oxidative stability, low dielectric constant, low moisture
absorption and chemical resistance.21
In addition they offer outstanding processability
and excellent thermal and mechanical properties.22,23,24
Huang et. al., synthesized high molecular weight polyarylene ether sulfones containing
the PFCB ring by solution polymerization in diphenyl ether.25
More recently, Fujitsu
Limited26
developed highly conducting PFCB polyelectrolytes (Figure 7) with low
methanol permeation for use in fuel cells. The reduction in the methanol permeation is
accomplished by the introduction of rigid segments within the polymeric structure
(Figure 7).
Besides the traditional thermal cycloaddition, TFVE monomers can react with
nucleophilic species to generate a new type of fluorinated polyethers (Figure 8).27
Iacono
et. al. prepared these polymers for potential use in PEM for fuel cells by post-sulfonation
with oleum.16

11
Figure 7. Monomer developed at Fujitsu Limited.
O O O
FF
FF
F F
OZO Z O
nSO3H SO3H
Z= CHFCF2 or CF=CF (50:50 cis:trans)
Figure 8. Sulfonated Fluorovinylene Aromatic Ether Polymers

12
1.7 Inorganic Fillers as Reinforcing Materials
The addition of inorganic fillers has shown to improve the processability and mechanical
properties of polymers.28,29
They can also reduce fuel permeation, and enhance proton
conductivity of proton exchange membranes.30,31,32
Silica has been used successfully to
improve water retention and thermal stability of Nafion membranes.33
Zirconium
hydrogen phosphate has also been incorporated to sulfonated poly(arylene ether ether
ketones) by direct blending or using the impregnation method. This procedure generates
films with methanol permeability ten times lower than that of Nafion 117.34
Table 3
shows some physical properties of Nafion and Nafion/Zirconium Hydrogen Phosphate
membranes.
Table 3. Physical characteristics of Nafion and Nafion/zirconium hydrogen phosphate
composite membranes35
Membrane Thickness
(µm)
Density
(g/cm3
)
IEC
(µeq/g)
EW
(g/mol H+
)
Nafion 130 2.0 996 1004
Nafion/zirconium
phosphate (25%)
170 1.6 1464 683

13
Recently there has been an increasing interest in use of aerogels and composite materials
prepared by the sol-gel process for use in fuel cells.36,37
Aerogels are sometimes called
frozen smoke, due to its appearance and to the fact that almost 99% of it is air. The
remaining 1% is composed of inorganic compounds such as zirconia, silica or titania.38
These types of materials are prepared by the sol-gel method followed by supercritical
fluid drying. This technique normally provides a very porous material, with irregular
patterned macropores having a large pore-size distribution.39
The large surface area and
pore volume of zirconia based aerogels, render it a promising material for many
applications, such as catalyst supports,40
inorganic fillers41
and solid oxide fuel cells.42
Moreover, its surface has both acid and basic properties, as well as oxidizing and
reducing properties,43
which gives them the ability to anchor to several organic
molecules.44,45

14
CHAPTER 2
POLYSULFONES CONTAINING THE PFCB ARYL ETHER LINKAGE
2.1. Introduction
The goal of this study was to prepare sulfonated polyarylene ether polymers with the
PFCB aryl ether linkage using the polycondensation of DCDPS, SDCDPS and novel
biphenol-T (1) (figure 9), commercialized by Tetramer Technologies LLC. Based on the
fact that PFCB polymers have high thermal and oxidative stability and can be processed
as solution cast membranes, and dichlorodiphenyl sulfone is such a readily available
monomer, the resulting polymer would exhibit characteristics of both materials,
representing a great improvement towards more efficient, low priced PEMs.
Figure 9. X-ray crystal structure of Bisphenol-T. (used with author’s permission)

15
2.2. Results and Discussion
Synthesis of Polymers
Nucleophilic aromatic condensation polymerization has been used extensively for the
synthesis of high molecular weight PAES. In this work, typical polymerization
conditions established by McGrath were used.7
Before polymerization (Scheme 4),
Bisphenol-T and SDCDPS were dried overnight at 60 o
C under vacuum. These reagents
are highly hygroscopic and need to be stored under an inert atmosphere and weighed
rapidly to avoid excessive water absorption.
HO O O OH
F
F
F
F
FF
S
O
O
Cl Cl
O O O O
F
F
F
F
FF
S
O
O n
K2CO3 DMAc
150-170 o
C
24 h
1
X X
P1, X= H
P2, X= SO3Na
P3, X= [2H] : [1 SO3Na]
X= H (DCDPS)
X= SO3Na (SDCDPS)
X X
Scheme 4. Synthesis of polymer P1, P2 and P3
High boiling point solvent, DMAc, was used and the reaction mixture heated to 150 o
C
for 4 hours to remove water by means of an azeotropic mixture with toluene. Complete

16
removal of water is a requirement to ensure the production of high molecular weight
polymers. Although water is less nucleophilic than phenoxy ions,46
it can react with
DCDPS to produce an unreactive bisphenol causing the polymer to stop chain growth
(Scheme 5).47
Scheme 5. Nucleophilic Aromatic Substitution.
Water not only comes from the solvent used but from the decomposition of potassium
carbonate as seen in Scheme 6.
Scheme 6 . Decomposition of Potassium Carbonate.
Afterwards, the temperature is raised to 170 o
C to allow polymerization. The
polymerization sequence for the preparation of polymer P1 is shown in Scheme 4.
Polymer P1 was isolated as white fibrous solid by precipitation in deionized water and

17
dried under vacuum. Polymer P2 was synthesized from Bisphenol-T (1) and SDCDPS
using the procedure outlined above (Scheme 4). However, P2 was water soluble and
hence isolated and purified by precipitation in hexane.
Copolymer P3 was synthesized from a 1.0 : 0.68 : 0.32 mixture of Bisphenol-
T : DCDPS : SDCDPS using a similar condensation procedure and was isolated by
precipitation into methanol as yellowish solid. Scheme 4 shows the synthetic route to
polymer P3. Even though SNAr are favored by electron withdrawing groups such as
SO3Na in the ortho or para position to the halide, higher temperatures were needed for
polycondensations using SDCDPS. This can be attributed to the fact that the chloride in
SDCDPS is sterically hindered and thus requiring higher temperatures.
FTIR and NMR Characterization
FTIR, 1
H NMR, and 19
F NMR were used to identify and characterize the new PFCB
containing SPAES series of polymers. FTIR analysis of the polymers allowed a
qualitative determination of functional groups (Figure 10). The peaks at 1322, 1012 and
956 cm-1
are characteristic of the Ar-O-Ar stretching, S=O stretching and C-F breathing
mode of hexafluroro cyclobutane, respectively. These peaks were observed for all
polymers P1-P3. The PFCB ring remained unaffected by the conditions of the
condensation reaction employed, as observed by FTIR. The peak at 1029 cm-1
was
observed for polymer P2 and P3 only, due to the vibrational stretching of the sulfonic

18
acid group. Due to the higher number of SO3Na groups, polymer P2 has the strongest
absorption at 1029 cm-1
.
Figure 10. FTIR spectra of polymers P1 (above), P2 (center) and P3 (below).
The 1
H NMR spectrum of polymer P1 exhibit 1:1 ratio of aromatic protons derived from
the Bisphenol-T and DCDPS moieties as expected. The signals representing protons
closest to the sulfone functionality appeared at 7.9 ppm. For polymers P2 and P3 the
signals representing aromatic protons adjacent to the sulfonic acid group appeared at 8.4
ppm.
1322
1322
1322
1012
1029 1012
1029
1012
956
956
956
1
2
3
Wavenumbers (cm-1)
1400 1200 1000 800
1322
1322
1322
1012
1029 1012
1029
1012
956
956
956
1
2
3
Wavenumbers (cm-1)
1400 1200 1000 800
Wavenumbers (cm-1)
1400 1200 1000 800
P1
P2
P3
Ar-O-Ar SO3 S=O PFCB breathing

19
The degree of sulfonation in polymer P3 was determined from the 1
H NMR spectrum
(Figure 11) as follows: signal A (8.34 ppm) represents 2 protons (labeled A) from unit X,
signal B (8.02 ppm) represents 4 protons (labeled B) from unit Y and signal C (7.91 ppm)
represents 2 protons (labeled C) from unit X (Figure 11). As singlets B and C are not
base-line separated, and the number of C protons is equal to the number of A protons, the
integral of B can be found by: (B+C)-A. Molar ratio of [unit X : unit Y] (i.e., sulfonated
to non-sulfonated) is found from the integrals of A and B as [(A/2) : (B/4)] to be [1 : 1.9],
representing a 34 % degree of sulfonation. Calculated degree of sulfonation from 1
H
NMR corresponded with the molar ratios used for the polymerization.
The 19
F NMR of polymer P1 (Figure 32) exhibited characteristic PFCB signals from -123
to -130 ppm. This confirms the stability of the perfluorinated ring to the condensation
polymerization conditions.

20
O OO O
FF
F
F F
F
S
O
O
O O O O
FF
F
F F
F
S
O
O
NaO3S SO3Na
y-x x
Unit X Unit Y
A
C
A
C
B
BB
B
Figure 11. 1
H NMR spectra of polymers P1-P3.
8.5 8.0 7.5 7.0
8.5 8.0 7.5 7.0 ppm
A
B
C
ppm8.0 7.5 7.0
B
C
A
ppm
P1
P2
P3

21
Thermal Behavior
The glass transition temperature (Tg) for polymer P1 was determined by DSC and a
reproducible value of 138 o
C was measured after multiple cycles from 0 to 300 o
C under
N2 atmosphere at a heating rate of 10 o
C/min (Figure 12). No Tg was observed for
polymers P2 and P3 below 250 o
C. This effect can be attributed to the SO3Na pendants
groups. Pendant groups can act as anchors and decrease chain mobility, hence increasing
the Tg. Noshay and Robeson48
found that for polysulfones, the increase in Tg is
proportional to the degree of sulfonation
Figure 12. DSC analysis of polymer P1 (10 °C/min, under N2).
The thermal stability of all three polymers was investigated by TGA programmed from
30-1000 o
C at a heating rate of 10 o
C/min in N2 and are depicted in Figure 13. Polymer
P1 exhibited a weight loss of only 5% before 500 o
C. Polymers P2 and P3 showed a
two-step degradation profile. The first weight loss was assigned to tightly bound water

22
associated with SO3Na groups that persisted even after drying the membranes at 100 o
C
overnight. The second weight loss is typically assigned to main chain polymer
degradation.5
It was also observed that an increase in the degree of sulfonation resulted
in a higher char yield.
Figure 13. TGA of polymers P1, P2 and P3 under N2 at 10 °C/min.
Membrane Preparation
Polymers P1 - P3 were dissolved in DMAc (1g / 10 mL) to give homogeneous solutions
and cast into glass substrates. Then they were dried under vacuum at 80 o
C for 16 h. and
annealed for 2 h at 130 o
C. After rinsing the membranes with DI water, P1 was
successfully peeled from the glass substrates. Although its Mn (MnGPC = 11200) was not
as high as common polyarylene ether sulfones, it formed free standing, tough, flexible
0
20
40
60
80
100
120
0 200 400 600 800 1000
Temperature (ºC )
%Sample
P3
P2
P1

23
films, as shown in Figure 14. Good quality films were not obtained from polymer P2 and
P3, breaking apart when pealed from the glass plate (P3), or being water soluble (P3).
The lower reactivity and highly hygroscopic nature of SDCDPS may have produced
lower molecular weight polymers, causing the membranes to be less ductile. Another
important aspect for obtaining high molecular weight step-growth polymers is the
stoichiometry. In this case a 1:1 ratio (bisphenol: dihalide) was used. However, impurities
can cause a significant decrease in the molecular weight.
Figure 14. Free standing film formed from Polymer P1.
Table 4. Selected properties of polymers P1-P3.
Solubility Experimental
IEC (meq/g)
Theorethical
IEC (meq/g)*
Mn(GPC)
**
Films
quality
P1 CH3Cl - - 12K Strong
P2 H2O 0.7 2.65 Not CHCl3
soluble
Water soluble
P3 MeOH:THF
1:1
0.34 - Not CHCl3
Soluble
Brittle
*Calculated using the chemical structure of P2. ** GPC measurements were run using
CHCl3 as solvent and polystyrene standards.

24
The experimental IEC of the membranes was determined once for P2 and P3 using back
titration with NaOH (0.01N). For more reliability several measurements would be
required.
Polymer P2 shows a theoretical IEC value, almost 4 times larger than the experimental
value (table 4). One of the possible reasons for a lower IEC, is the fact that when the
equivalence point is reached, unreacted protons are still trapped inside the membrane,
generating a lower value.

25
2.3. Conclusions
PFCB containing aryl ether sulfone polymers were synthesized with a controlled degree
of sulfonation from the versatile Bisphenol-T, DCDPS and SDCDPS by simple
condensation polymerization under basic, anhydrous conditions. The degree of
sulfonation was varied by changing the ratio of sulfonated to non-sulfonated sulfone.
Even though all polymers exhibited catastrophic weight loss above 350 o
C, a moderate
decrease in the thermal oxidative stability of the polymers was observed as the
sulfonation increased.
Solution cast of polymer P1, generated flexible, though membranes with distinct Tg (138
o
C) as opposed to sulfonated polymers P2 and P3. The difficulty to obtain mechanically
strong membranes was attributed to impurities that could have changed the stoichiometry
of the reaction. Furthermore sulfonation could have prevented the formation of high
molecular weight polymers. Suggested experiments include post-sulfonation of
unsulfonated polymer P1, as this polymer showed good mechanical properties.

26
CHAPTER 3
ZIRCONIA DOPED PFCB ARYL ETHER POLYMERS
3.1 Introduction
The objective of this part of the research was to obtain functionalized zirconia based
inorganic-organic composites to improve mechanical properties of sulfonated PFCB aryl
ether polymer. The porous morphology of zirconia aerogel would serve as a mechanical
framework to host the polyelectrolyte, providing a more mechanically stable membrane.
For this purpose, the grafting of zirconia aerogel with p-trifluorovinyloxy phenyl
phosphonic acid, followed by reaction with BPVE and sulfonated BPVE monomer and/or
blending with sulfonated BPVE, was devised (Scheme 7).
Scheme 7. Proposed route towards zirconia doped sulfonated PFCB aryl ether polymers.

27
3.2 Results and Discussion
Zirconia Aerogel Preparation and Surface Modification
To ameliorate the mechanical properties of sulfonated membranes containing the PFCB
ring, the incorporation of highly porous inorganic fillers was proposed. Zirconium
compounds can enhance other properties as well. Zhang et. al. were able to improve the
proton conductivity of PEEK membranes by addition of sulfated zirconia.49
For this
particular case, zirconia aerogel was used due to the high surface area, strong adsorption
with phosphates and its water retention.50,51
Zirconia aerogel was prepared using a previously reported method,52
which included a
sol-gel process followed by supercritical drying. A mixture of ZrO(NO3)2 · 2H2O, ethanol
and water was heated to 80 °C in a Parr reactor (Figure 15) and kept for about an hour.
To exceed the critical condition without formation of a vapor–liquid interface inside the
pores, the mixture was heated and pressurized. The autoclave was heated in order to
surpass the Tc (241 o
C) and Pc (6.2 MPa) of ethanol. The final temperature and pressure
were about 280 o
C, 17.0 MPa. Then the fluid (ethanol + HNO3) was slowly flushed with
nitrogen in several batches to maintain the supercritical conditions. Finally the vessel
was slowly cooled to room temperature (Scheme 8). The zirconia particles had an
average diameter of 5 nm and a surface area of 231 m2
/g.

28
Figure 15. Parr reactor. Scheme 8. Formation of ZrO2 aerogel.
The surface area of zirconia was then modified by reacting it with p-trifluorovinyloxy
phenyl phosphonic acid (4) (Scheme 9).
OBr
F F
F OP
F F
FO
OEt
OEt1) t-BuLi, -78 o
C, Et2O
2) ClP(O)OEt2
OP
F F
FO
OH
OH
1) BrSiMe3, CH2Cl2, r.t.
2) MeOH
62 %
85%
4
Scheme 9. Synthesis of p-trifluorovinyloxy phenyl phosphonic acid (4).53
Ethanol Water ZrO(NO3)
2
Starting Solution
Gel
Heating 80 o
C
Supercritical Drying
280 o
C 17 MPa

29
p-Trifluorovinyloxy phenyl phosphonic acid was prepared from the lithiation of 4-
trifluorovinyloxy phenyl bromide followed by the addition of chlorodiethylphosphite and
dealkylation with bromotrimethylsilane as reported by Souzy et. al.53
Literature
suggested that p-trifluorovinyloxy phenyl phosphonic acid was isolated as a yellowish oil.
However in this study, it was isolated as colorless crystals. Figure 16 shows the crystal
structure of p-trifluorovinyloxy phenyl phosphonic acid.
Figure 16. X-ray crystal structure of p-trifluorovinyloxy phenyl phosphonic acid.
The surface chemistry of zirconia is quite different from that of silica. The dominant
surface features of zirconia include: Brønsted acid, Brønsted base, and Lewis acid sites
(Figure 17).54,55
It is the Lewis acid site that sets zirconia apart from silica and allows for
its modification with hard Lewis bases such as phosphonic acids. Yuchi et. al. found that
phenyl phosphonic acid was irreversibly absorbed on zirconia at pH < 7.50

30
Figure 17. Surface chemistry of zirconia56
Complexation of p-trifluorovinyloxy phenyl phosphonic acid with zirconia was
accomplished by mixing an aqueous solution of p-trifluorovinyloxy phenyl phosphonic
acid with aqueous dispersion of zirconia powder. After adding p-trifluorovinyloxyl
phenyl phosphonic acid to the zirconia dispersion, the suspended particles were
precipitated as a coarse white powder, thus indicating an increase in the hydrophobicity
of the surface of zirconia (Scheme 10).

31
PO
OH
OH
O F
F F
Zr02
H2O, 80 o
C
P O F
F F
Zr02
O
O
O
4 5
Aqueous suspension of 4 and zirconia powder hydrophobic precipitate (5)
Scheme 10. Surface modification of zirconia
Guerrero et.al.57
found that the coupling of organophosphorus compound with the surface
of titania (TiO2) proceeds through the ligand exchange mechanism which involved
coordination of the phosphoryl oxygen to Lewis acid sites and cleavage of the M-O-M
bond. In this work, a similar mechanism is proposed (Figure 18).
Lewis Acid Brønsted Acid
Figure 18. Adsorption of aryl phosphonic acid on the surface of zirconia

32
The solid was dried overnight at 60 o
C and weighed. The final weigh (550 mg) suggested
that only 50 mg (0.39 meq) out of 500 mg of p-trifluorovinyloxyl phenyl phosphonic
acid, reacted with zirconia. Although there could have been more active sites on the
surface of zirconia, these might be non-accessible sites, due to morphological
impediments.
TGA analysis suggests a 10 % mass loss before 550 o
C which corresponds to the p-
trifluorovinyloxy aryl phenyl phosphonic acid attached to the surface of zirconia (Figure
19).
Figure 19. TGA of surface modified zirconia.
The grafting of zirconia was confirmed by FTIR using the P-O stretching band at 1017
cm-1
, which is characteristic of arylphosphonic acids.58
This band disappears after
complexation takes place suggesting covalent bonding between zirconia and PA-TFVE.

33
Figure 20. FTIR of zirconia (above), TFVE-PA (center) and modified zirconia (below)
Sulfonated BPVE Monomer
One alternative for the preparation of sulfonated monomers containing the TFVE group,
was the direct sulfonation of BPVE (Scheme 11). Sulfonation of monomers prior to
polymerization has been reported previously. This method allows for precise control of
the degree of sulfonation. In this study, direct sulfonation produced a sulfolane bisphenol
type of structure and not the intended product (Figure 21).
OO
1) H2SO4/ SO3
70 %
S
O O
OHHO
F
F
F F
F
F
.H2O
OO
F
F
F F
F
F
NaO3S SO3Na
2) NaCl (aq)
6
7
Scheme 11. Direct sulfonation of BPVE
ZrO2
aerogel
O
FC CF2
P
O
O
O
ZrO2
aerogel
O
FC CF2
P
OH
OH
O
P-O in P-OH: 1040-910 cm
-
1
1017 cm
-
1

34
Figure 21. X-ray crystal structure of sulfolane bisphenol structure 7.
Literature concerning the synthesis of 7 is scarce and outdated. Joullie et. al., reported
the synthesis of 7 from the diazotization of benzidine sulfone which can be obtained by
reacting it with fuming sulfuric acid (Scheme 12)59,60
.
Scheme 12. Previously reported synthesis of 7.59,60

35
There has not been any literature reporting the synthesis of bisphenol sulfolane 7 directly
from bisphenol. The results in this study may suggest that the trifluorovinyl ether group is
favoring the formation of the five-member ring sulfolane. Further attempts to generate
the same sulfolane structure starting from bisphenol, yielded a water soluble product that
did not precipitate upon addition of excess sodium chloride. 1
H NMR analysis of the
crude product showed only a large signal at 4 ppm that was assigned to water protons.
Due to the reactivity of the trifluorovinyl ether groups, a more convenient approach to
sulfonated BPVE reported in the literature was investigated.8
The synthesis started with
the sulfonation of 4-bis(tetrafluorodibromoethyl) aryl ether with chlorosulfonic acid, as
reported in the literature. This procedure generates 4,4’-di-(2-bromotetrafluoroethoxy)-
3,3’-biphenyldisulfonyl chloride as colorless needles (Figure 22).
OO
Br
F F
F
F
Br
F
F
F
F
S
S
OO
Cl
O O
Cl
KF, r.t.
OO
Br
F F
F
F
Br
F
F
F
F
S
S
OO
F
O O
F
CH3CN
OO
Br
F F
F
F
Br
F
F
F
F ClSO3H
CH3Cl
0-35 o
C
9
8
10
Scheme 13. Synthesis of bromo-precursor 10.

36
Transhalogenation of the sulfonyl chloride with KF was successfully carried out at room
temperature and not at 80 o
C as literature suggested (Scheme 13). This process generated
the sulfonyl fluoride as colorless needles. 19
F NMR signals for the SO2F group appeared
at 60 ppm.
Figure 22. X-ray crystal structure of 4,4’-di-(2-bromotetrafluoroethoxy)-3,3’-
biphenyldisulfonyl chloride.
During the elimination step of the reaction, Zn dust was used to attempt the synthesis of
the TFVE compound. Numerous attempts generated the hydrogenated product as the
major product. Just a small quantity of the elimination product was detected by 19
F NMR.
As opposed to the elimination of unsulfonated aromatic rings where the reaction proceeds
smoothly once the formation of the zinc salt is generated, the sulfonyl fluoride
intermediate took in most cases 24 h to generate the zinc intermediate, after that point and
for approximately seven days the only products that were detected by 19
F NMR, were; the
organozinc salt (11), the hydrogenated product (12) and small amounts of the

37
trifluorovinyl compound (13) (Figure 24). Scheme 14 shows the synthetic route
employed to obtained 13. Similar results were obtained using dyglime and CuCl to assist
the deahalogenation. This time the temperature was kept at 110 o
C.
Scheme 14. Attempted elimination of 10.
Nelson et al.,61
, attempted the synthesis of perfluorinated BPVE monomer (Figure 23).
Zinc mediated elimination of the bromo-precursor yielded only 5% of the desired
compound. The major products detected after 3 days were the organozinc intermediate
and starting material. These results suggest that electron withdrawing groups on the
aromatic ring, such as fluorine atoms strongly deactivates the dehalogenation step.
Figure 23. Previously attempted TFVE monomer.

38
Figure24.19
FNMRspectrumofcrudereactionmixture
OO
Br
FF
F
F
Br
F
F
F
F
S
S
OO
F
OO
F
OO
ZnBr
FBFB
FA
FA
BrZn
FB
FB
FA
Fa
S
S
OO
F
OO
F
Zn,80o
C
OO
FE
FF
FG
FF
FEFGS
S
OO
F
OO
F
OO
H
FDFD
FC
FC
H
FD
FD
FC
FC
SS
OO
F
OO
F
+
MeCN
+
FD
FC
FAFB
FEFF
FG
38

39
Fluoride ion elimination of organozinc salts is not always facile. Klabunde et. al.62
did
not observe the elimination product of perfluoro-n-octylzinc bromide. This was attributed
to the formation of a very stable adduct with acetonitrile (Figure 25b). Kawakami et. al.
63
reported the isolation and use of ethyl bromozincacetate, obtained as a stable 8-member
ring dimer (Figure 25a). In both cases the Zn2+
cation is coordinated to solvents with
donor properties such as acetronitrile,64
or THF.65
CH
Zn
O
H2
C
Zn
O
Br
Br
O
O
OEt
EtO
F3C (CF2)6 C
F
F
Zn
Br
N
N C CH3
C CH3
2+
2+
(a) (b)
2+
-
-
Figure 25. Previously reported organozinc salts.
Zn2+
is regarded as a borderline acid according to Pearson’s HSAB principle.66
Zn2+
has
shown the ability to coordinate to sulfonyl 67
and sulfite 68
containing compounds which
are considered borderline bases. It has also been reported that Zn2+
and SO3
2-
can form
various inorganic clusters, 1D chains or 2-D sheets with the use of different bifunctional
organic ligands such as ethylendiamine and piperazine.69

40
Coordination through the sulfonyl oxygen is likely to stabilize the zinc intermediate
through the formation of an 8-member ring (Figure 26), which could have played a
deactivating roll towards fluoride ion elimination.
S
O
F2
C
O
CF2
Zn
O
F Br
Figure 26. Proposed organozinc intermediate: Lewis acid-base cyclocoordination
Blending of Modified Zirconia and Sulfonated PFCB Polymers
An alternative route towards zirconia doped sulfonated PFCB polymers was proposed.
This approach involved casting S-BPVE polymers of different IEC values with 5 wt %
zirconia powder and modified zirconia powder.
It has been reported previously that inorganic fillers can improve several properties of
films without being covalently attached to the polymer chains. Specific Lewis acid-base
type interactions between the inorganic and organic components confer to the membrane
a new structural arrangement which improves mechanical properties and water
management.70
In this work, three samples (5 g each) of bisphenylvinyl ether (BPVE)
polymer were reacted with 2.5, 3.7 and 5 g of ClSO3H during 1 h, affording polymers
with different IEC values: 0.96 (P4), 1.05 (P5), 1.12 meq/g (P6) respectively. These

41
values were obtained from the titration method outlined in chapter 4. Figure 27 shows
that the addition of 10 % (w) modified ZrO2 increased the IEC of all three polymers (P5-
P7) while a moderate decrease was observed for polymers with a 10 wt % concentration
of unmodified zirconia powder. For more accuracy more IEC experimentes are required.
Figure 27. IEC of sulfonated BPVE polymers.
It has been shown that incorporation of phosphate and phosphonates in ZrO2 enhances
Brønsted acidity on the surface and decreases Lewis acidity (Figure 18).39
Moreover,
monodentate anchoring leaves one acid proton available,71,72
thus increasing the IEC of
the membranes (Figure 28).

42
Figure 28. Adsorption modes for arylphosphonic acids.
To obtain the IEC values, the membranes were convertred to the SO3Na form by
immersion in boiling NaOH 0.1 M for two hours. Then, the membranes were immersed
in distilled water 24 h. Finally, the membranes were immersed in NaCl 0.1M for 24 h
and the solution was titrated with NaOH 0.01 N. The number of NaOH meq was then
divide by the weight of the dry membrane.
The IEC values of zirconia, modified zirconia and modifier (TFVE-PA) are shown in
table 5. Calculated IEC values were obtained from the equation 1,59
and were in
agreement with experimental values.
IEC = Σ[(IECi)(Xi)] (1)
IECi is the experimental IEC value of each component of the hybrid composite and Xi is
the weight ratio of each component. For example, the calculated IEC for modified ZrO2 is
the sum: (zirconia’s IEC)(g of ZrO2) + (TFVE-PA’s IEC)(g of TFVE-PA)

43
Table 5. IEC values of PFCB polymers.
Compound IEC (meq/g)
(experimental)
IEC (meq/g)
(calculated)
ZrO2 0.86 -
TFVE-PA 8.83 -
Modified ZrO2 1.08 1.60
P2 0.7 -
P3 0.34 -
P4 0.96 -
P4 + 10% ZrO2 0.73 0.95
P4 + 10% mod ZrO2 0.98 0.97
P5 1.05 -
P5 + 10% ZrO2 0.96 1.03
P5 + 10% mod ZrO2 1.2 1.05
P6 1.12 -
P6 + 10 % ZrO2 1.04 1.09
P6 + 10% mod ZrO2 1.22 1.11
Sulfonated PFCB polymers P4 and P5 with 5 w % modified zirconia also showed a
noticeable improvement in thermal-oxidative stability as shown in figures 29 and 30.

44
Figure 29. TGA analysis of P4, P4 10% mod ZrO2 and BPVE (10 o
C/min under
N2).
Figure 30. TGA analysis of P5, P5 10% mod ZrO2 and BPVE (10 o
C/min under N2).
0
20
40
60
80
100
120
0 200 400 600 800 1000
Temperature (C)
P4 P4 + 10 % mod ZrO2
Weight
loss (%)
0
20
40
60
80
100
120
0 200 400 600 800 1000
Temperature (C)
Weight
loss (%)
BPVE P5 P5 + 10% mod ZrO2
BPVE

45
3.3 Conclusions
Surface modification of zirconia aerogel was accomplished by complexation with p-
trifluorovinyloxyphenyl phosphonic acid. The FTIR band of the P-O bond was used to
determine the adsorption of the organophosphonic acid. DSC analysis of the grafted
particles, showed a 10 % mass loss at 500 o
C which was attributed to the anchored
organophosphonic acid.
Several attempts to obtained sulfonated BPVE generated the hydrogenated product and
the organozinc intermediate. Only unrecoverable amounts of the target compound were
obtained as evidenced by 19
F NMR. The difficulty to obtain the trifluorovinyl ether
compound was attributed to the possible formation of an adduct where Zn2+
is
coordinated to the sulfonyl oxygen.
Incorporation of 10 w-% modified zirconia as a filler improved the ionic exchange
capacity of sulfonated PFCB membranes. This was attributed to the increased Brönsted
acidity on the surface of zirconia. Conversely, unmodified zirconia doped membranes
showed a decrease in their IEC values. Highly porous zirconia seems to be a promising
reinforcing material for use in PEMs.

46
CHAPTER 4
EXPERIMENTAL
4.1. Instruments
1
H NMR (300 MHz), proton decoupled 13
C NMR (75 MHz), 19
F NMR (282 MHz)
spectra were obtained with a JEOL Eclipse+
500 spectrometer. Chloroform-d, or DMSO-
d6 was used as solvents and chemical shifts reported were internally referenced to
tetramethylsilane (0 ppm), CDCl3 (77 ppm), and CFCl3 (0 ppm) for 1
H, 13
C, and 19
F
nuclei, respectively. Infrared analyses were performed on KBr pellets using a
ThermoNicolet Magna-IRTM
550 FTIR spectrometer. Gas chromatography - Mass
spectrometry (GC-MS) data were obtained using a GC/MS-QP5000 chromatograph. Gel
permeation chromatography (GPC) data were collected using a Waters 2690 Alliance
System with refractive index detection at 35 °C, and equipped with two consecutive
Polymer Labs PLGel 5mm Mixed-D and Mixed-E columns. Retention times were
calibrated against Polymer Labs Easical PS-2 polystyrene standards and using in CHCl3
HPLC grade as the solvent. Differential scanning calorimetry (DSC) data and thermal
gravimetric analysis (TGA) data were obtained on a Mettler-Toledo 851 TGA/SDTA
and TA Instruments Q 1000 DSC system, respectively at a heating rate of 10 o
C/min in a
N2 atmosphere. The glass transition temperatures (Tg) were obtained from a second
heating after quick cooling.

47
4.2. Materials
4,4’-Dichlorodiphenyl sulfone (DCDPS) was generously donated by Solvay Advanced
Polymers. 3,3’-Difulfonated-4,4’-dichlorodiphenyl sulfone (SDCDPS) was prepared
from DCDPS by a reported method.73
All other reagents and solvents were obtained
from Fisher Scientific or Aldrich and used as received unless otherwise noted.
Bisphenol-T and p-Bromotrifluorovinyloxy phenyl ether were provided by Tetramer
Technologies L.L.C.. Bisphenol-T was recrystallized from hot toluene. p-
Bromotrifluorovinyloxy phenyl ether was purified over alumina column. Caution:
Bisphenols should be treated with caution as possible irritants. Zirconia aerogel powder
was prepared using a Parr 4843 reactor.
4.3. Procedures
Synthesis of the Disodium salt of 3,3'-disulfonated-4,4'-dichlorodiphenyl sulfones
(SDCDPS): DCDPS (28.7 g, 99 mmol) was dissolved in 60 mL of 30% oleum in a 100
mL, two necked flask equipped with a magnetic stirrer, condenser and a nitrogen
inlet/oulet. The solution was heated to 110 °C for 6 h. It was then cooled to room
temperature and dissolved in 400 mL of ice/water. Then, 180 g of sodium chloride was
added producing the disodium salt of SDCDPS as a white precipitate. The powder was
filtered and redissolved in 400 mL of deionized water, and then pH was reduced to 6-7 by

48
the addition of aqueous 2 N sodium hydroxide. Next, 180 g of NaCl were added to salt
out the sodium form of the disulfonated monomer. The crude product was filtered and
recrystallized from a heated mixture of methanol and deionized water (7/3 v/v),
producing needlelike crystals (80% yield). 1
H NMR was used to confirm the structure
and purity of the monomer. 1
H NMR (300 MHz, DMSO-d6), δ: 8.3 (1H, d, Jmeta = 2.4
Hz ), 7.83 (1H, dd, Jortho = 8.2 Hz, Jmeta = 2.4 Hz), 7.64 (1H, d, Jortho= 8.2 Hz) ppm
Synthesis of poly(arylene ether sulfone) containing PFCB unit (P1) :
To a 150 mL three necked flask equipped with a mechanical stirrer, argon inlet and a
Dean-Stark trap were added Bisphenol-T (2.546 g, 6.7 mmol) and DCDPS (1.923 g, 6.7
mmol). Potassium carbonate (2.19 g, 15.9 mmol), toluene (50 mL) and DMAc (21 mL)
were added to the flask and the reaction mixture was heated to reflux (150 o
C) for 4 h to
remove water (via Dean-Stark trap). After complete removal of toluene, the solution was
heated at 170 o
C for 24 h. After polymerization, the solution was cooled, diluted with
DMAc and the product was precipitated into cold water (1 L). The solid polymer was
further washed with water three times and dried at 70 o
C under reduced pressure. The
analysis of P1 is as follows. IR (KBr): ν 1506, 1488, 1321, 1258 (Ar-O-Ar), 1104 (Ar-O-
Ar), 957 cm-1
. 1
H NMR (300 MHz, DMSO-d6) δ: 7.8 (2H, m), 7.2 (2H, m), 7.1 (2H, m),
6.9(2H, m) ppm; 13
C NMR (75 MHz, DMSO-d6) δ: 161.6, 152.4, 148.8, 135.9, 130.7,
130.4, 129.7, 122.5, 120.6, 118.4 ppm; 19
F NMR (282 MHz, CDCl3) δ: -127.6, -128.3, -
129.1, -129.9 ppm.

49
Synthesis of sulfonated poly(arylene ether sulfone) containing PFCB unit (P2) : To a
150 mL three necked flask equipped with a mechanical stirrer, argon inlet and a Dean-
Stark trap were added bisphenol-T (2.546 g, 6.7 mmol) and SDCDPS (3.291 g, 6.7
mmol). Potassium carbonate (2.19 g, 15.9 mmol), toluene (10 mL) and NMP (20 mL)
were added to the flask and the reaction mixture was heated to reflux (150 o
C) for 4 h to
remove water (via Dean-Stark trap). After complete removal of toluene, the solution was
heated at 190 o
C for 24 h. The solution was cooled and the product precipitated into
hexane. The solid (water soluble) polymer was further washed with hexane three times
and dried at 70 o
C under reduced pressure. The analysis of P2 was as follows. IR (neat):
ν 1678, 1582, 1498, 1467, 1322, 1250 (Ar-O-Ar), 1095 (Ar-O-Ar), 1029 (SO3
-
), 1012 cm-
1
. 1
H NMR (300 MHz, DMSO-d6) δ: 8.2 (2H, m), 7.75 (2H, m), 7.19 (4H, m, ), 7.05 (4H,
m), 6.87 (2H, m) ppm; δ: 19
F NMR (282 MHz, CDCl3) exhibits a series of multiplets
representing the perfluorocyclobutane fluorine signals ranging from -127 to -130 ppm.
Synthesis of copolymer containing Bisphenol-T, DCDPS and SDCDPS (P3):
Partially sulfonated copolymer 7 was prepared by the above method using a
1.0 : 0.68 : 0.32 mixture of Bisphenol-T : DCDPS : SDCDPS, and precipitated into
methanol. The analysis of P3 is as follows. IR (neat): ν 1683, 1585, 1458, 1250 (Ar-
OAr), 1098 (Ar-O-Ar), 1031 (SO3
-
), 1012, 961 (s, cyclobutane-F6), 602 cm-1
. 1
H NMR
(300 MHz, CDCl3) δ: 8.35 (2H, s), 7.98 (4H, s), 7.91 (2H, s), 7.34-7.29 (16 H, m,) , 7.18
(4H, m), 7.01 (2H, s); 19
F NMR (282 MHz, CDCl3) δ: exhibits a series of multiplets
representing the perfluorocyclobutane fluorine signals ranging from –127 to –130 ppm.

50
Membrane Preparation (polymers P1-P3): Polymers were dissolved in DMAc (1g/ 10
mL) forming homogenous yellowish solutions. The solutions were deposited onto glass
plates and dried at 80 o
C for 16 h. The membranes were annealed at 130 o
C for 2 h. and
removed by rinsing with deionized water.
Synthesis of 4-trifluorvinyloxybenzene diethylphosphonate: To a two-necked round
bottom flask, equipped with nitrogen inlet and a magnetic bar, 4-bromo-trifluorovinyl
ether (9 g, 0.035 mol) and diethyl ether (20 mL) were added. The solution was cooled to -
78 o
C and 21.61 mL of 1.7 M t-BuLi (in hexane) was added dropwise. The reaction
mixture was stirred for 2 h while maintaining the temperature at -78 o
C. Then diethyl
chlorophosphate (13.58 g , 78 mmol) were added slowly and stirred overnight. After that,
100 mL of DI water was added to the crude reaction mixture forming an organic and an
aqueous layer. The organic layer was extracted three times using chloroform, and dried
over magnesium sulfate. The solvent was removed by rotovaporation, yielding 4-
trifluorvinyloxybenzene diethylphosphonate (6.9 g, 62%) as a colorless liquid. 1
H NMR
(300 MHz, CDCl3) δ: 1.209 (6 H, t, J = 7.2), 4.001 (4 H, q, J = 5.8 Hz ), 7.076 (2H, d,
Jortho = 3.0 Hz, Jmeta =1.0 Hz), 7.742 (2H, d, Jortho = 12.6, Jmeta = 8.2 ); 19
F NMR (470
MHz, CDCl3) δ: -118.0 (2F, dd, trans-CF=CF2), -125.0 (2F, dd, cis-CF=CF2), -134.0 (2F,
dd, -CF=CF2) ; 31P NMR (121 MHz, CDCl3) δ: 18.240 (1P, s).

51
Synthesis of p-trifluorovinyloxyphenyl phosphonic acid (4).
A two necked round bottom flask equipped with nitrogen inlet and a magnetic bar was
charged with 6.45 g (0.021 mol) of 4-trifluorvinyloxybenzene diethylphosphonate, and
20 mL of dichloromethane. 13.56 g of BrSiMe3 was added dropwise. The reaction
mixture was stirred at room temperature overnight. Then, the solvent was rotovaporated
and 50 mL of methanol was added. The mixture was stirred for two 2 hours. The solvent
was evaporated and 4 was recrystallized in hot chloroform, yielding colorless needles
(5.01 g, 85%); mp = 150 o
C; 1
H NMR (300 MHz, CDCl3) δ: 2.4 (1H, m, J = 2.0 ), 7.3
(2H, d, Jortho = 8.2 Hz, Jmeta = 2.0 Hz), 7.7 (2H, d, Jortho = 12.3 Hz, Jmeta = 8.5 Hz); 19
F
NMR (282 MHz, CDCl3) δ: -117.89 (2F, dd, trans-CF=CF2), -125.76 (2F, dd, cis-
CF=CF2), -134.6 (2F, dd, -CF=CF2) ; 31
P NMR (121 MHz, CDCl3) δ: 12.1 (1P, s).
Zirconia aerogel preparation and surface modification
Zirconyl nitrate dihydrate was used as a starting material. Deionized water and ethanol
were used for preparing alcohol–aqueous mixture. ZrO(NO3)2 · 2H2O (12.5 g) was added
to an alcohol–water (400:100 mL) mixture at room temperature. The mixture was heated
to 80 °C and kept for about an hour. Then, the gel was dried with the supercritical drying
method. To exceed the critical condition without formation of a vapor–liquid interface
inside the pores, the mixture as described above was heated and pressurized. By heating,
the temperature and pressure of the liquid in the autoclave would surpass the Tc (241 o
C)
and Pc (6.2 MPa) of ethanol. The final temperature and pressure were about 280 o
C, 17.0
MPa. Then the fluid (ethanol + HNO3) was slowly flushed with nitrogen in several

52
batches (complete removal was achieved within 1 hour). Then the vessel was cooled to
room temperature (1 hour). The final zirconia particles had an average diameter of 5 nm
and surface area of 231 m2
/g.
Sulfonation of BPVE (3)
In a test tube with a magnetic stirring bar, BPVE (5 g, 14.4 mmol) was added. Then,
fuming sulfuric acid (20% SO3) (15 mL)was added dropwise with the formation a dark
viscous solution. After 2 hours, the contents of the test tube were added to a beaker
containing ice-water. An excess of sodium chloride (60 g) was added to the mixture,
generating a palid yellow precipitate. The solid was filtered and redissolved in 10 mL of
water and neutralized with NaOH 1M. Addition of another excess of sodium chloride
precipitates 7 as a yellow solid. 7 was recrystallized from hot water (2.69 g, 70 %) 1
H
NMR (300 MHz, DMSO-d6) δ: 7.050 (1H, dd, J = 8.5 Hz), 7.130 (1 H, dd, Jortho = 8.5,
Jmeta = 2.4 Hz ), 7.762 (1 H, d, J = 2.4 Hz), 10.467 (H, s); 13
C NMR (75 MHz, CDCl3) δ:
108.5, 121.5, 123.0, 124.0, 138.7, 158.9 ppm.
Sulfontation of Bisphenol
The same procedure outlined for the sulfonation of BPVE, was employed. However
addition of sodium chloride did not produce any precipitate.
Sulfonation of 4, 4-di(2-bromotetrafluoroethoxy)biphenyl

53
To a 1L round bottom flask resting in an ice-water bath, 4,4-di(2-
bromotetrafluoroethoxy)biphenyl (70,72 g, 0.13 mol) and chloroform (250 mL) were
added. To this solution, chlorosulfonic acid (500 g) was added dropwise, and stirred for
two days at room temperature, under nitrogen gas. The reaction mixture was then slowly
poured into a 2 L beaker filled with crushed ice. The chloroform layer was transferred to
a separation funnel and washed with ice water. After drying over sodium sulfate, the
crude product was recrystallized from hot chloroform, yielding 4,4’-di(2-
bromotetrafluoroethoxy)-3,3’-biphenyldisulfonyl chloride (83.15 g, 85%) as colorless
needles. 1
H NMR (300 MHz, CDCl3) δ: 7.7 (1H, d, J = 8.9 Hz), 7.9 (1H, dd, Jortho = 8.5,
Jmeta = 1.3), 8.2 (1H, d, Jmeta = 1.3 Hz); 19
F NMR (282 MHz, CDCl3) δ: -85.2 (1F, s), -
67.8 (1F, s) ppm.
Fluorination of 4,4’-di(2-bromotetrafluoroethoxy)-3,3’-biphenyldisulfonyl chloride
To a 1 L round bottom flask placed in a dry box, 4,4’-di(2-bromotetrafluoroethoxy)-3,3’-
biphenyldisulfonyl chloride (70 g, 94 mmol), dry potassium fluoride (43.6g) and dried
CH3CN (400 mL) were added. The mixture was magnetically stirred for two days at
room temperature. The completion of the reaction was confirmed by 19F NMR. The
inorganic salts were filtered and washed with acetone three times. The combined layers
were washed with saturated sodium chlorine solution three times and dried over
magnesium sulfate. After filtration of the solid material and evaporation of the solvent,
the crude was recrystallized from hot chloroform, yielding 4,4’-di(2-
bromotetrafluoroethoxy)-3,3’-biphenyldisulfonyl fluoride as colorless needles (60 g, 90%)

54
1
H NMR (300 MHz, CDCl3) δ: 7.830 (1H, dt, J = 8.5, 2.0 Hz), 8.180 (1 H, dd, Jortho = 8.9,
Jmeta = 2.4 Hz), 8.346 (1 H, d, J = 2.4 Hz); 19
F NMR (282 MHz, CDCl3) δ: -84.913 (1F,
s), -70.400 (1F, s), 63.277(1F, s) ppm.
Attempted synthesis of 4,4’-di(trifluorovinyloxy)-3,3’-biphenyldisulfonyl fluoride
(13)
A 250 mL round bottom flask equipped with reflux condenser, nitrogen inlet and a
magnetic bar, was charged with activated zinc powder (3.64 g, 0.056 mol). The flask was
flame dried and purged with nitrogen three times. 10 mL of acetonitrile was added to the
flask using a syringe and the contents were heated to 80 o
C. A solution of 10 g (0.0141
mol) of 4,4’-di(trifluorovinyloxy)-3,3’-biphenyldisulfonyl fluoride in 60 mL of well
dried acetonitrile was added dropwise. The formation of the zinc intermediate was
evident by the turbidity of the mixture. The contents of the flask were stirred for 4 days.
After that, the 19
F NMR spectrum showed that the only species present, were the
intermediate zinc salt, the hydrogenated product, and small amounts of the elimination
product. No further work up was carried out.
Blending of sulfonated BPVE polymer with modified Zirconia.
BPVE (3) monomer (10 g) was heated to 160 o
C in a glass ampoule for two days.
Two samples of BPVE polymer (Mn = 30000) were dissolved in chlorosulfonic acid.
Sample 1 was reacted for 10 h. (P4) and Sample 2 was reacted for 20 h. (P5). Polymers
P4 and P5 were dissolved in DMAc (1g/ 10 mL) and mixed with 5 % modified zirconia

55
and sonicated for 1 h. The polymer solutions were deposited onto a glass plates and dried
under vacuum at 80 o
C. The membranes were annealed at 130 o
C for 2 h. and peeled off
of the glass plate by rinsing with DI water.
IEC measurements
Ion-exchange capacity was determined by equilibrating the membranes in boiling 1.0 M
NaOH solutions for 2 h to insure that all the charged sites of the membrane were in the
SO3Na form. The membranes were then immersed in distilled water during 24 h before
equilibration in 0.10 M NaCl for 24 h. Ion-exchange capacity was determined from the
increase in basicity by NaOH 0.01N titration. The total molar number of OH−
was
obtained and IEC was calculated by dividing this number by the dry membrane weight.
Theoretical IEC value for polymer P2 was calculated as follows:
IEC = repeat unit molecular weight = (754 g/mol) = 377 g/eq 2.65 meq/g
equivalents per unit 2 eq

57
Appendix A
Crystal Data for compound (4)
Crystal Data and Structure Refinements for p-trifluorovinyloxy phenyl phosphonic acid
(4)
Empirical formula C8 H6 F3 O4 P
Formula weight 254.10
Temperature 153(2) K
Wavelength 0.71073 A
Crystal system, space group Monoclinic, P2(1)/c
Unit cell dimensions a = 21.142(4) Å
b = 6.8748(14) Å
c = 6.6968(13) Å
α = 90 o
β = 97.49(3) o
γ = 90 o
V = 965.1(3) Å3
Z, Calculated density 4, 1.749 Mg/m3
Absorption coefficient 0.328 mm-1
F(000) 512
Crystal size 0.60 x 0.58 x 0.02 mm
Theta range for data collection 3.54 to 25.05o
.
Limiting indices -25<=h<=25, -8<=k<=5, -7<=l<=7
Reflections collected / unique 5878 / 1652 [R(int) = 0.0736]
Completeness to theta = 25.05 97.2 %
Absorption correction REQAB (multi-scan)
Max. and min. transmission 0.9935 and 0.8277
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 1652 / 0 / 147
Goodness-of-fit on F2
1.099
Final R indices [I>2sigma(I)] R1 = 0.0767, wR2 = 0.1969
R indices (all data) R1 = 0.0854, wR2 = 0.2137
Largest diff. peak and hole 0.989 and -0.719 e.A-3

58
Atomic coordinates ( x 104
) and equivalent isotropic
displacement parameters (A2
x 103
)
x y z U(eq)
P(1) 872(1) 4587(1) 2697(1) 22(1)
O(1) 1019(1) 4864(4) 4993(3) 28(1)
O(2) 562(1) 2649(4) 2185(3) 26(1)
O(3) 487(1) 6335(4) 1758(4) 31(1)
O(4) 3306(1) 5363(4) -779(4) 39(1)
C(1) 1609(2) 4822(5) 1706(5) 23(1)
C(2) 1624(2) 5529(5) -246(5) 25(1)
C(3) 2195(2) 5685(5) -1026(5) 27(1)
C(4) 2754(2) 5151(6) 159(6) 30(1)
C(5) 2759(2) 4472(6) 2096(6) 32(1)
C(6) 2180(2) 4295(5) 2857(5) 27(1)
C(7) 3864(2) 4958(9) 333(6) 47(1)
C(8) 4271(2) 6251(10) 1057(7) 58(1)
F(1) 4011(1) 3056(5) 513(5) 63(1)
F(2) 4836(1) 5880(7) 2005(5) 84(1)
F(3) 4148(2) 8134(6) 885(5) 76(1)

59
Bond lengths [Å] and angles [deg].
P(1)-O(2) 1.504(3)
P(1)-O(3) 1.539(3)
P(1)-O(1) 1.540(2)
P(1)-C(1) 1.778(3)
O(4)-C(7) 1.340(5)
O(4)-C(4) 1.403(4)
C(1)-C(6) 1.393(5)
C(1)-C(2) 1.399(5)
C(2)-C(3) 1.382(5)
C(3)-C(4) 1.384(5)
C(4)-C(5) 1.377(5)
C(5)-C(6) 1.390(5)
C(7)-C(8) 1.286(8)
C(7)-F(1) 1.346(6)
C(8)-F(2) 1.304(6)
C(8)-F(3) 1.322(7)
O(2)-P(1)-O(3) 113.98(15)
O(2)-P(1)-O(1) 111.24(14)
O(3)-P(1)-O(1) 109.77(15)
O(2)-P(1)-C(1) 111.83(15)
O(3)-P(1)-C(1) 102.69(14)
O(1)-P(1)-C(1) 106.81(15)
C(7)-O(4)-C(4) 116.9(3)
C(6)-C(1)-C(2) 119.0(3)
C(6)-C(1)-P(1) 120.6(3)
C(2)-C(1)-P(1) 120.5(3)
C(3)-C(2)-C(1) 120.5(3)
C(2)-C(3)-C(4) 119.1(3)
C(5)-C(4)-C(3) 122.1(3)
C(5)-C(4)-O(4) 123.5(3)
C(3)-C(4)-O(4) 114.4(3)
C(4)-C(5)-C(6) 118.4(3)
C(5)-C(6)-C(1) 121.0(3)
C(8)-C(7)-O(4) 124.2(6)
C(8)-C(7)-F(1) 120.2(5)
O(4)-C(7)-F(1) 115.3(4)
C(7)-C(8)-F(2) 124.9(6)
C(7)-C(8)-F(3) 122.0(5)
F(2)-C(8)-F(3) 113.0(5)

60
Anisotropic displacement parameters (A2
x 103
).
The anisotropic displacement factor exponent takes the form:
-2π2
[ h2
a*2
U11 + ... + 2 h k a* b* U12 ]
U11 U22 U33 U23 U13 U12
P(1) 25(1) 29(1) 12(1) 0(1) 3(1) 0(1)
O(1) 39(1) 35(2) 12(1) -2(1) 5(1) -6(1)
O(2) 27(1) 35(2) 17(1) -4(1) 6(1) -4(1)
O(3) 28(1) 37(2) 29(1) 13(1) 11(1) 8(1)
O(4) 29(1) 57(2) 32(2) 3(1) 10(1) 0(1)
C(1) 26(2) 27(2) 17(2) -1(1) 3(1) 0(1)
C(2) 24(2) 30(2) 20(2) 0(1) 2(1) 2(1)
C(3) 33(2) 34(2) 15(2) -2(1) 8(1) -3(1)
C(4) 27(2) 40(2) 25(2) 1(2) 8(2) 0(2)
C(5) 24(2) 45(3) 27(2) 4(2) 1(1) 4(2)
C(6) 30(2) 35(2) 17(2) 5(1) 2(1) 1(2)
C(7) 30(2) 78(3) 33(2) 2(2) 8(2) 1(2)
C(8) 33(2) 92(4) 48(3) -11(3) 10(2) -7(3)
F(1) 47(2) 70(2) 73(2) 3(2) 12(1) 14(1)
F(2) 34(2) 162(4) 55(2) -13(2) -1(1) -11(2)
F(3) 74(2) 81(3) 75(2) -23(2) 23(2) -21(2)

61
Hydrogen coordinates ( x 104
) and isotropic
x 103
).
x y z U(eq)
H(1) 838 4000 5573 34
H(3) 154 6449 2285 37
H(2) 1234 5909 -1050 30
H(3) 2205 6158 -2371 32
H(5) 3152 4129 2901 38
H(6) 2174 3803 4196 33

62
Appendix B
Crystal data for compound (7)
Crystal data and structure refinement for sulfolane bisphenol (7).
Empirical formula C24 H20 O10 S2
Crystal system, space group Triclinic, P-1
b = 8.6957(17) Å
c = 10.017(2) Å
α = 104.22(3)o
β = 103.99(3)o
γ = 98.98(3)o
V= 569.45(19) A3
F(000) 276
Theta range for data collection 2.78 to 25.10 deg.
Refinement method Full-matrix least-squares on F^2
Goodness-of-fit on F^2 1.056
Largest diff. peak and hole 0.276 and -0.330 e.A^-3

63
Atomic coordinates (x104
x 103
) for sulfolane bisphenol (7).
U(eq) is defined as one third of the trace of the orthogonalized
Uij tensor.
x y z U(eq)
S(1) 3720(1) 9363(1) 2710(1) 23(1)
O(1) -601(2) 5431(2) -2195(2) 35(1)
O(2) 7685(2) 15333(2) 4929(1) 33(1)
O(3) 5310(2) 8536(2) 2976(2) 33(1)
O(4) 2380(2) 9276(2) 3576(1) 34(1)
O(5) 9030(2) 18019(2) 4365(2) 38(1)
C(1) 2432(3) 8767(2) 863(2) 22(1)
C(2) 1347(3) 7209(2) 64(2) 25(1)
C(3) 448(3) 6966(2) -1394(2) 26(1)
C(4) 645(3) 8256(2) -1986(2) 25(1)
C(5) 1746(3) 9803(2) -1142(2) 23(1)
C(6) 2671(2) 10078(2) 310(2) 21(1)
C(7) 3924(2) 11594(2) 1406(2) 20(1)
C(8) 4496(3) 13125(2) 1252(2) 25(1)
C(9) 5735(3) 14391(2) 2433(2) 27(1)
C(10) 6422(3) 14128(2) 3764(2) 24(1)
C(11) 5835(3) 12618(2) 3954(2) 23(1)
C(12) 4604(3) 11396(2) 2764(2) 21(1)

64
Bond lengths [Å] and angles [deg] for sulfolane bisphenol (7)..
S(1)-O(3) 1.4419(15)
S(1)-O(4) 1.4435(14)
S(1)-C(1) 1.7592(19)
S(1)-C(12) 1.7645(19)
O(1)-C(3) 1.362(2)
O(2)-C(10) 1.366(2)
C(1)-C(2) 1.384(3)
C(1)-C(6) 1.390(3)
C(2)-C(3) 1.394(3)
C(3)-C(4) 1.396(3)
C(4)-C(5) 1.390(3)
C(5)-C(6) 1.387(3)
C(6)-C(7) 1.480(2)
C(7)-C(8) 1.387(3)
C(7)-C(12) 1.393(2)
C(8)-C(9) 1.395(3)
C(9)-C(10) 1.393(3)
C(10)-C(11) 1.388(3)
C(11)-C(12) 1.379(3)
O(3)-S(1)-O(4) 116.01(9)
O(3)-S(1)-C(1) 110.83(9)
O(4)-S(1)-C(1) 111.52(9)
O(3)-S(1)-C(12) 111.79(9)
O(4)-S(1)-C(12) 111.04(9)
C(1)-S(1)-C(12) 93.47(9)
C(2)-C(1)-C(6) 124.50(17)
C(2)-C(1)-S(1) 125.02(15)
C(6)-C(1)-S(1) 110.48(14)
C(1)-C(2)-C(3) 116.70(17)
O(1)-C(3)-C(2) 117.14(17)
O(1)-C(3)-C(4) 122.45(17)
C(2)-C(3)-C(4) 120.41(17)
C(5)-C(4)-C(3) 120.94(17)
C(6)-C(5)-C(4) 119.90(17)
C(5)-C(6)-C(1) 117.55(16)
C(5)-C(6)-C(7) 129.56(16)
C(1)-C(6)-C(7) 112.89(15)
C(8)-C(7)-C(12) 117.73(16)
C(8)-C(7)-C(6) 129.21(16)
C(12)-C(7)-C(6) 113.06(16)
C(7)-C(8)-C(9) 119.79(17)
C(10)-C(9)-C(8) 120.59(17)
O(2)-C(10)-C(11) 117.45(16)
O(2)-C(10)-C(9) 121.87(17)
C(11)-C(10)-C(9) 120.69(17)
C(12)-C(11)-C(10) 117.13(16)
C(11)-C(12)-C(7) 124.03(17)
C(11)-C(12)-S(1) 125.84(14)
C(7)-C(12)-S(1) 110.10(14

65
Anisotropic displacement parameters (A2
x 103
)
for sulfolane bisphenol (7).
-2 π2
[ h2
a*2
U11 + ... + 2 h k a* b* U12 ]
U11 U22 U33 U23 U13 U12
S(1) 26(1) 20(1) 18(1) 7(1) 3(1) 0(1)
O(1) 41(1) 24(1) 25(1) 1(1) -3(1) -4(1)
O(2) 40(1) 24(1) 23(1) 4(1) 0(1) -6(1)
O(3) 34(1) 27(1) 34(1) 11(1) -2(1) 7(1)
O(4) 40(1) 34(1) 25(1) 9(1) 13(1) -3(1)
O(5) 31(1) 34(1) 53(1) 20(1) 13(1) 5(1)
C(1) 21(1) 24(1) 20(1) 7(1) 6(1) 4(1)
C(2) 27(1) 22(1) 24(1) 7(1) 6(1) 2(1)
C(3) 23(1) 22(1) 25(1) 1(1) 4(1) 1(1)
C(4) 23(1) 30(1) 19(1) 5(1) 3(1) 4(1)
C(5) 22(1) 26(1) 22(1) 9(1) 5(1) 4(1)
C(6) 19(1) 22(1) 21(1) 6(1) 6(1) 4(1)
C(7) 18(1) 22(1) 19(1) 5(1) 5(1) 3(1)
C(8) 28(1) 25(1) 22(1) 10(1) 3(1) 3(1)
C(9) 30(1) 20(1) 29(1) 8(1) 6(1) 1(1)
C(10) 22(1) 22(1) 22(1) 2(1) 4(1) 1(1)
C(11) 26(1) 25(1) 17(1) 6(1) 5(1) 4(1)
C(12) 22(1) 21(1) 21(1) 7(1) 7(1) 3(1)

66
Hydrogen coordinates (x104
) and isotropic displacement parameters
(A2
x103
) for sulfolane bisphenol (7).
x y z U(eq)
H(1) -1093 5422 -3037 42
H(2) 8041 16143 4676 39
H(5A) 10100 18372 3980 75(10)
H(5B) 8154 18645 4152 79(10)
H(2A) 1219 6340 493 30
H(4) 10 8073 -2991 30
H(5) 1865 10680 -1562 28
H(8) 4041 13312 335 30
H(9) 6118 15453 2328 32
H(11) 6267 12431 4873 28

67
Appendix C
Crystal data for compound (9)
Crystal data and structure refinement for sulfonated BPVE precursor (9).
Empirical formula C16 H6 Br2 Cl2 F8 O6 S2
Crystal system, space group Monoclinic, P2(1)/c
b = 27.202(5) Å
c = 15.356(3) Å
α = 90o
β = 90.07(3)o
γ = 90o
deg
V= 4714.5(16) Å3
F(000) 2864
Theta range for data collection 2.34 to 25.05 deg.
Refinement method Full-matrix least-squares on F2
Goodness-of-fit on F2
1.054
Largest diff. peak and hole 1.638 and -1.258 e.A-3

68
Atomic coordinates (x104
x103
) sulfonated BPVE precursor (9).
U(eq) is defined as one third of the trace of the orthogonalized
Uij tensor.
x y z U(eq)
Br(1') 8212(1) 4833(1) 4808(1) 61(1)
Br(1) 14666(1) 97(1) -1302(1) 82(1)
Br(2) 4237(1) 4097(1) 108(1) 60(1)
S(1) 11997(1) 1876(1) -3524(1) 25(1)
S(2) 7866(2) 3384(1) 818(1) 31(1)
S(1') 6914(1) 3114(1) 5686(1) 28(1)
S(2') 2765(2) 1601(1) 1357(1) 29(1)
Cl(1) 11417(2) 1203(1) -3889(1) 40(1)
Cl(2) 8330(2) 4102(1) 749(1) 50(1)
Cl(1') 6405(2) 3789(1) 6085(1) 41(1)
Cl(2') 3271(2) 889(1) 1441(1) 49(1)
Br(2') -483(2) 138(1) 3593(2) 80(1)
F(8') -483(2) 138(1) 3593(2) 80(1)
Br(2") -730(2) 765(1) 2083(1) 78(1)
F(8") -730(2) 765(1) 2083(1) 78(1)
F(8'') -862(15) 927(7) 2700(9) 89(6)
Br(2X) -862(15) 927(7) 2700(9) 89(6)
O(5') 3609(4) 1839(2) 816(3) 39(1)
O(3) 11389(4) 2223(2) -4061(3) 33(1)
O(5) 8727(5) 3148(2) 1359(3) 41(1)
O(2') 8179(4) 3115(2) 5674(3) 39(1)
O(1) 12735(4) 1275(2) -2053(3) 35(1)
O(4) 6451(4) 3673(2) -685(3) 39(1)
O(6) 6650(4) 3374(2) 1045(3) 44(1)
O(1') 7565(4) 3745(2) 4224(3) 37(1)
F(1') 9774(4) 4558(2) 3611(3) 58(1)
F(2') 9584(8) 4188(3) 5216(7) 17(2)
F(2") 9696(4) 4069(2) 4693(4) 19(1)
F(3') 7509(4) 4287(2) 3127(3) 45(1)
F(4') 8848(4) 3729(2) 3124(3) 45(1)
F(5') 191(5) 1185(2) 3994(3) 69(2)
F(6') 1738(5) 773(2) 3920(5) 85(2)
F(7') 1167(9) 269(3) 2601(7) 73(3)
F(7") 626(17) 510(8) 2177(13) 85(6)
O(6') 1540(4) 1596(2) 1128(3) 42(1)

69
O(3') 6298(5) 2773(2) 6232(3) 39(1)
C(1) 10107(5) 2312(2) -1444(3) 19(1)
C(2) 10583(5) 2014(2) -789(4) 25(1)
C(3) 11478(6) 1675(2) -955(4) 28(1)
C(4) 11891(6) 1619(2) -1792(4) 24(1)
C(5) 11453(5) 1917(2) -2456(4) 22(1)
C(6) 10574(5) 2265(2) -2291(4) 22(1)
C(7) 9140(5) 2661(2) -1262(4) 22(1)
C(8) 8323(6) 2805(2) -1916(4) 28(1)
C(9) 7427(6) 3141(3) -1748(4) 30(2)
C(10) 7315(6) 3338(2) -936(4) 28(1)
C(11) 8070(5) 3185(2) -262(4) 23(1)
C(12) 8976(5) 2853(2) -431(4) 22(1)
C(13) 13180(6) 935(2) -1500(4) 31(2)
C(14) 13910(6) 568(3) -2037(5) 41(2)
C(15) 5938(5) 3981(2) -1255(4) 26(1)
C(16) 5252(6) 4371(3) -737(4) 37(2)
O(2) 13254(4) 1856(2) -3541(3) 35(1)
F(1) 14729(4) 812(2) -2487(3) 52(1)
F(2) 13207(4) 337(2) -2606(4) 72(2)
F(3) 13845(4) 1143(2) -881(3) 45(1)
F(4) 12318(4) 688(2) -1088(3) 57(1)
F(5) 6706(4) 4202(2) -1777(3) 50(1)
F(6) 5186(4) 3742(2) -1780(3) 45(1)
F(7) 4484(5) 4696(2) -1367(3) 63(2)
F(8) 6038(4) 4662(2) -338(4) 63(1)
O(4') 1350(5) 1310(2) 2867(3) 46(1)
C(1') 4984(5) 2690(2) 3617(4) 24(1)
C(2') 5462(6) 2987(2) 2960(4) 26(1)
C(3') 6333(6) 3329(2) 3124(4) 30(1)
C(4') 6760(5) 3385(2) 3960(4) 25(1)
C(5') 6339(5) 3084(2) 4626(3) 21(1)
C(6') 5456(5) 2738(2) 4458(4) 23(1)
C(7') 4012(5) 2334(2) 3428(4) 20(1)
C(8') 3234(6) 2188(2) 4079(4) 25(1)
C(9') 2336(6) 1849(2) 3928(4) 30(1)
C(10') 2211(6) 1649(2) 3097(4) 27(1)
C(11') 2957(5) 1809(2) 2431(4) 23(1)
C(12') 3863(5) 2137(2) 2598(4) 24(1)
C(13') 8200(6) 4018(3) 3655(4) 35(2)
C(14') 9021(7) 4350(3) 4168(5) 39(2)
C(15') 910(6) 979(3) 3426(4) 33(2)
C(16') 218(9) 577(4) 2945(6) 69(3)

70
Bond lengths [Å] and angles [deg]
for sulfonated BPVE precursor (9).
Br(1')-C(14') 1.879(8)
Br(1)-C(14) 1.910(7)
Br(2)-C(16) 1.885(7)
S(1)-O(2) 1.421(5)
S(1)-O(3) 1.428(5)
S(1)-C(5) 1.756(6)
S(1)-Cl(1) 2.022(2)
S(2)-O(6) 1.417(5)
S(2)-O(5) 1.429(5)
S(2)-C(11) 1.760(6)
S(2)-Cl(2) 2.026(3)
S(1')-O(2') 1.428(5)
S(1')-O(3') 1.430(5)
S(1')-C(5') 1.753(5)
S(1')-Cl(1') 2.020(2)
S(2')-O(5') 1.420(5)
S(2')-O(6') 1.426(5)
S(2')-C(11') 1.757(6)
S(2')-Cl(2') 2.025(3)
Br(2')-C(16') 1.745(11)
Br(2")-F(8'') 1.055(13)
Br(2")-F(7") 1.69(2)
Br(2")-C(16') 1.777(11)
F(8'')-C(16') 1.59(2)
O(1)-C(13) 1.353(8)
O(1)-C(4) 1.394(7)
O(4)-C(15) 1.344(8)
O(4)-C(10) 1.389(7)
O(1')-C(13') 1.353(8)
O(1')-C(4') 1.395(7)
F(1')-C(14') 1.332(8)
F(2')-F(2") 0.875(10)
F(2')-C(14') 1.784(11)
F(2")-C(14') 1.346(9)
F(3')-C(13') 1.341(8)
F(4')-C(13') 1.348(8)
F(5')-C(15') 1.317(8)
F(6')-C(15') 1.326(8)
F(7')-F(7") 1.11(2)
F(7')-C(16') 1.459(14)
F(7")-C(16') 1.280(19)
C(1)-C(2) 1.397(8)
C(1)-C(6) 1.410(8)
C(1)-C(7) 1.474(8)
C(2)-C(3) 1.392(9)
C(3)-C(4) 1.377(9)
C(4)-C(5) 1.392(8)
C(5)-C(6) 1.395(8)
C(7)-C(12) 1.392(8)
C(7)-C(8) 1.417(8)
C(8)-C(9) 1.388(9)
C(9)-C(10) 1.363(9)
C(10)-C(11) 1.403(9)
C(11)-C(12) 1.389(9)
C(13)-F(3) 1.336(8)
C(13)-F(4) 1.341(8)
C(13)-C(14) 1.535(10)
C(14)-F(1) 1.331(9)
C(14)-F(2) 1.336(9)
C(15)-F(5) 1.326(7)
C(15)-F(6) 1.338(7)
C(15)-C(16) 1.536(9)
C(16)-F(8) 1.337(9)
C(16)-F(7) 1.570(9)
O(4')-C(15') 1.341(8)
O(4')-C(10') 1.385(8)
C(1')-C(2') 1.400(9)
C(1')-C(6') 1.403(8)
C(1')-C(7') 1.492(8)
C(2')-C(3') 1.376(9)
C(3')-C(4') 1.379(8)
C(4')-C(5') 1.394(9)
C(5')-C(6') 1.394(8)
C(7')-C(8') 1.390(8)
C(7')-C(12') 1.392(8)
C(8')-C(9') 1.389(9)
C(9')-C(10') 1.394(8)
C(10')-C(11') 1.395(9)
C(11')-C(12') 1.381(9)
C(13')-C(14') 1.515(10)
C(15')-C(16') 1.533(10)
O(2)-S(1)-O(3) 119.6(3)

71
O(2)-S(1)-C(5) 111.7(3)
O(3)-S(1)-C(5) 109.2(3)
O(2)-S(1)-Cl(1) 106.5(2)
O(3)-S(1)-Cl(1) 106.5(2)
C(5)-S(1)-Cl(1) 101.7(2)
O(6)-S(2)-O(5) 120.5(3)
O(6)-S(2)-C(11) 110.8(3)
O(5)-S(2)-C(11) 108.7(3)
O(6)-S(2)-Cl(2) 106.3(3)
O(5)-S(2)-Cl(2) 106.7(2)
C(11)-S(2)-Cl(2) 102.2(2)
O(2')-S(1')-O(3') 119.7(3)
O(2')-S(1')-C(5') 110.9(3)
O(3')-S(1')-C(5') 109.6(3)
O(2')-S(1')-Cl(1') 106.7(2)
O(3')-S(1')-Cl(1') 105.8(2)
C(5')-S(1')-Cl(1') 102.7(2)
O(5')-S(2')-O(6') 120.7(3)
O(5')-S(2')-C(11') 108.7(3)
O(6')-S(2')-C(11') 110.6(3)
O(5')-S(2')-Cl(2') 106.5(2)
O(6')-S(2')-Cl(2') 106.3(2)
C(11')-S(2')-Cl(2') 102.3(2)
F(8'')-Br(2")-F(7") 102.9(11)
F(8'')-Br(2")-C(16') 62.4(11)
F(7")-Br(2")-C(16') 43.3(7)
Br(2")-F(8'')-C(16') 81.6(12)
C(13)-O(1)-C(4) 122.2(5)
C(15)-O(4)-C(10) 122.0(5)
C(13')-O(1')-C(4') 122.9(5)
F(2")-F(2')-C(14') 46.8(6)
F(2')-F(2")-C(14') 104.9(8)
F(7")-F(7')-C(16') 57.9(11)
F(7')-F(7")-C(16') 75.0(15)
F(7')-F(7")-Br(2") 142.6(17)
C(16')-F(7")-Br(2") 72.1(11)
C(2)-C(1)-C(6) 117.9(5)
C(2)-C(1)-C(7) 121.4(5)
C(6)-C(1)-C(7) 120.7(5)
C(3)-C(2)-C(1) 122.0(5)
C(4)-C(3)-C(2) 119.4(6)
C(3)-C(4)-C(5) 119.9(6)
C(3)-C(4)-O(1) 125.1(5)
C(5)-C(4)-O(1) 115.0(5)
C(4)-C(5)-C(6) 120.9(5)
C(4)-C(5)-S(1) 121.5(5)
C(6)-C(5)-S(1) 117.6(4)
C(5)-C(6)-C(1) 119.7(5)
C(12)-C(7)-C(8) 117.3(5)
C(12)-C(7)-C(1) 121.0(5)
C(8)-C(7)-C(1) 121.7(5)
C(9)-C(8)-C(7) 121.6(5)
C(10)-C(9)-C(8) 119.8(6)
C(9)-C(10)-O(4) 125.3(6)
C(9)-C(10)-C(11) 120.1(6)
O(4)-C(10)-C(11) 114.5(5)
C(12)-C(11)-C(10) 120.1(5)
C(12)-C(11)-S(2) 118.2(4)
C(10)-C(11)-S(2) 121.6(5)
C(11)-C(12)-C(7) 120.9(5)
F(3)-C(13)-F(4) 106.6(6)
F(3)-C(13)-O(1) 111.3(5)
F(4)-C(13)-O(1) 111.7(6)
F(3)-C(13)-C(14) 110.9(6)
F(4)-C(13)-C(14) 108.6(6)
O(1)-C(13)-C(14) 107.8(6)
F(1)-C(14)-F(2) 107.9(7)
F(1)-C(14)-C(13) 109.3(6)
F(2)-C(14)-C(13) 109.7(6)
F(1)-C(14)-Br(1) 109.4(5)
F(2)-C(14)-Br(1) 109.6(5)
C(13)-C(14)-Br(1) 110.9(5)
F(5)-C(15)-F(6) 105.8(5)
F(5)-C(15)-O(4) 113.4(5)
F(6)-C(15)-O(4) 111.1(5)
F(5)-C(15)-C(16) 109.3(5)
F(6)-C(15)-C(16) 109.1(5)
O(4)-C(15)-C(16) 108.1(5)
F(8)-C(16)-C(15) 108.2(6)
F(8)-C(16)-F(7) 108.4(5)
C(15)-C(16)-F(7) 110.3(5)
F(8)-C(16)-Br(2) 108.8(5)
C(15)-C(16)-Br(2) 113.0(5)
F(7)-C(16)-Br(2) 108.1(4)
C(15')-O(4')-C(10') 122.9(5)
C(2')-C(1')-C(6') 117.6(6)
C(2')-C(1')-C(7') 121.2(5)
C(6')-C(1')-C(7') 121.1(5)

72
C(3')-C(2')-C(1') 122.3(6)
C(2')-C(3')-C(4') 119.5(6)
C(3')-C(4')-C(5') 120.0(6)
C(3')-C(4')-O(1') 125.0(6)
C(5')-C(4')-O(1') 114.9(5)
C(6')-C(5')-C(4') 120.3(5)
C(6')-C(5')-S(1') 117.8(4)
C(4')-C(5')-S(1') 121.9(5)
C(5')-C(6')-C(1') 120.2(5)
C(8')-C(7')-C(12') 118.1(5)
C(8')-C(7')-C(1') 120.8(5)
C(12')-C(7')-C(1') 121.1(5)
C(9')-C(8')-C(7') 122.1(5)
C(8')-C(9')-C(10') 119.0(6)
O(4')-C(10')-C(9') 124.3(6)
O(4')-C(10')-C(11') 116.4(5)
C(9')-C(10')-C(11') 119.3(6)
C(12')-C(11')-C(10') 120.8(5)
C(12')-C(11')-S(2') 118.2(5)
C(10')-C(11')-S(2') 121.0(5)
C(11')-C(12')-C(7') 120.5(5)
F(3')-C(13')-F(4') 105.6(5)
F(3')-C(13')-O(1') 112.4(6)
F(4')-C(13')-O(1') 111.0(6)
F(3')-C(13')-C(14') 110.1(6)
F(4')-C(13')-C(14') 109.3(6)
O(1')-C(13')-C(14') 108.4(5)
F(1')-C(14')-F(2") 105.3(6)
F(1')-C(14')-C(13') 108.0(6)
F(2")-C(14')-C(13') 108.5(6)
F(1')-C(14')-F(2') 117.2(6)
F(2")-C(14')-F(2') 28.3(4)
C(13')-C(14')-F(2') 122.6(5)
F(1')-C(14')-Br(1') 110.5(5)
F(2")-C(14')-Br(1') 111.0(5)
C(13')-C(14')-Br(1') 113.1(5)
F(2')-C(14')-Br(1') 82.8(5)
F(5')-C(15')-F(6') 103.7(6)
F(5')-C(15')-O(4') 111.5(6)
F(6')-C(15')-O(4') 112.9(6)
F(5')-C(15')-C(16') 108.0(6)
F(6')-C(15')-C(16') 109.4(7)
O(4')-C(15')-C(16') 111.0(6)
F(7")-C(16')-F(7') 47.1(11)
F(7")-C(16')-C(15') 111.3(10)
F(7')-C(16')-C(15') 102.1(7)
F(7")-C(16')-F(8'') 98.3(15)
F(7')-C(16')-F(8'') 145.1(10)
C(15')-C(16')-F(8'') 94.4(8)
F(7")-C(16')-Br(2') 126.2(12)
F(7')-C(16')-Br(2') 98.4(8)
C(15')-C(16')-Br(2') 116.4(7)
F(8'')-C(16')-Br(2') 101.4(8)
F(7")-C(16')-Br(2") 64.6(12)
F(7')-C(16')-Br(2") 109.7(7)
C(15')-C(16')-Br(2") 117.4(8)
F(8'')-C(16')-Br(2") 36.0(5)
Br(2')-C(16')-Br(2") 110.4(5)

73
Anisotropic displacement parameters (Å2
x 103
) for sulfonated BPVE precursor (9).
-2 π2
[ h2
a*2
U11 + ... + 2 h k a* b* U12 ]
U11 U22 U33 U23 U13 U12
Br(1') 60(1) 46(1) 77(1) -25(1) -8(1) 10(1)
Br(1) 80(1) 67(1) 101(1) 37(1) 24(1) 44(1)
Br(2) 52(1) 66(1) 62(1) -6(1) 22(1) 2(1)
S(1) 29(1) 31(1) 15(1) -2(1) 3(1) 2(1)
S(2) 40(1) 39(1) 14(1) -6(1) 1(1) 9(1)
S(1') 34(1) 35(1) 15(1) -3(1) -4(1) 0(1)
S(2') 37(1) 36(1) 15(1) -6(1) -2(1) -6(1)
Cl(1) 51(1) 38(1) 30(1) -14(1) 1(1) -4(1)
Cl(2) 63(1) 37(1) 50(1) -19(1) -12(1) 5(1)
Cl(1') 56(1) 41(1) 26(1) -13(1) 1(1) 5(1)
Cl(2') 60(1) 34(1) 52(1) -15(1) 12(1) 0(1)
Br(2') 76(1) 47(1) 116(2) 2(1) -15(1) -15(1)
F(8') 76(1) 47(1) 116(2) 2(1) -15(1) -15(1)
Br(2") 57(1) 101(1) 77(1) -10(1) -15(1) -12(1)
F(8") 57(1) 101(1) 77(1) -10(1) -15(1) -12(1)
F(8'') 98(12) 136(15) 33(7) -45(8) -8(7) -29(10)
Br(2X) 98(12) 136(15) 33(7) -45(8) -8(7) -29(10)
O(5') 48(3) 52(3) 15(2) -7(2) 5(2) -14(2)
O(3) 40(3) 45(3) 15(2) 6(2) 4(2) 10(2)
O(5) 56(3) 48(3) 20(2) -6(2) -8(2) 17(2)
O(2') 30(3) 57(3) 31(2) -6(2) -6(2) 6(2)
O(1) 45(3) 39(3) 21(2) 3(2) -1(2) 18(2)
O(4) 49(3) 48(3) 19(2) -2(2) 2(2) 21(2)
O(6) 44(3) 66(4) 23(2) 1(2) 16(2) 12(3)
O(1') 45(3) 46(3) 21(2) -1(2) 1(2) -23(2)
F(1') 57(3) 63(3) 53(3) 10(2) 1(2) -21(2)
F(2') 20(5) 12(5) 18(5) 16(4) -28(4) -28(4)
F(2") 20(3) 17(3) 19(3) -4(2) -15(2) 5(2)
F(3') 49(2) 39(2) 48(2) 10(2) -20(2) -2(2)
F(4') 40(2) 60(3) 33(2) -10(2) 5(2) 6(2)
F(5') 77(3) 60(3) 69(3) -27(3) 43(3) -26(3)
F(6') 73(4) 46(3) 135(5) 21(3) -48(4) -14(3)
F(7') 72(6) 53(5) 94(7) -39(5) -6(5) 0(4)
F(7") 75(12) 105(16) 77(13) -65(12) 15(10) -41(11)
O(6') 42(3) 61(3) 23(2) 4(2) -11(2) -7(2)
O(3') 55(3) 45(3) 18(2) 4(2) -8(2) -7(2)

74
C(1) 26(3) 21(3) 11(2) -5(2) -3(2) -2(2)
C(2) 33(3) 26(3) 15(3) 0(2) 3(2) -4(3)
C(3) 38(4) 26(3) 19(3) 2(2) -1(3) 8(3)
C(4) 34(3) 24(3) 15(3) -1(2) 0(2) 6(3)
C(5) 28(3) 23(3) 15(3) -2(2) -1(2) -2(2)
C(6) 29(3) 20(3) 16(3) 0(2) 0(2) -1(2)
C(7) 25(3) 23(3) 17(3) 1(2) 3(2) 1(2)
C(8) 31(3) 36(4) 16(3) -3(3) 2(2) 3(3)
C(9) 35(4) 41(4) 16(3) -3(3) -10(3) 5(3)
C(10) 33(3) 31(3) 19(3) 0(3) 5(2) 10(3)
C(11) 31(3) 29(3) 11(3) -1(2) 1(2) -3(3)
C(12) 30(3) 19(3) 16(3) 0(2) -1(2) 0(2)
C(13) 32(3) 26(3) 35(4) 10(3) 6(3) -1(3)
C(14) 36(4 33(4) 53(5) 3(3) -3(3) 11(3)
C(15) 24(3) 27(3) 27(3) 1(3) 4(2) 1(3)
C(16) 41(4) 38(4) 31(4) 4(3) 1(3) 7(3)
O(2) 30(2) 50(3) 24(2) -2(2) 9(2) 2(2)
F(1) 53(3) 48(3) 55(3) 8(2) 21(2) 7(2)
F(2) 53(3) 62(3) 100(4) -49(3) -12(3) 14(3)
F(3) 46(2) 57(3) 33(2) -9(2) -11(2) 7(2)
F(4) 47(3) 36(2) 86(4) 19(2) 28(2) 11(2)
F(5) 53(3) 39(2) 58(3) 6(2) 23(2) 0(2)
F(6) 44(2) 48(3) 44(2) -16(2) -10(2) 6(2)
F(7) 101(4) 45(3) 44(3) -26(2) 48(3) -30(3)
F(8) 60(3) 48(3) 82(4) -32(3) -1(3) 1(2)
O(4') 53(3) 65(4) 20(2) -2(2) -2(2) -35(3)
C(1') 28(3) 27(3) 17(3) -2(2) 1(2) 0(3)
C(2') 35(3) 29(3) 15(3) -2(2) -1(2) 0(3)
C(3') 33(3) 39(4) 18(3) -4(3) 1(3) -1(3)
C(4') 28(3) 27(3) 19(3) -9(3) 2(2) -5(3)
C(5') 27(3) 26(3) 10(3) -4(2) -1(2) 4(2)
C(6') 29(3) 24(3) 15(3) -2(2) 3(2) 0(3)
C(7') 28(3) 18(3) 15(3) -3(2) -3(2) 2(2)
C(8') 34(3) 28(3) 14(3) -3(2) -2(2) 0(3)
C(9') 39(4) 36(4) 16(3) -1(3) 6(3) -4(3)
C(10') 32(3) 30(3) 19(3) -3(3) -2(2) -2(3)
C(11') 28(3) 25(3) 18(3) -2(2) -2(2) 5(3)
C(12') 31(3) 24(3) 18(3) 2(2) 2(2) 2(3)
C(13') 40(4) 34(4) 30(3) 4(3) -6(3) -3(3)
C(14') 47(4) 30(4) 40(4) 10(3) -2(3) -11(3)
C(15') 33(4) 34(4) 31(3) -2(3) -5(3) -7(3)
C(16') 61(6) 83(7) 61(6) -36(5) 5(5) -28(5)

75
Hydrogen coordinates (x104
) and isotropic
displacement parameters (Å2
x 103
) for sulfonated BPVE precursor (9).
x y z U(eq)
H(2) 10283 2045 -207 30
H(3) 11805 1482 -490 33
H(6) 10288 2472 -2752 26
H(8) 8391 2667 -2489 33
H(9) 6887 3235 -2202 36
H(12) 9496 2754 33 26
H(2') 5173 2951 2376 31
H(3') 6640 3528 2659 36
H(6') 5171 2532 4919 27
H(8') 3319 2325 4652 30
H(9') 1810 1753 4389 36
H(12') 4394 2230 2139 29

76
Appendix D
Selected spectra
S
O
O
ClCl
NaO3S SO3Na
HA HB
HC
Figure 31. 1
H NMR of SDCDPS
. .
8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4
HA
HB
HC

77
S
O
O
O O O
FF
F F
FF
n
Figure 32. 19
F NMR of P1

78
S
O
O
O O O
FF
F F
FF
SO3NaNaO3S
n
Figure 33. 1
H NMR of P2

79
S
O
O
O O O
FF
F F
FF
S
O
O
O O O
FF
F F
FF
SO3NaNaO3S
n m
p
Figure 34. 1
H NMR of P3

80
Figure35.1
HNMRofsulfolanestructureinDMSO-d6
80

81
S
OO
OHHO
Figure36.13
CNMRofsulfolanestructureinDMSO-d6
81

82
P O
OH
OH
O
F
F
F
Figure 37. 31
P NMR of p-trifluorovinyloxyphenyl phosphonic acid

83
P O
OH
OH
O
FX
FM
FA
Figure 38. 19
F NMR of p-trifluorovinyloxyphenyl phosphonic acid
A
M
X

84
OO
Br
F F
F
F
Br
F
F
F
F
S S
OO
Cl
O O
Cl
Figure 39. 1
H NMR of 9

88
Figure 43. H1
NMR of polymer P4

89
Figure 44. H1
NMR of polymer P5

90
Figure 45. H1
NMR of polymer P6

91
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