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5-2008

PERFLUOROCYCLOBUTYL ARYL ETHERPOLYMERS FOR PROTON EXCHANGEMEMBRANESRaul HernandezClemson University, raulh@clemson.edu

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Recommended CitationHernandez, Raul, "PERFLUOROCYCLOBUTYL ARYL ETHER POLYMERS FOR PROTON EXCHANGE MEMBRANES"(2008). All Theses. 315.https://tigerprints.clemson.edu/all_theses/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 1H 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 oC. and catastrophic

weight loss in N2 at 350-450 oC. 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 oC/min, under N2) ........................................ 21

13. TGA of polymer P1, P2 and P3 under N2 at 10 oC/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. 19F 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. 1H NMR of SDCDPS ......................................................................................... 76

32. 19F NMR of P1 ................................................................................................... 77

33. 1H NMR of P2 .................................................................................................... 78

34. 1H NMR of P3 .................................................................................................... 79

35. 1H NMR of sulfolane structure in DMSO-d6 .................................................... 80

36.13C NMR of sulfolane structure in DMSO-d6 ..................................................... 81

37. 31P NMR of p-trifluorovinyloxyphenyl phosphonic acid ................................... 82

38. 19F NMR of p-trifluorovinyloxyphenyl phosphonic acid ................................... 83

xii

List of Figures (Continued) Page

39. 1H NMR of 9 ...................................................................................................... 84

40. 19F NMR of 9...................................................................................................... 85

41. 1H NMR of 10 .................................................................................................... 86

42. 19F NMR of 10.................................................................................................... 87

43. H1 NMR of P4 .................................................................................................... 88

44. 1H NMR of P5 .................................................................................................... 89

45. 1H 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 FFF

F F

O O Ar

F FFF

F F n

160 oCOAr

O

F

F

F

F

FF

O O ArAr

F FFF

F FOHHO 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

FFFF

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 oC 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 OHF

FF

F

FFSO

OCl Cl

O O O OF

FF

F

FFSO

O n

K2CO3 DMAc

150-170 oC

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 oC

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 oC 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, 1H NMR, and 19F 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 1H 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

10291012

956

956

956

1

2

3

Wavenumbers (cm-1)

1400 1200 1000 800

1322

1322

1322

1012

1029 1012

10291012

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 1H 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 1H

NMR corresponded with the molar ratios used for the polymerization.

The 19F 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 OFF

FF F

F

SO

OO O O O

FFF

F FF

SO

O

NaO3S SO3Na

y-x x

Unit X Unit Y

A

C

A

C

B

BB

B

Figure 11. 1H 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

ppm 8.0 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 oC was measured after multiple cycles from 0 to 300 oC under

N2 atmosphere at a heating rate of 10 oC/min (Figure 12). No Tg was observed for

polymers P2 and P3 below 250 oC. 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 oC at a heating rate of 10 oC/min in N2 and are depicted in Figure 13. Polymer

P1 exhibited a weight loss of only 5% before 500 oC. 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 oC

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 oC for 16 h. and

annealed for 2 h at 130 oC. 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 )

% S

ampl

e

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 oC, 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

oC) 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.49For 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 oC) and Pc (6.2 MPa) of ethanol. The final temperature and pressure

were about 280 oC, 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 oC, 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 oC

Supercritical Drying 280 oC 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

Zr02H2O, 80 oC

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 oC 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 oC 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).

OO1) 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

OZrO2

aerogel

OFC 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. 1H 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

FF

Br

FF

F

F

S

S

OO

Cl

O O

Cl

KF, r.t.OO

Br

F F

FF

Br

FF

F

F

S

S

OO

F

O O

F

CH3CN

OO

Br

F F

FF

Br

FF

F

F ClSO3H

CH3Cl

0-35 oC

98

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 oC as literature suggested (Scheme 13). This process generated

the sulfonyl fluoride as colorless needles. 19F 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 19F 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 19F 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 oC.

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

Fig

ure

24. 19

F N

MR

spe

ctru

m o

f cr

ude

reac

tion

mix

ture

OO

Br

FF

FF

Br F

FF

F

S

S

OO F

OOF

OO

ZnB

r

FB

FB

FA

FA

BrZ

n

FB

FB

FA

Fa

S

S

OO F

OOF

Zn,

80o C

OO

FE

FF

FG

FFFE

FG

S

S

OO F

OOF

OO

HFD

FD

FCF

C

HFD F

D

FC

FC

SS

OO F

OO F

+

MeC

N

+

FD

FC

FA

FB

FE

FF

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.

63reported 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

H2C

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 68containing compounds which

are considered borderline bases. It has also been reported that Zn2+ and SO32- 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

F2C

O

CF2

Zn

OF 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 oC/min under

N2).

Figure 30. TGA analysis of P5, P5 10% mod ZrO2 and BPVE (10 oC/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 oC 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 19F 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

1H NMR (300 MHz), proton decoupled 13C NMR (75 MHz), 19F 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 1H, 13C, and 19F

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 oC/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). 1H NMR was used to confirm the structure

and purity of the monomer. 1H 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 oC) for 4 h to

remove water (via Dean-Stark trap). After complete removal of toluene, the solution was

heated at 170 oC 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 oC 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. 1H NMR (300 MHz, DMSO-d6) δ: 7.8 (2H, m), 7.2 (2H, m), 7.1 (2H, m),

6.9(2H, m) ppm; 13C 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; 19F 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 oC) for 4 h to

remove water (via Dean-Stark trap). After complete removal of toluene, the solution was

heated at 190 oC 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 oC 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. 1H 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: 19F 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. 1H 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); 19F 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 oC for 16 h. The membranes were annealed at 130 oC 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 oC 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 oC. 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. 1H 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 ); 19F 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 oC; 1H 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); 19F

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) ; 31P 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 oC)

and Pc (6.2 MPa) of ethanol. The final temperature and pressure were about 280 oC, 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 %) 1H

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); 13C 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. 1H 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); 19F 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

1H 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); 19F 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 oC. 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 19F 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 oC 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 oC. The membranes were annealed at 130 oC 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 à 2.65 meq/g

equivalents per unit 2 eq

56

APPENDICES

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 displacement parameters (A2 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 Formula weight 532.52 Temperature 173(2) K Wavelength 0.71073 A Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 7.1399(14) Å 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 Z, Calculated density 1, 1.553 Mg/m3 Absorption coefficient 0.295 mm-1 F(000) 276 Crystal size 0.46 x 0.31 x 0.24 mm Theta range for data collection 2.78 to 25.10 deg. Limiting indices -8<=h<=8, -10<=k<=9, -11<=l<=11 Reflections collected / unique 4835 / 2004 [R(int) = 0.0160] Completeness to theta = 25.10 98.4 % Absorption correction REQAB (multi-scan) Max. and min. transmission 0.9327 and 0.8764 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 2004 / 0 / 167 Goodness-of-fit on F^2 1.056 Final R indices [I>2sigma(I)] R1 = 0.0356, wR2 = 0.0898 R indices (all data) R1 = 0.0387, wR2 = 0.0923 Largest diff. peak and hole 0.276 and -0.330 e.A^-3

63

Atomic coordinates (x104) and equivalent isotropic displacement parameters (A2 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). The anisotropic displacement factor exponent takes the form: -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 Formula weight 741.05 Temperature 173(2) K Wavelength 0.71073 A Crystal system, space group Monoclinic, P2(1)/c Unit cell dimensions a = 11.286(2) Å 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 Z, Calculated density 8, 2.088 Mg/m3 Absorption coefficient 3.939 mm-1 F(000) 2864 Crystal size 0.60 x 0.29 x 0.07 mm Theta range for data collection 2.34 to 25.05 deg. Limiting indices -11<=h<=13, -32<=k<=29, -18<=l<=17 Reflections collected / unique 28278 / 8334 [R(int) = 0.0636] Completeness to theta = 25.05 99.6 % Absorption correction REQAB (multi-scan) Max. and min. transmission 0.7700 and 0.2009 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 8334 / 0 / 676 Goodness-of-fit on F2 1.054 Final R indices [I>2sigma(I)] R1 = 0.0689, wR2 = 0.1883 R indices (all data) R1 = 0.0932, wR2 = 0.2037 Largest diff. peak and hole 1.638 and -1.258 e.A-3

68

Atomic coordinates (x104) and equivalent isotropic displacement parameters (A2 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)

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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)

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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)

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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)

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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)

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Anisotropic displacement parameters (Å2 x 103) for sulfonated BPVE precursor (9). The anisotropic displacement factor exponent takes the form: -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. 1H 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

SO

OO O O

FF

F F

FF

n

Figure 32. 19F NMR of P1

78

SO

OO O O

FF

F F

FF

SO3NaNaO3S

n

Figure 33. 1H NMR of P2

79

SO

OO O O

FF

F F

FFSO

OO O O

FF

F F

FF

SO3NaNaO3S

n mp

Figure 34. 1H NMR of P3

80

Fig

ure

35. 1 H

NM

R o

f su

lfol

ane

stru

ctur

e in

DM

SO

-d6

80

81 SO

O

OH

HO

Fig

ure

36. 13

C N

MR

of

sulf

olan

e st

ruct

ure

in D

MS

O-d

6

81

82

P O

OH

OH

O

F

F

F

Figure 37. 31P NMR of p-trifluorovinyloxyphenyl phosphonic acid

83

P O

OH

OH

O

FX

FM

FA

Figure 38. 19F NMR of p-trifluorovinyloxyphenyl phosphonic acid

A

M

X

84

OO

Br

F F

FF

Br

FF

F

F

S S

OO

Cl

O O

Cl

Figure 39. 1H NMR of 9

85

Fig

ure

40. 19

F N

MR

of 9

85

86

Fig

ure

41. 1 H

NM

R o

f 10

86

87

Fig

ure

42. 19

F N

MR

of 10

87

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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