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“HESIS

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TYLI IBRAFTI

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3 1293 0155

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This is to certify that the

dissertation entitled

SYNTHESIS AND CHARACTERIZATION OF
ETHYLENE OXIDE-SEGMENTED POLYMERS

presented by

Jun Qiao

has been accepted towards fulfillment
of the requirements for

Ph . D. degree in Chemistry

 

 

 

’éM Major professor\

Date 9 fltf/écfi/ /9;é

MS U i: an Affirmative Action/Equal Opportunity Institution 0-12771

 

LIBRARY
Michigan State
University

 

 

 

PLACE IN RETURN BOX to remove this checkout from your record.
TO AVOID FINES return on or before data duo.

DATE DUE DATE DUE DATE DUE

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

MSU In An Affirmative MONEqual Opportunlly Inflation
Wm:

SYNTHESIS AND CHARACTERIZATION OF ETHYLENE OXIDE-SEGMENTED
POLYMERS

By

Jun Qiao

A DISSERTATION
Submitted to
Michigan State University

in partial fulfillment of the requirements
for the degree of

DOCTOR OF PHILOSOPHY

Department of Chemistry

1996

ABSTRACT

SYNTHESIS AND CHARACTERIZATION OF ETHYLENE OXIDE-SEGMENTED
POLYMERS

By

Jun Qiao

Novel unsaturated ethylene oxide-segmented polymers were synthesized
from oligo(ethylene glycol) a,co-dialkenyl ethers via acyclic diene metathesis
(ADMET) polymerization using Schrock’s molybdenum alkylidene catalyst. The
unsaturated polymers were prepared in high yields (above 92%) and the
molecular weights were found to range from 15,100 to 93,900 Daltons according
to gel permeation chromatography (GPC) measurements. The structures of the
polymers were confirmed by 1H and 13C nuclear magnetic resonance (NMR)
spectroscopy and infrared (IR) spectroscopy. Approximately 82 to 86% of the
internal double bonds on the unsaturated polymer backbone were found to have
a trans geometry by quantitative 130 NMR measurements. The polymers have
good solubility in a variety of polar and nonpolar organic solvents.

The unsaturated polymers exhibited good thermal stability. Thermal
gravimetric analysis (TGA) data indicated that the polymers were stable up to
300 °C, followed by rapid thermal breakdown above 300 °C. Differential
scanning calorimetry (DSC) study revealed that the glass transition temperatures

(T9) of the unsaturated polymers are segment length-dependent. Some of the

unsaturated polymers displayed interesting multiple crystallization and melting
transitions in their DSC scans.

Perfectly alternating polyethylenelpolyethylene oxide (AB)n copolymers
were prepared by hydrogenating several unsaturated polymers. The thermal
behavior of these hydrogenated polymers were studied by DSC.

Polymer electrolytes based on the unsaturated polymers were prepared
using lithium perchlorate as salt. The Tg’s of these polymer-salt complexes
were dependent on the salt concentration, increasing with increasing salt
content. The ionic conductivity of the electrolytes was obtained by impedance
spectroscopy (IS) measurements. For each polymer electrolyte, as the salt
content increased, the conductivity increased, reached a maximum and then
dropped rapidly at higher salt concentrations. The conductivity was also found
to increase with increasing temperature. The temperature-dependent

conductivity fit the Vogel-Tammann-Fulcher (VTF) equation.

To my wife Lei, my parents, and my brother Bin.

ACKNOWLEDGMENTS

I wish to express my deep appreciation to Professor Gregory L. Baker for
his guidance, assistance and constant encouragement throughout the course of
this research. I would also like to thank Professors James Jackson, Robert
Cukier, Milton Smith and Peter Wagner for their guidance and assistance. My
thanks go to all Baker group members as well, for making my stay in the lab an
enjoyable one.

Financial support from Department of Chemistry and Center for
Fundamental Materials Research at Michigan State University, and the U. S.
Department of Energy is also acknowledged.

Finally, I want to thank my wife Lei for her constant love and support. I

thank my parents and brother for their love and encouragement.

TABLE OF CONTENTS

Page
List of Schemes .............................................................................................. ix
List of Tables .................................................................................................. xi
List of Figures ................................................................................................. xiii
INTRODUCTION ............................................................................................ 1
l; Polymer Electrolytes .................................................................. 1
1. General ............................................................................. 1
2. PEG-based electrolytes .................................................... 2
3. ionic conduction ................................................................ 5
4 Synthesis of modified hosts ............................................... 7
ll. Target Polymers in This Work ................................................... 15
Ill. ADMET Polymerization ............................................................. 17
IV. Ionic Conductivity Measurements ............................................. 28
RESULTS ...................................................................................................... 35
I. Monomer Preparation ................................................................ 35
ll. Unsaturated Ethylene Oxide-Segmented Polymers .................. 38
1. ADMET polymerization of oligo(ethylene glycol) (1,0)-
dialkenyl ethers ................................................................. 38
2. Properties of the unsaturated polymers ............................ 40
3. Spectroscopic characterization of the unsaturated
polymers ............................................................................ 42
4. Thermal stability of the unsaturated polymers .................. 47
5. Thermal behavior of the unsaturated polymers ................. 52
Ill. Alternating (AB)n Copolymers from the Unsaturated
‘ Polymers ................................................................................... 66

vi

1 Reduction of the unsaturated polymers ............................. 66
2. Physical properties of the hydrogenated polymers ........... 67
3. Thermal behavior of the hydrogenated polymers .............. 71
4 Morphology of the hydrogenated polymers ....................... 77
IV. Polymer Electrolytes Based on the Unsaturated Polymers ....... 81
1. Thermal behavior of the polymer electrolytes ................... 81
2. Impedance spectroscopy of the polymer electrolytes ....... 96
3 Conductivity behavior of the polymer electrolytes ............. 99
4 Temperature dependent conductivity ................................ 107
DISCUSSION .................................................................................................. 114
l. Scope of ADMET Polymerization in Synthesizing Target
Polymers. .................................................................................. 114
1. ADMET polymerization catalysts ....................................... 114
2. Polymerizability of the monomers ..................................... 116
3. Controlling molecular weights ........................................... 120
II. Unsaturated Ethylene Oxide-Segmented Polymers .................. 122
1. Segment length dependent glass transition
temperature ............................................................................... 122
2. Melting‘transitions ............................................................. 127
Ill. Electrolytes from the Unsaturated Polymers ............................. 129
1. Conductivity and E0 content ............................................. 129
2. Parameters in the VTF equation ....................................... 130
IV. Summary..'...............: ................................................................. 132
V. Suggestions for Further Research ............................................ 134
EXPERIMENTAL ............................................................................................ 136
I. General ..................................................................................... 1 36
1 . Solvents ............................................................................ 1 38
2. Argon ................................................................................. 139
3. Sodium mirror .................................................................... 140
II. Preparation of Monomers .......................................................... 141
1. Diethylene glycol a,co-diallyl ether ..................................... 141
2. Diethylene glycol a,co-di-3-butenyl ether ........................... 142
3. Diethylene glycol a,co-di-4-pentenyl ether ......................... 142

vii

4. Triethylene glycol a,co-di-4-pentenyl ether ........................ 144
5. Tetraethylene glycol a,co-di-4-pentenyl ether .................... 145
6. Diethylene glycol a,m-di-5-hexenyl ether .......................... 145
7. Triethylene glycol a,m-di-5-hexenyl ether .......................... 146
8. Tetraethylene glycol a,co-di-5-hexenyl ether ..................... 146
9. Pentaethylene glycol a,co-di-5-hexenyl ether .................... 147
10. Diethylene glycol a,co-di-7-octenyl ether ........................... 147
11. Tetraethylene glycol a,co-di-7-octenyl ether ...................... 148
Ill. ADMET Polymerization Catalysts .............................................. 150
IV. Synthesis of Unsaturated Ethylene Oxide-Segmented
Polymers ................................................................................... 151
1. Polymer from diethylene glycol a,co-di-3-butenyl ether ...... 151
2. Polymer from diethylene glycol a,ro-di-4-pentenyl ether....151
3. Polymer from triethylene glycol a,w-di-4-pentenyl ether 152
4. Polymer from tetraethylene glycol a,co-di-4-pentenyl
ether .................................................................................. 153
5. Polymer from diethylene glycol a,co-di-5-hexenyl ether ..... 154
6. Polymer from triethylene glycol a,co-di-5-hexenyl ether ..... 154
7. Polymer from tetraethylene glycol a,m—di-5-hexenyl
ether .................................................................................. 155
8. Polymer from pentaethylene glycol a,co-di-5-hexenyl
' ether ................................................................................. 1 55
9. Polymer from diethylene glycol a,a)-di-7-octenyl ether ...... 156
10. Polymer from tetraethylene glycol a,o)—di-7-octenyl
ether .................................................................................. 156
V. Preparation of Saturated Ethylene Oxide-Segmented
Polymers ................................................................................... 157
1. Hydrogenated polymer from PH2 ...................................... 157
2. Hydrogenated polymer from PH3 ...................................... 158
3. Hydrogenated polymer from PH4 ...................................... 158
4 Hydrogenated polymer from PH5 ...................................... 158
VI. Preparation of Polymer Electrolytes .......................................... 160
APPENDIX ...................................................................................................... 161
BIBLIOGRAPHY ............................................................................................. 178

viii

LIST OF SCHEMES

Scheme Page
Scheme 1. Preparation of methylene-linked PEO copolymer... 7

Scheme 2. Preparation of poly(dimethy| siloxane—co-ethylene oxide)s ...... 8

Scheme 3. Copolymerization of ethylene oxide and propylene oxide... .. 9
Scheme 4. Preparation of comb polymer with PEO branches... .. 10
Scheme '5. Preparation of oombbranched poly(SIloxanes) with PEO side

. chains... 10
Scheme 6. Preparation of MEEP from inorganic polyphosphazene. .. ... 11
Scheme 7. Crosslinking PEO by hydrosilylation... 14
Scheme 8. Target polymer electrolyte hosts... 15
Scheme 9. General ADMET polymerization... ....17
Scheme 10. ADMET polymerization mechanism... 18

Scheme 11. Synthesis of unsaturated polyalkanes via ADMET
polymerization... 21

Scheme 12. Synthesis of unsaturated polyethers via ADMET polymerization
.. 22

Scheme 13. Synthesis of conjugated polyenes via ADMET polymerization. 24

Scheme 14. Synthesis of liquid crystalline materials via ADMET
polymerization... 25

Scheme 15. Synthesis of cubane-containing polymer via ADMET
polymerization............................................................... 26

Scheme 16. A generalized ADMET copolymerization... .. 27

Scheme 17.

Scheme 18.
Scheme 19.

Scheme 20.

Scheme 21.
Scheme 22.

Scheme 23.

Scheme 24.

Monomer preparation by Williamson ether coupling . 36

Monomer preparation by reaction of ditosylates with sodium
alkenoxides............... ....37

ADMET polymerIzatIon of olIgo(ethylene glycol) a ,co—dialkenyl

ethers... . . 38
Hydrogenation of the unsaturated polymers... . 66
Failed ADMET polymerization to make an unsaturated polyether

. . 117
Competition between ring-closing metathesis reaction and
ADMET polymerization.................................................... 118
Mechanism for ring-closing metathesis reaction... .. 118
An example of ring-closing metathesis reaction to prepare a
cyclic ether... 119

late 4
Teale 5
Table I

Table i

iabie E

IabLe S

Table

Table 1.

Table 2.

Table 3.

Table 4.
Table 5.
Table 6.

Table 7.

Table 8.

Table 9. .

Table 10.

Table 11.

Table 12.

Table 13.

Table 14.

LIST OF TABLES

Page
Some Representative ADMET Polymers Prepared by Wagener
eta/... . . ........23
Acronyms for Monomers... .....35
Polymerizability of Monomers Wby ADMET Polymerization Using
Schrock’s Mo Catalyst... . ........40
Properties ofthe Unsaturated Polymers... 41 _
Thermal Stability of the Unsaturated Polymers... 51
Thermal Transition of the Unsaturated Polymers ..................... 64

GPC Data Comparison Between the Hydrogenated Polymers and
Their Unsaturated Precursors. . .. .. .70

Thermal Transition Temperatures for the Hydrogenated

Polymers77
The Measured and Calculated Tg of Some Unsaturated
Polymers 126
Peak Conductivity of the Unsaturated Polymers at 20 °C, 50 °C

and 100°C... 130
The VTF Parameters for Polymer-Salt Complexes with an OzLi
Ratio of32131
Conductivity Data for PPZ-LiCIOI Complexes..... .. 172
Conductivity Data for PP3-LiCl04 Complexes..... .. 173
Conductivity Data for PP4-LiCl04 Complexes..........................174

xi

Fable 1!
Table 11

12529 1'

Table 15. Conductivity Data for PH3-LiCIO.. Complexes..... . ..175
Table 16. Conductivity Data for PH4-LiClO. Complexes... ..176

Table 17. Conductivity Data for PH5-LiCl04 Complexes... ..177

xii

Figure

Figure 1.

Figure 2.

Figure 3.

Figure 4.

Figure 5.

Figure 6.

Figure 7.

Figure 8.

Figure 9.

Figure 10.

Figure 11.

LIST OF FIGURES

Page

Arrhenius plot of temperature-dependent conductivity in PEO-LiCIO4
complex (O:Li = 6) reported by Chabagno... 3

Conductivity of the amorphous PEO-LiClOI electrolytes of
different salt concentrations at 50 °C reported by Prud’homme et

aI...... ....4
Li’ ion transport in PEO-salt complex as the combined result of
polymer segmental motion and Li+ ion movement... 5
Conductivity scale for different materials............ 29

Polymer electrolyte contained between two inert electrodes:
before (left) and after (right) a d. c. voltage of fixed potential is
applied. . .. .. 30

Current decay as a function of time when a dc. voltage is applied
to a polymer electrolyte sample... 31

The sinusoidal voltage applied to a polymer electrolyte cell and
the resulting current......... 32

Complex impedance vector Z and the real and imaginary
components in the rectangular complex plane. The phase angle
is 8 .................................................................................................... 33

Complex impedance diagram of a polymer electrolyte cell
sandwiched between two inert electrodes... ....34

A schematic cross section polymer electrolyte cell of known
dimensions... .....34

1H NMR spectra of monomer P3 “(top)”. and polymer PP3a
(bottom)... . ... . ..........43

xiii

Figure 12.

Figure 13.
Figure 14.

Figure 15.

Figure 16.

Figure 17.
Figure 18.
Figure 19.
Figure 20.
Figure 21.
Figure 22.
Figure 23.
Figure 24.
Figure 25.
Figure 26.

Figure 27.

13C NMR spectra of monomer P3 ”(top)” and polymer PP3a

(bottom). ...45
IR spectra of monomer P3 (top) and polymer PP3a (bottom)... 46
TGA profiles of PP2 (heating rate 10°Clmin)........................48
TGA profiles of PP4 and PEG10K In nitrogen (heating rate 10
°Clmin)... 4.......9
TGA profiles of PH2 (heating rate 10°Clmin)............... .. ....50
Second DSC heating and cooling scans for PBZ (heating and
cooling rate 10°ClmIn) 53
Second DSC heating and cooling scans for PP2 (heating and
cooling rate 10°ClmIn) 54
Second DSC heating and cooling scans for PP3 (heating and
cooling rate 10°ClmIn) 55
Second DSC heating and cooling scans for PP4 (heating and
cooling rate 10°Clmin)................................ 57
Second DSC heating and cooling scans for PH2 (heating and
cooling rate 10°ClmIn) 58
Second DSC heating and cooling scans for PH3 (heating and
cooling rate 10°ClmIn) 59
Second DSC heating and cooling scans for PH4 (heating and
cooling-rate10°C/mIn) 60
Second DSC heating and cooling scans for PH5 (heating and
cooling rate 10°C/mIn) 61
Second DSC heating and cooling scans for P02 (heating and
cooling rate 10°ClmIn) . 62
Second DSC heating and cooling scans for P04 (heating and
cooling rate 10°C/min)...... 63
1H NMR spectrum ofhydrogenated polymer PH5H................68

xiv

Figure 12.

Figure 13.
Figure 14.

Figure 15.

Figure 16.

Figure 17.
Figure 1-8.
Figure 19.
Figure 20.
Figure 21.
Figure 22.
Figure 23.
Figure 24.
Figure 25.
Figure 26.

Figure 27.

“C NMR spectra of monomer P3 (top)” and polymer PP3a

(bottom)... 45
IR spectra of monomer P3 (top) and polymer PP3a (bottom)... 46
TGA profiles of PP2 (heating rate 10 °Clmin)....... ..48

TGA profiles of PP4 and PEG10K In nitrogen (heating rate 10
°Clmin)... . .......49

TGA profiles of PH2 (heating rate 10 °Clmin)....... .. ..50
Second DSC heating and cooling scans for P82 (heating and

cooling rate 10 °Clmin).................. 53

Second DSC heating and cooling scans for PP2 (heating and

cooling rate 10 °Clmin)... 54

Second DSC heating and cooling scans for PP3 (heating and

cooling rate 10 °Clmin)... 55

Second DSC heating and cooling scans for PP4 (heating and

cooling rate 10 °Clmin)... 57

Second DSC heating and cooling scans for PH2 (heating and

cooling rate 10°Clmin)............................. 58

Second DSC heating and cooling scans for PH3 (heating and

cooling rate 10 °Clmin)... 59

Second DSC heating and cooling scans for PH4 (heating and

cooling-rate 10 °Clmin)... .. 60

Second DSC heating and cooling scans for PH5 (heating and
cooling rate 10 °Clmin)... 61

Second DSC heating and cooling scans for P02 (heating and

cooling rate 10 °Clmin)... 62

Second DSC heating and cooling scans for P04 (heating and

cooling rate 10 °Clmin)... 63

1H NMR spectrum of hydrogenated polymer PHSH... . 68

xiv

Figure 28.

Figure 29.
Figure 30.
Figure 31.
Figure 32.

Figure 33.
Figure 34.

Figure, 35.

Figure 36.

Figure 37.

Figure 38.

Figure 39.

Figure 40.

Figure 41.

Figure 42.

13C NMR spectrum of hydrogenated polymer PH5H... 69

Second DSC heating and cooling scans for PH2H (heating and
cooling rate 10 °Clmin)... 72

Second DSC heating and cooling scans for PH3H (heating and
cooling rate 10°C/mIn) 73

Second DSC heating and cooling scans for PH4H (heating and
cooling rate 10 °Clmin)... 75

Second DSC heating and cooling scans for PH5H (heating and

cooling rate 10 °Clmin)..... 76
Polarized light optical micrograph of Pl-IZI-I... .. 78
Polarized light optical micrograph of PH3H... 79

2nd heating DSC'scans of PP2 and its LiCl04 salt complexes at
different salt concentrations. Numbers refer to molar O:Li ratios

for each sample. Heating rate is 10 °Clmin... .....82
T9 as a function of the salt molar fraction for PP2-salt
complexes.................................. 83

2nd heating DSC scans of PP3 and its LiCl04 salt complexes at
different salt concentrations. Numbers refer to molar O:Li ratios

for each sample. Heating rate is 10 °Clmin......... .....84
To as a function of the salt molar fraction for PP3-salt
complexes... 85

2nd heating DSC scans of PP4 and its LiClOI salt complexes at
different salt concentrations. Numbers refer to molar O:Li ratios

for each sample. Heating rate is 10 °Clmin... .....87
To as a function of the salt molar fraction for PP4-salt
complexes................................... 88

2nd heating DSC scans of PH3 and its LiClO4 salt complexes at
different salt concentrations. Numbers refer to molar O:Li ratios

for each sample. Heating rate is 10 °Clmin... .....89
T9 as a function of the salt molar fraction for PH3-salt
complexes... 90

XV

FI’

Figure 43.

Figure 44.

Figure 45.

Figure 46.
Figure 47.
Figure 48.
Figure 49.
Figure 50.
Figure 51.
Figure 52.
Figure 53.
Figure 54.

Figure 55.

Figure 56.

2nd heating DSC scans of PH4 and its LiCIO. salt complexes at
different salt concentrations. Numbers refer to molar O:Li ratios
for each sample. Heating rate is 10 °Clmin... .. 92

To as a function of the salt molar fraction for PH4-salt

complexes ..........93

2nd heating DSC scans of PH5 and its LiCIOI salt complexes at
different salt concentrations. Numbers refer to molar O:Li ratios

for each sample. Heating rate is 10 °Clmin...... ....94
To as a function of the salt molar fraction for PH5-salt
complexes.................. .. 95
Complex impedance diagram for PP4-salt complex (O:Li = 4) at
Complex impedance diagram for PH4-salt complex (O:Li = 32) at

Conductivity of PP2-LiCI04 complexes as a function of salt content
at 20 °C, 50 °C and 100 °C... 100

Conductivity of PP3-LICIO4 complexes as a function of salt content
at 20 °C, 50 °C and 100 °C... ....101

Conductivity of PP4-LiClO4 complexes as a function of salt content
at 20 °C and 50 °C... 102

Conductivity of PH3-LiCIO4 complexes as a function of salt content
at 20 °C, 50 °C and 100 °C... 103

Conductivity of PH4-LiCI04 complexes as a function of salt content
at 20 °C, 50 °C and 100 °C............ .......104

Conductivity of PH5-LiCl04 complexes as a function of salt content
at 20°C, 50 °C and 100°C105
VTF plots” for PP2-LiClO4 complexes with 0: Li ratio of 32, 16,12,
and4... ..108
VTF plots” for PP3-LiCl04 complexes with 0: Li ratio of64,32,16,
and12... .. .109

Figure 57.

Figure 58.

Figure 59.

Figure 60.

Figure 61.

Figure 62.

Figure 63.

Figure 64.
Figure 65.
Figure 66.
Figure 67.
Figure 68.
Figure 69.
Figure 70.
Figure 71.
Figure 72.

Figure 73.

VTF plotsm for PP4-LiClO4 complexes with 0: Li ratio of64,32,16,
and8... ... ..110

VTF plots” for PH3-LiCl04 complexes with 0: Li ratio of64, 32,8,
and4... ..111

VTF plots for PH4-LiCIO4 complexes with O:Li ratio of 64, 32, and

VTF plots for PH5-LiCl04 complexes with O:Li ratio of 64, 32, 8,
and 4 .. 113
Ethylene oxide segment length dependent T9 in unsaturated
polymers123
Methylene unit dependent Tg in several unsaturated
polymers ..............124

Melting temperature as a function number of ethylene oxide units

in unsaturated polymers... .. 127
TGA profiles ofPBZ (heating rate10°Clmin)...... 162
TGA profiles of PP2a (heating rate 10 °Clmin)... ....163
TGA profiles of PP3a (heating rate 10°Clmin)......................164
TGA profiles of PP3 (heating rate 10°Clmin).................... ...165
TGA profiles of PP4a (heating rate 10°C/min)......................166
TGA profiles of PH3 (heating rate 10°C/min)........................167
TGA profiles of PH4 (heating rate 10 °Clmin)... .. ...168
TGA profiles of PH5 (heating rate 10°Clmin)........................169
TGA profiles of P02 (heating rate 10°Clmin)....................... 170
TGA profiles of P04 (heating rate 10°C/min)....................... 171

xvii

I! ’7
,I’II'

ig‘

INTRODUCTION

l. Polymer Electrolytes

1. General

Polymer electrolytes” refer to polymer-salt complexes formed by
dissolving salts (mainly alkali metal salts) in appropriate polymers. After the
pioneering work done by Wright and coworkers5 in 1973, and Armand and
coworkers6 in 1979, polymer electrolytes have attracted considerable interest
owing to their potential applications as new solid ionic conductors.

The ionic conductivities of polymer electrolytes usually range from 10'8 to
1045 S/cm at room temperature, and reach 10‘4 to 10'3 S/cm at 100 °C for many
polymer-salt complexes. Although their conductivity at ambient temperature
needs to improve in order to be useful for many applications, solid polymer
electrolytes can be processed into very thin films with large surface area, so that
power densities comparable to liquid electrolytes or molten salts (>100 W/dm3)
can be maintained. However, in contrast to conventional ionic conducting
materials, they have the advantage of operating in solvent-free conditions and
avoid the use of flammable organic solvents or corrosive aqueous solutions.
Thus, polymer electrolytes can find applications in energy generation and
storage as rechargeable solid state lithium batteries, in electrochromic devices
such as sunglasses and smart windows, as well as in solid state ionic sensors

and photoelectrochemical cells.

I
rm

As an ideal electrolyte host. a polymer should have electron donating
atoms or groups that can form coordinate bonds with cations, good chain
segmental mobility to enable transport of ions,7 and a suitable distance between
coordinating sites. While a number of polymers, including polyethers,8‘9

10-11

polyimines, polythioethers12 and polyesters”15 fit these criteria, the most

widely studied polymer host to date has been poly(ethylene oxide) (PEO).

2. PEG-based electrolytes

PEO is usually prepared by the catalyzed ring-opening polymerization of
ethylene oxide. Since the linear PEO chains adopt a regular helical
conformation,16 PEO is a highly crystalline material with a degree of crystallinity
above 70% at room temperature. Depending on molecular weight, the melting
point of PEO ranges from 60 °C for a molecular weight of 4,000 to 66 °C as the
molecular weight reaches 200,000. Due to the presence of traces of catalyst,
the ionic conductivity of commercial PEO is between 10‘11 to 10'9 S/cm.

When a salt is dissolved in PEO, the resulting PEO-salt complex can be
amorphous, semi-crystalline or crystalline, depending on composition of the
electrolyte and temperature, as illustrated in a phase diagram for PEO-LiClO4
complex reported by Robitaille et al.17 According to the phase diagram, a
crystalline phase exists with an O:Li ratio of 10 and it melts around 65 °C.
However, conductivity is adversely affected by the crystallinity in the electrolyte,
and as studies by Berthier and coworkers18 confirmed, the amorphous phase in

polymer electrolytes is responsible for the high ionic conductivity. The crystalline

phase in a polymer electrolyte reinforces the mechanical strength, but lowers the
overall conductivity. At elevated temperatures, the crystalline phase melts and
the conductivities of PEO-salt complexes are promising (> 10'4 S/cm at 100 °C),
but the disappearance of crystalline phase leads to decreased dimensional
stability. The temperature-dependent conductivity of a PEO-based polymer

electrolyte is exemplified in Figure 1.

 

10‘2
10‘3 t

4 .
10 E

10'5 .

o (S/cm)

10‘6 _.

10'7 .

 

 

 

10‘8 I I . I

2.4 2.6 2.8 3.0 3.2 3.4
1000/T (1/K)

 

Figure 1. Arrhenius plot of temperature-dependent conductivity in PEO-LiClO4

complex (O:Li = 6) reported by Chabagno.19

The conductivity of a PEO-salt complex is also closely related to its salt
content. Figure 2 shows that at low salt concentration, the conductivity

increases with increasing salt content and reaches a peak value. However, with

 

 

 

 

10'3
AA
A
104 -. ‘
- A
A
E 10'5
g; .
b
10'6 .
10'7
0.00 0.05 0.10 0.15 0.20 0.25

Xsalt (molar fraction)

Figure 2. Conductivity of the amorphous PEO-LiClO4 electrolytes of different

salt concentrations at 50 °C reported by Prud’homme et al.9

continued increases in salt concentration, the ions tend to form aggregates that
are much larger in mass and thus have a greatly reduced mobility. Also, the

oxygen-ion coordination complexes act as transient crosslinking points that

decrease the chain mobility and conductivity. At the highest salt concentrations,
the number of oxygen atoms available to form new coordinating sites decreases.
As a result of these factors, the conductivity drops significantly when more salt is

added.

3. Ionic conduction
Mechanistically, ion transport in PEO-based electrolytes can be illustrated
by the model in Figure 3. In a PEO matrix, a Li+ cation forms a complex with

surrounding oxygen atoms from a single PEO chain or from different chains.

Wgsd‘o) V0 0 o
o 0
five L'gjio’) —_>’\o>x LVOXCK

Figure 3. Li+ ion transport in PEO-salt complex as the combined result of

polymer segmental motion and Li+ ion movement.

The Li-O complexes are in dynamic equilibrium. Local polymer segmental
motion and Li+ ion movement result in diffusion of Li+ ions from one site to a

neighboring site. WIthout an electric field, cation diffusion is random, but in an

electric field, the ions diffuse preferentially in the field direction and transport
charge.
The electrical conductivity in such a polymer electrolyte can be expressed

by the general equation
0' = Z 11; PI Q

where 0' is conductivity, n,, pi, and Qi are the total number, mobility and charge of

the species i respectively. This equation includes contributions from all charge

carriers, both cations and anions, and relates the conductivity to the mobility of
each carrier. The mobility of a charge carrier, Iii. is temperature dependent. In

order to describe the relationship of temperature and conductivity of a
homogeneous electrolyte, an Arrhenius type equation, the Vogel-Tammann-
Fulcher (VT F) equation was derived“

o(T) = A exp[-B/(T — To)]
In the VTF equation, A and B are empirical terms related to the number of
charge carriers and the activation energy for ion transport, and To is the
temperature at which the conductivity is zero and is usually taken as the glass
transition temperature of the electrolyte determined from thermal analysis. This
equation indicates that the lower the glass transition temperature of a polymer
electrolyte, the higher the conductivity at a certain temperature T. Therefore it is
desirable to make polymer electrolytes with low Tg’s. F urtherrnore, the

conductivity increases exponentially with increasing values of (T - To).

4. Synthesis of modified hosts

Practical solid state electrolytes require both a high ionic conductivity and
stable mechanical properties, but the preparation of polymer electrolytes that
combine both of these characteristics has been problematic. Not surprisingly,
numerous synthetic efforts have aimed at altering the basic PEO structure to
obtain both high conductivity and mechanical stability. In general, three
approaches have been attempted to achieve this goal: introducing defects into
regular PEO backbone to reduce crystallinity, making comb-branched polymers
that have low Tg backbones and flexible oligo(ethylene oxide) side chains, and
crosslinking the polymer to stabilize dimensional stability.

1) introducing defects into regular PEO backbone

Defects have been introduced into PEO backbones to eliminate
crystallinity. Booth and colleagues”'” inserted methylene units into regular PEO
chains by stepwise condensation polymerization of oligo(ethylene glycol)s and

methylene chloride as shown in Scheme 1.

Scheme 1. Preparation of methylene-linked PEO copolymer

KOH r
HO(CHZCH20)mH + CH2Cl2 W —[—CH2—0(CHZCH20)m—IF
. ., 2 ‘

Depending on the length of the ethylene glycol segment used, the resulting

oxymethylene—linked PEO has a lower melting point (below 26 °C) and a reduced

degree of crystallinity (below 31 °/o). The ionic conductivity of pclymer—LiCF3803
complexes reached 5x10'5 S/cm at room temperature.

Similarly, a series of linear poly(dimethyl siloxane-co-ethylene oxide)s,
were prepared by Nagaoka, Naruse, Shinohara and Watanabe23 by
condensation polymerization of dimethyldichlorosilane and oligo(ethylene

glycol)s (Scheme 2).

Scheme 2. Preparation of poly(dimethyl siloxane-co-ethylene oxide)s

(EH3 CH3
CI—SIIi—CI + HO(CH2CH20)mH ——> +Sli—O(CH2CH20)m—jm

CH3 CH3
(m = 1,2,4, and 9)

The peak ionic conductivity of the amorphous copolymer-LICIO4 complexes was
determined to be 1.5x104 S/cm for m = 4 at room temperature. However, these
polymers were neither chemically nor mechanical stable when used as real
electrolyte hosts.
Likewise, highly viscous liquid polyesters of the general structure
0 O
. II II
Tc—CHZCHz—R—CHZCHz—c—OCH20H2—0(CHZCH20)n—I7

where R is a sulfur atom or CH2 group and n ranged from 0 to 4, were prepared
and studied as electrolyte hosts?“ The low molecular weights (Mn in the range of

970 to 4,340) and low Us (in the range of -40 to -54 °C) of these materials led to

y}

A\U
RAH

€
A

h"
'u

xi

room temperature conductivities of the order of 10'5 S/cm for the resulting
polymer-LiCIO. complexes.

The copolymerization of ethylene oxide and propylene oxide was carried
out by Passiniemi et al25 to give random copolymers, whose T9 and Tm were
dependent on the composition of the two monomers. The increase in propylene
oxide content resulted in a decrease of both T9 and Tm, as the methyl group on
the oxypropylene repeating unit disrupts the PEO crystalline structure. However,
the total conductivity of the copolymer-LiClO, Complexes was found to decrease

as PO content in the copolymer increased.

Scheme 3. Copolymerization of ethylene oxide and propylene oxide

0 O I
A + ——* +(CH20H20In—(CH2C'3H0M-F

CH3 CH3

2) comb-branched polymers

Coordinating oligo(ethylene oxide) side chains have been attached to
flexible backbones with low Us to form comb-branched polymers. For example,
polysiloxanes usually have low US (-127 °C), therefore Hall et al.26 and Smid et
3!.”29 used the following catalyzed reaction to obtain liquid oligo(ethylene oxide)

side-chain poly(methyl siloxane) comb polymers (Scheme 4).

Sc

The i:

5.37 .
VI‘C" l
UVI‘

10

Scheme 4. Preparation of comb polymer with PEG branches

‘1“? 1”“
catalyst .
—[—sio+n— + HO(CHZCH20)mCH3 —H——-> +5104;
" 2
H O(CHZCH20)mCH3

The highest conductivity for such polymer-LICIO4 complexes was 1x10'4 S/cm at
room temperature. Hydrosilation reactions of poly(methyl siloxane) with allyl

ethers were carried out to produce similar polymers (Scheme 5).28

Scheme 5. Preparation of comb-branched poly(siloxanes) with PEG side

 

chains
CH CH
I 3 catalyst | 3
+2101. > +501;
I H2C:CHCH20(CH20H20)mCH3 |
H (m=2,7,9and 12) €sz
CH2
CH20(CH2CH20)mCH3

The polymers had similar conductivities to those obtained using Scheme 4.
Polyphosphazene has a Tg of -70 °C. Polyphosphazenes with
oligo(ethylene oxide) side chains7' 30'3“ represent another class of comb-
branched polymers synthesized and studied as electrolyte hosts. The first such
polymer, MEEP, was prepared by reaction of poly(dichlorophosphazene) with

sodium 2-(2-methoxyethoxy) ethoxide as illustrated in Scheme 6.

11

Scheme 6. Preparation of MEEP from inorganic polyphosphazene

 

CI 0(CH2CH20)2CH3
I N80<CH20H20>2CH3 l" N P 1
+N=P+ p j— : T
I " n-Bu4NBr,THF,A ‘ l n
‘ CI O(CH2CH20)2CH3

Compared to traditional electrolytes from PEO, MEEP-LiCF3SO3 complexes
showed improved ionic conductivity (2x10"5 S/cm) at room temperature, however,
these materials lack the mechanical stability needed for most applications. Aside
from cross-linking?“36 Pomerantz et at” reported polyphosphazene-based
electrolytes with enhanced mechanical properties by modifying the polymer
backbone with organo-If—phosphazenes of the kind

CH3(OCH2CH2)mO O(CHZCH20)mCH3
iEN—ORGr—NzP—ORGZ—let

n

 

CH3(OCHZCH2)mO O(CH2CH20)mCH3

where ORG1 and ORG2 were organic spacer groups. The conductivity of one of
these polymer-LiCF:,SO3 complexes reached 3.2x10“‘3 S/cm at 22 °C. The mixed
side chains were adjusted on phosphazene backbones of
O(CHZCH20)XR
+N=P1x

O(CHZCH20)yR'

12

by Allcock and his colleagues,33 where R and R’ could be CH3 and/or CIzH25,
and x and y were variables. The peak conductivities of some of these polymer-
LiCF3$O3 complexes were found to be between 1.6x10'6 and 3.9x10'5 S/cm.
Comb-branched polymers with low Tg backbones usually have the
required chain flexibility for a highly conductive electrolyte. Unfortunately most
are not mechanically stable enough to allow their use as electrolyte hosts at
room temperature. In order to overcome this drawback, main chain flexibility
was sometimes intentionally sacrificed to gain good dimensional stability. For
this reason, flexible oligo(ethylene oxide) side chains were incorporated into
polymers with relatively rigid backbones. Polymethacrylates with pendant PEO

side chains, poly(MEEMA), of the formula

1”“
r
TOW—('31?

COO(CH2CH20)mCH3

where m was of varying values, were designed and prepared as host materials
with improved mechanical strength.”39 A recent study39 reported a conductivity
of 3x10‘5 S/cm at 25 °C for poly(MEEMA) with a short (m = 2) side PEO chain.
The need for more PEO content in the polymer and more flexible side chains

gave rise to related materials, poly(itaconate ester)-based polymers40

CHZCOO(C H2CH20)mCH3

‘I—CHz—‘i‘i:

COO(CH2CH20)mCH3

where two PEG-containing side chains were attached to each repeating unit.

Il‘
' .

r1: ,,
.54“

13

Recently, Inoue and coworkers‘"“2

reported their work on a polycascade

polymer, poly(STEP) (shown below). Though the conducting side chains were

connected to a relatively rigid polystyrene backbone, the conductivity of

poly(STEP)-LiCIO4 complexes was found to be 1

reached as high as 10'4 S/cm at 60 °C.

+CH2—CH-}F

CH3(OCH2CH2)3O\

CH3(OC HzCH2)3O/

.5x10'5 S/cm at 30 °C and

o /O(CHZCH20)3CH3

/O(CH2CH20)3CH3

O(C HzCH20)3CH3

3) crosslinking polymers to stabilize mechanical properties

The polymer electrolytes are often crosslinked as final processing step to

form a three-dimensional network of reasonable stability. Crosslinking methods

include photo-irradiation to give polymer electrolytes that have the following

schematic structure.

”555

 

MW

Usually crosslinked electrolytes have lower conductivities after crosslinking as a

result of reduced chain mobility.

14

An example of crosslinking PEO by hydrosilylation is shown in Scheme
7.43 Conductivity for the crosslinked polymer-salt complexes reached 10'5 to 10’6

S/cm at room temperature.

Scheme 7. Crosslinking PEO by hydrosilylation

H2C=CH--CH2—O(C H2CH20)n—-CH2—CH=CH2

 

 

1‘
_L -_ ‘
L “T" 01*?
CH3
catalyst
I o

 

l
O(CHZCH20)n——CH2—CHz—CHz—Si—CH3

(n = 22 or 45)

15

ll. Target Polymers in This Work

In this project, a new series of polymer electrolyte hosts was designed to
have the general structure depicted in Scheme 8. It is desirable for a polymer
electrolyte to have a low glass transition temperature, high ionic conductivity and
stable mechanical properties. The target polymers satisfy these important
requirements for a good electrolyte host in the following ways: (1) with mainly
polyethylene and PEO segments in the polymers, the glass transition
temperature was expected to be low; (2) oligo(ethylene oxide) blocks were
incorporated into the polymer backbone as ionic conducting segments; (3)
adjustable spacers were expected to stabilize the mechanical strength of the
material some extent; (4) carbon-carbon double bonds were Introduced as

crosslinking or branching sites to modify the structure of the material.

Scheme 8. Target polymer electrolyte hosts

crosslinking or
ionic conducting segment branching site

i l

+(CH2)m—0(cH20H20)n—(CH2)m—CH=CH—};

‘ ___i
spacer

 

 

16

From the synthetic point of view, it should be possible to prepare the
target polymers by an easy, clean and straightforward polymerization in large

quantity. Recent developments in acyclic diene metathesis (ADMET)

44-57

polymerization offer a convenient synthetic route to the target polymers.

17

Ill. ADMET Polymerization

ADMET polymerization is a stepwise condensation polymerization as
generalized in Scheme 9. In the presence of a metathesis catalyst, an acyclic
axe-diene can be polymerized to give an unsaturated linear polymer by
equilibrium polymerization. Like common condensation polymerizations,58 a
volatile small molecule by-product (ethylene) is eliminated from the reaction, and

the removal of ethylene drives the equilibrium towards high molecular weights.

Scheme 9. General ADMET polymerization

/\x/\ fatalyfi‘ MU? * "02H4i

 

 

The mechanism of ADMET chemistry (Scheme 10) as proposed by
Wagener et al.“5 consists of an initiation step followed by a polymerization cycle.
In the initiation step, the initiator (for example, a metal alkylidene) reacts with
monomer to generate a metallocyclobutane, which decomposes to form a
metallocarbene species derived from the monomer. This step is an example of
the olefin metathesis reaction. The polymerization cycle involves the formation
of metallocyclobutane intermediates that leads to dimer, trimer, etc., and
eventually leads to high polymers. As noted in the scheme, each step is
reversible, and removal of ethylene is crucial for obtaining high molecular

weights.

18

j

588. __o

co LoEocoE xjiif ark; QHONI

 

m
N .. _I<_,.5
ION—2: .— XIOHE I_ i “
ii... m /

 

x \/ 2.... _ \j mIoHof

i/ _i _ LoEogo

\ / ...O ..mEOCOE

\lx xl/

 

.EmEosooE 5.33.3822“ hmso< .3 85:3

x/

(VA/N

mIonj

19

There are two types of ADMET polymerization catalysts that have been
reported in the literature. The first type includes classical olefin metathesis
catalysts. In 1987 Wagener and his colleagues“ employed the WCl6/EtAlCl2
catalyst system to polymerize 1,9-decadiene and 1,5-hexadiene. Later Nubel et
al.“ described WCl6/EtAlCl2lPrOAc as a modified catalyst to synthesize
polypentenamer from 1,5-hexadiene. However, both catalysts polymerized
hydrocarbon diene monomers with limited success. Since classical metathesis
catalysts are generally strong Lewis acids, they do not tolerate a wide variety of
organic functional groups in monomers.

The second type of catalyst, Lewis acid-free transition metal alkylidene
complexes have been very successful in carrying out ADMET polymerization of
diene monomers having different organic functionalities. The most widely used

59-62

ADMET catalysts were developed by Schrock and coworkers and have the

following general structure:

...... M
O \
F3C9/ O/ \CHC(CH3)2R

where the metal is either tungsten or molybdenum (M = W, R = CH3; M = M0, R

= Ph). The homogeneous W catalyst has a much higher reactivity than the Mo

20

analog, but due to its reactivity, the tungsten catalyst has a shorter lifetime, less
tolerance towards functional groups and less control over metathesis reactions.
This makes Schrock’s Mo catalyst the favored choice for most ADMET
polymerizations.

Grubbs reported that ruthenium carbene metathesis catalysts“65 (shown
below) are effective for ring-opening metathesis polymerization.63 66‘“ Recent
work by Walba et al.56 showed the ruthenium catalyst was also a good catalyst
for ADMET polymerization. These well-defined ruthenium complexes are much

less sensitive to oxygen and are more tolerant of organic functional groups.

CI i ..... \ Ru: /
"'Ru=" Ph CI/ I
CI/ I PCY3
PR3
X
(R = Ph or Cy) (x = H or CI)

The reaction conditions for ADMET are relatively mild. Polymerization
initiated by Schrock’s alkylidene catalysts requires that the temperature not
exceed 60 °C. Above this limit the catalysts tend to decompose and lose
reactivity. The work by Walba et al.56 indicated that the Grubbs’ ruthenium
catalyst can be used at 80 °C for 24 hours.

A number of unsaturated linear polymers containing different organic
functional groups have been synthesized via ADMET polymerization. The first
high molecular weight polymers from ADMET were reported in 1991 .‘5 By using

Schrock’s W alkylidene catalyst, Wagener et al. prepared two unsaturated

21

polyalkanes (Scheme 11). The polymerization generated clean polymers and

ethylene without any other products.

Scheme 11. Synthesis of unsaturated polyalkanes via ADMET

polymerization

H20=C H"'—(C H2)n—CH=C H2

l Schrock's W alkylidene catalyst

+(CH2)n—CH=CH&7

n e 6, Mn = 108,000; n = 2, Mn = 28,000

Unsaturated polyethers, which are structurally relevant to the target
polymers in this project, were the next polymers prepared via ADMET
polymerization.46 As Scheme 12 shows, polymers were obtained when n = 3
and 4. It was found, however, that high polymers were not produced when there
were less than three methylene units separating the oxygen atom and the
terminal vinyl group in the monomers (n = 0, 1 or 2). This was attributed to
catalyst poisoning caused by the interaction of the vinyl group and the oxygen

atom with the metal center that blocked further metathesis steps.

22

Scheme 12. Synthesis of unsaturated polyethers via ADMET

polymerization

H2C=CH—(CH2)n_O—(CH2)n—CH:CH2
1 catalyst, -C2H4

+(CH2)n—o—(CH2)n—CH=CH—117

ADMET polymerization also found application in the synthesis of
unsaturated polycarbosilanes,47 unsaturated polycarbosiloxanes,50 and
unsaturated polythioethers52 (Table 1). Two other types of polymers prepared
via ADMET polymerization are unsaturated polyesters48 and unsaturated
polycarbonates.49 Metathesis reactions involving compounds with carbonyl
groups led to catalyst poisoning before Schrock’s Lewis acid-free catalysts were
invented, and the successful preparation of polymers containing carbonyl groups
demonstrates the versatility of ADMET polymerization with these improved
catalyst systems.

One interesting aspect of the ADMET chemistry is the relationship
between the monomer structure and its polymerizability. More specifically, it has
been found that when a functional group is separated by three or more
methylene units from terminal vinyl group, unsaturated linear polymers can be
prepared. However, monomers with two or less methylene units may not be

polymerized by AMDET. This phenomenon was termed the “negative

23

Table 1. Some Representative ADMET Polymers Prepared by Wagener

 

 

at a, 47-50.52
Unsaturated polymer Structure
CH3 CH3
. l, l, J.
polycarbosflane CHz—sl SlI—CHz—CH=CH J
L . x
CH3 CH3

polycarbosiloxane

polythioether

polyesters

polycarbonates

CH3 CH3 CH3
. . I. I. 4
CHz—SII—O—SI—O—SI—CHz—CH=CH J
L X
CH3 CH3 CH3

 

 

—{—(CH2)4—s—(CH2)4—CH=CH—};

O O

i ll
+1.1.-._CQI_._.H..

(n = 2, 3, and 4)

7%

ii

,

—1L—(CH2)n—0—C—O—(CH2)n-}7
(n = 2, 3, and 4)

 

24

neighboring group effect". Since we intended to vary the number of methylene
spacers to adjust the mechanical properties of the targetpolymers, attention was
paid to how this would affect the polymerizability of the monomers.

ADMET polymerization of conjugated monomers has been explored as
well.53 Methyl terminated polyenes with up to 20 conjugated double bonds were

prepared from 2,4-hexadiene (Scheme 13).

Scheme 13. Synthesis of conjugated polyenes via ADMET polymerization

catalyst r 1
H3C—CH=CH—CH=CH—CH3 ———> H3C+CH=CHTCH3
- 2-butene . x

The effect of double bond substitution on the ADMET polymerizability of a
monomer is of general interest,70 yet in this reaction, neither monosubstitution on
the terminal carbon atoms of the double bonds nor conjugation in the monomer
affected the ADMET reactivity of the monomer. The determining factor in
achieving high molecular weight seemed to be the solubility of the resulting
oligomers or polymers, as their precipitation prevented further growth of the
chains.

ADMET polymerization proved to be a convenient method to prepare
liquid crystalline materials as well. A series of main-chain ferroelectric liquid
crystalline oligomers were’synthesized by ADMET polymerization using Grubbs’

ruthenium carbene metathesis catalyst, illustrated in Scheme 14.56

[EIQP‘
. “'1‘

0348
W‘g-I

11C:

25

Scheme 14. Synthesis of liquid crystalline materials via ADMET

polymerization

r102
HZC=CH—(CH2)3—O—Ph—Ph—C \___.——(0H2),,/

 

 

\\
O
n = 2, 3 and 4

TCY3 Ph
0' """" Ru=:~"“"' ‘Ph
01/ l

PCY3

I
N02
CH—(CH2)8—O—Ph—Ph—C ;L(CH2)n/
T \\O ,x

The polymerization was carried out in bulk at 80 0C for 24 hours. The degree of
polymerization was about 10, determined by end group analysis from 1H NMR
spectra.

An unsaturated polymer with a cubane-containing backbone, which is of
interest as high-energy material, was synthesized recently by Chauvin and
Saussine57 through ADMET chemistry (Scheme 15). The molecular weight,
which was limited by the poor solubility of the polymer, was determined to be

1,100 to 1,300 by 1H NMR end group analysis.

26

Scheme 15. Synthesis of cubane-containing polymer via ADMET

polymerization

H2C:C H—(C H2)2 ’9‘ (C H2 )2—0 H=C H2

1 Schrock's Mo catalyst

(C H2)2—C HT:-

 

 

=L—'CH—-(CH2)2 $

ADMET polymerization can also be used to generate copolymers from
two cum-diene monomers. When two dienes can be polymerized through
ADMET individually, they are able to form random ADMET copolymers as well
(Scheme 16). ADMET copolymerization was performed in several

“"3'52'57 and the process can be easily explained by Scheme 10, where

systems,
either monomer can add to the reactive species in the polymerization cycle, thus

producing a random copolymer.

27

Scheme 16. A generalized ADMET copolymerization

H2C=CH—X—CH=CH2 + H2C=CH—Y—CH:CH2
1 catalyst, -C2H4

1
iCHZCH—XHCHZCH—Y—jy—

L JXL

Finally, it is worthwhile to mention the geometry of the internal double
bonds in the ADMET polymers. The ratio of the cis and trans double bonds are
usually determined by quantitative 13C NMR measurements. The content of
trans double bonds in ADMET polymers has been reported to range from 40 to

93%, but most polymerizations yield around 80% trans content.

28

IV. Ionic Conductivity Measurements

There are two distinct types of conducting materials in terms of charge
carriers. Electronic conducting materials conduct electric currents by the flow of
electrons. Metals, semiconductors such as Si, and conjugated polymers all are
examples of electronic conductors. Ionic conducting materials, as the name
implies, conduct electricity by the migration of ions. Molten salts, some inorganic
conductors, aqueous electrolyte solutions, and polymer electrolytes fall into this
category. Figure 4 lists various conducting materials and their conductivity.

Like all other conducting materials, the most important electric property of

a polymer electrolyte is its conductivity. Conductivity, c, is defined as the

reciprocal of resistivity p

0'=—p—

while resistivity, an intrinsic physical property of a material which is independent
of its geometry, is given by

A
”RT/-

where A is the area and! is the length of the sample. The resistance R can be

measured or calculated using Ohm’s law

where V is the applied voltage and l is the resulting current. Ohm’s law reveals

that for a metal conductor of fixed dimension, there exists a linear relationship

29

 

 

 

 

 

 

Electronic Conduction o (S/cm) Ionic Conduction

Superconductors __ 10+..

(R = zero) __

Hg, best ceramics __

best doped __

inorganic polymers __

some organics

Conductors __ 10“8

Au, Ag, Cu __

best doped organic __

polymers __

Semiconductors __ 10"2

GaAs, doped Si :: 10° molten salts
__ 10'1 best ceramics
__ 10'2 best liquids

10‘3 best plastic gels

__ 10" best solid polymer
__ electrolytes

Insulators __ 10'7
:: 10‘12 most organic
__ polymers

mica, silica __

most organic __

polymers
_"'—— 10-17

 

Figure 4. Conductivity scale for different materials.

 

. l,
58.?!

.7153

F’Gure 5

30

between the voltage applied and the current. Thus the resistance can be
measured and the conductivity of the sample can be derived.

However, the linear relationship between voltage and current does not
hold when a dc. voltage of fixed potential is applied to a polymer electrolyte
sample contained between two inert electrodes (Figure 5). As shown in
Figure 6, the current decays as a function of time. This phenomenon is caused
by the accumulation of cations at the negative electrode and anions at the
positive electrode. and the reduction in number of charge carriers in the bulk
polymer electrolyte (Figure 5). The current decay makes it difficult to measure
the resistance and thus conductivity by direct current methods. Moreover,
resistance at the interface between the bulk polymer electrolyte and the

electrodes makes d.c. measurements complicated.

  

++++++++++

     

Figure 5. Polymer electrolyte contained between two inert electrodes: before

(left) and after (right) a dc. voltage of fixed potential is applied.

31

current

 

>
time

 

Figure 6. Current decay as a function of time when a dc. voltage is applied to a

polymer electrolyte sample.

While the measurement of ionic conductivity of polymer electrolytes by
direct current methods has some difficulties, impedance spectroscopy"75 (IS),
an alternating current method, proves more successful. When an alternating
voltage signal of a certain frequency is applied to a polymer electrolyte cell, a
resulting ac. current, usually not in phase with the voltage, can be measured
(Figure 7). The voltage V and current I can be expressed in their sinusoidal
forms as

V = M sin (cot)
and
l= |l| sin (wt - 4))
where M is the potential magnitude and III is the current magnitude, (0 is the

angular frequency of the ac. voltage, which is related to the applied frequency

32

as (0 = 2nf, t is the time, and it: is the phase shift of the current from the voltage

and is dependent on the angular frequency.

v = M sin (mt) I = Ill sin (wt - ct)

\m/

Figure 7. The sinusoidal voltage applied to a polymer electrolyte cell and the

 

 

resulting current.

The concept of impedance is introduced when Ohm’s law is applied in the
ac. measurement. Impedance 2 is given by Z = V I I, the same form as its d.c.
counterpart, resistance R, but 2 is a function of frequency of the voltage.
Impedance is a vector quantity and can be treated in complex form as

Z = Z’ - jZ"

where Z’ is the real component, Z” is the imaginary component, and j is the
imaginary symbol. Figure 8 shows how the complex impedance vector 2 relates
to its real and imaginary components in the rectangular complex plane at a

phase angle of 6.

33

 

 

Z”=Zsin9 2:2,”?
9
a?

Z’=Zcose

Figure 8. Complex impedance vector Z and the real and imaginary components

in the rectangular complex plane. The phase angle is 9.

In a typical IS measurement, the magnitude of the applied voltage is fixed
at an appropriate value, but the frequency is changed over a wide range, usually
from several hertz to several megahertz. At each frequency, the complex
impedance is obtained and is plotted as a point in the complex plane. Figure 9
displays the complex impedance diagram of a polymer electrolyte cell. The
plotted data is composed of a semicircle for impedance data in the high
frequency range followed by a linear spike for low frequency data. The real bulk
impedance of the electrolyte, Rb, is taken as the intercept of the linear spike on
the real axis.

Since the dimensions of the polymer electrolyte cell are known (Figure
10), the conductivity of the bulk polymer electrolyte can be calculated according

to

- Z"

 

Figure 9. Complex impedance diagram of a polymer electrolyte cell sandwiched

between two inert electrodes.

polymer electrolyte with bulk impedance Rb

7 d..-“‘1 . ft). ‘ ‘ . ' ".... y . . u »
1’3. .\. . ,L'f,’.i,du Sc" 5.7st .. I‘ . . 1 ;:,’ ”5";-
“mw hw v—vv

thickness I inert electrodes

 

 

\
...“ . /

‘h ‘ .1. ‘-t_ J _ ' K " ..
, '~: magi: i H: vs. 12>. ,.i:~'5 333.9 :1? he
‘ ' "I W 5"!" .rr'ifirj;H. ..

 

area A

Figure 10. A schematic cross section polymer electrolyte cell of known

dimensions.

RESULTS

l. Monomer Preparation

In order to synthesize the target polymers via ADMET polymerization,
oligo(ethylene glycol) a,w-dialkenyl ethers were prepared that have the general
structure shown in Table 2. For simplicity, the nomenclature shown in Table 2 is
used in place of the full names of the monomers. The corresponding

abbreviations for the polymers are “P” followed by the monomer abbreviation.

Table 2. Acronyms for Monomers'

H2C=CH—(C H2)m——O(C H20H20)n—(C H2)m—-C H=CH2

 

 

n 2 3 4 5
m
1 A2
2 32
3 , P2 P3 P4
4 H2 H3 H4 H5
6 02 O4

 

 

a A, B, P, H, 0 refer to allyl, 3-butenyl, 4-pentenyl, 5-

hexenyl, and 7-octenyl respectively.

35

36

Two synthetic routes were chosen to prepare the monomers with different
numbers of methylene units between the terminal vinyl groups and the
oligo(ethylene oxide) segment. The first route (Scheme 17) involved the
Williamson coupling of 4-bromo-1-pentene with the di-sodium salt of di-, tri-, and
tetra-ethylene glycol to make P2, P3 and P4 respectively. The yields (not

optimized) ranged from 62% to 81%.

Scheme 17. Monomer preparation by Williamson ether coupling

NaH,THF
HO(CHZCH20)nH RT %- NaO(CH7_CH20)nNa

 

H2C:CH—(C H2)3Br
THF, reflux

HZCZCH—(CH2)3——-O(CH2CH20)n—(CH2)3—CH=CH2

(n = 2, 3 and 4 respectively)

All other monomers were prepared in 64 to 88% yield by coupling the
sodium salts of alkenols and oligo(ethylene glycol) ditosylates (Scheme 18).
The key reagents, allyl alcohol, 3-buten-1-ol, and 5-hexen-1-ol were purchased
from commercial sources. 7-Octen-1-ol was prepared by the following one-step

elimination reaction:

37

KOC(CH3)3
CI—(CH2)8—OH > HgC=CH—(C H2)50H
orvrso, RT.
68%

 

Scheme 18. Monomer preparation by reaction of ditosylates with sodium

alkenoxides
NaH, THF
H2C:C H—(CH2)mOH -_RT—.- H2C=CH—(CH2)mONa
TSO(C HQCH20)nTS
THF, reflux

H20=C H—(C H2)m—O(C H2C H20)n_(C H2 )m—C HZC H2

m=2zn=2;
and5;

.An

N_NN
m

35»
‘11:

333
Illlll
9.3.1???
:3:

The purification of the monomers was performed by repeated vacuum
distillation over calcium hydride. Most monomers were further dried by stirring
over a fresh sodium mirror under argon, followed by distillation in vacuo. All

purified monomers were stored in a drybox for future polymerization.

38

II. Unsaturated Ethylene Oxide-Segmented Polymers

1. ADMET polymerization of oligo(ethylene glycol) a,m-dialkenyl ethers

Both WCl6/Sn(CH3)4lPrOAc and Schrock’s Mo catalyst were tested as
ADMET polymerization catalysts in this research. Attempted ADMET
polymerization of P3 and H4 using WCl6/Sn(CH3),/PrOAc as the catalyst system
was carried out in the same manner as described in literature. No sign of
initiation and polymerization was observed.

ADMET polymerizations of oligo(ethylene glycol) a,m-dialkenyl ethers
using Schrock’s molybdenum alkylidene catalyst were successful.
Polymerization of monomers were carried out in scale running from 0.5 g to 15.0

g as generalized in Scheme 19.

Scheme 19. ADMET polymerization of oligo(ethylene glycol) a,m-dialkenyl

ethers

H2C=C H—(C H2)‘m—“'O(C H20 H20)n—(CH2)m—C HZC H2

1) Schrock's Mo catalyst, R. T.
2) 50 °C, vacuum

3) toluene, 50 °C

 

i

+(CH2)m—O(CH2CH20)n—(CH2)m‘_CH:CH_}—X- + C2H4T

39

In most cases, the addition of catalyst to monomers resulted in an
immediate, vigorous release of ethylene gas and the mixtures became
homogeneous. Since the monomers and oligomers have high boiling points and
their volatility at room temperature is minimal, high vacuum was applied
throughout the bulk polymerization stage. After 6 h, the polymerization
temperature was raised to 50 °C. When the polymerization systems became too
viscous to stir, dry toluene was added to lower the viscosity and vacuum was
only occasionally applied. With time the color of the polymerization changed
from yellow to orange to dark brown, presumably due to partial decomposition of
the catalyst. After a certain period of time the polymerization was terminated by
exposing it to air.

When A2 and Schrock’s Mo catalyst were mixed, the immediate evolution
of ethylene was also observed. However, the polymerization stopped at early
stage and no high molecular weight polymer was obtained.

Except for A2, whose polymerizability needs further investigation, all
monomers in Table 3 were polymerized to give high molecular weight polymers
via ADMET polymerization. The polymer work-up procedure included
precipitating the polymers from toluene solutions into n-heptane and drying
under high vacuum until constant weight was obtained. The polymers were all

prepared in good yield (92% and above).

40

Table 3. Polymerizability of Monomers by ADMET Polymerization Using

Schrock’s Mo Catalyst'

H2C:C H—(C H2)m—O(C H2C H20)n—(C H2)m—C HZC H2

 

 

n 2 3 4 5
m
1 :t
2 +
3 + + +
4 + + + +
6 + _ +

 

 

a (+) monomer has been polymerized into polymer. (:t)

needs further investigation; no polymer was obtained

2. Properties of the unsaturated polymers
The properties of the unsaturated polymers are collected in Table 4. The
molecular weights are comparable to the published results for other ADMET
polymerizations.“"'52 The polydispersity index (PDI) values are all near 2, typical
for step-grth polymerizations. Despite attempts to remove all catalyst
residues, the purified polymers had a slight greenish-brown tinge that is believed
to correspond to catalyst residues. All the polymers, except for P02 and P04,

were extremely tacky regardless of molecular weight. Polymers P02 and P04

‘ Ill‘lllhl

 

41

 

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42

both have six methylene units on each side of oligo(ethylene oxide) segment in
the repeating unit, and appear to be crystalline and stiff.

The polymers are soluble in an unusually broad range of organic solvents,
including toluene, tetrahydrofuran, chloroform, carbon tetrachloride, methanol,
acetonitrile, acetone, and ethyl acetate. This high solubility likely results from the
combination of hydrophobic (alkenyl) and hydrophilic (ethylene oxide) segments

in the polymer backbone.

3. Spectroscopic characterization of the unsaturated polymers
The chemical structures of the unsaturated polymers were characterized
by 1H NMR, 13C NMR and FTIR spectroscopy. The spectroscopic data appears
in the Experimental section.

Monomers having same terminal alkenyl groups and different number of
ethylene oxide units in the middle are homologous, and the spectra of these
monomers look very similar. Polymers from these monomers also have very
similar NMR spectra. As a representative example, the 1H NMR spectra of
monomer P3 and polymer PP3a are shown in Figure 11 for comparison. In this
figure, peaks between 3.64 and 3.54 ppm, corresponding to protons on the
ethylene oxide segment, are common to all monomers and unsaturated
polymers and show no shift in going from monomer to polymer. However,
resonances at 5.80 and 4.97 ppm from vinyl protons on monomerP3 disappear,
while a new peak appears at 5.38 ppm in the spectrum of polymer PP3a that

corresponds to the protons on the internal double bonds.

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44

In the 13C NMR spectra (Figure 12), signals from carbon atoms of the
ethylene oxide unit appear at 70.8 and 70.5 ppm. Peaks from the terminal vinyl
groups of the monomer at 138.3 and 114.7 ppm disappear, while two new
resonances appear at 130.0 and 129.5 ppm that correspond to the trans and cis
double bond carbons respectively. The peak at 30.2 ppm in the monomer
spectrum splits into two resonances (29.5 and 23.6 ppm) in the polymer
spectrum, corresponding to the trans and cis geometries of carbon 4 in the
polymer.

The relative proportion of cis and trans carbon-carbon double bonds in the
polymers wasdetermined by comparing the integration of the peaks at 130.0
and 129.5 ppm from quantitative 13C NMR measurements. The percentage of
trans double bonds in the polymers was consistently between 82-86%, which
agrees well with results by other research groups who reported that ADMET
polymerizations result in trans double bond contents ranging from 40% to 90%,
with most around 80%.‘“"52

Spectroscopic changes in going from monomer P3 to polymer PP3a are
also noticeable in the IR spectra (Figure 13). Not surprisingly, the strong
absorption at 1121 cm'1 is the common feature in the spectra, attributable to C-
O—C asymmetrical stretching in ethers. As expected, the bands at 3080, 1642,
994 and 914 cm“1 characteristic of the vinyl group disappear after polymerization,
while a new sharp band corresponding to the trans double bond appears at 968

cm". The absorption band for the cis internal double bond,

45

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46

which was expected to appear between 730-665 cm" was not seen. due to the

low cis double bond content in the polymer and overlap from other bands.

 

 

a)
o
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i:
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4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm’1)

Figure 13. IR spectra of monomer P3 (top) and polymer PP3a (bottom).

MA

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47

4. Thermal stability of the unsaturated polymers

The thermal stability of the unsaturated polymers was investigated by
thermogravimetric analysis (TGA). For each polymer, measurements were taken
both in inert (nitrogen) and in oxidative (air) atmospheres.

Typical TGA curves of an unsaturated polymer are represented in Figure
14. It shows that the onset of decomposition for polymer PP2 is above 320 °C in
both nitrogen and air, and the polymer decomposes rather rapidly afterwards.
Only trace residues remained above 500 °C. There is no significant difference in
thermal stability for PP2 in nitrogen and in air, although the samples appeared to
be slightly more stable in inert atmosphere.

The nitrogen TGA profiles of polymer PP4 and polyethylene glycol with a
molecular weight of 10,000 (PEG10K) are plotted in Figure 15 for comparison.
The TGA curves of PP4 look similar to those of PP2, with the onset of thermal
breakdown at comparable temperatures. The similarity in the TGA profiles
indicates that the unsaturated polymer and PEG10K have similar thermal
stabilities, and implies that ether breakdown is responsible for the decomposition
of the polymers.

Thermal decomposition of PH2, shown in Figure 16, gave similar results.
Compared with PP2 and PP4, the degradation onset for PH2 occurred at a lower
temperature, and following a slow initial decomposition it rapidly degraded like
the previous polymers.

The TGA profiles of the other unsaturated polymers appear in the

Appendix. Table 5 compiles the temperatures for 5%, 50% and 90% weight

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51

Table 5. Thermal Stability of the Unsaturated Polymers'

 

 

weight lossb in nitrogen weight lossb in air
Polymer 5% 50% 90% 5% 50% 90%
P82 386 433 450 372 430 464
PPZa 401 442 464 367 424 457
PP2 410 435 453 393 427 451 .
PP3a 395 440 462 382 430 451
PP3 389 428 453 356 422 454
PP4 398 439 461 388 433 454
PP4a 405 428 447 377 418 453
PH2 374 433 466 317 432 487
PH3 338 430 478 342 424 469
PH4 343 425 472 320 424 478
PH5 341 418 460 335 421 460
P02 415 447 471 406 443 ' 474
P04 338 428 463 312 421 466

 

‘ Temperatures are reported in °C.

" Defined as the temperature where the weight loss reached the indicated levels.

52

losses for all the unsaturated polymers. The temperatures where 5% weight loss
occurred varied from 312 to 406 °C in air, with a shift to higher temperatures for
measurements taken in nitrogen. Interestingly, the midpoint of the thermal
breakdowns of all polymers appeared in a much smaller temperature range
suggesting a common degradation mechanism. Usually a polymer lost 90% of

its weight by the time temperature reached 450 °C.

5. Thermal behavior of the unsaturated polymers

The unsaturated polymers were analyzed by DSC to study their thermal
properties. Samples were heated at 10 °lmin from -100 to 100 °C, quenched to
-100 °C at 200 °Clmin, heated at 10 °lmin to 100 °C, and finally cooled to -100 °C
at 10 °lmin. As described below, nearly all samples exhibited unique thermal
properties with combinations of crystallization and melting transitions.

The thermograms in Figure 17 are the second DSC heating and cooling
scans for P82. After a glass transition seen at -72 °C in the heating scan, an
exothermic crystallization at -33 °C was followed by two overlapping melting
peaks at -9 and 0 °C respectively. No crystallizing or melting transitions were
observed in the second cooling scan.

The thermal behavior of polymers PP2 (Figure 18) and PP3 (Figure 19)
is simple. Except for the glass transition, no other peaks appeared during the
measurements, indicating these two polymers are amorphous over the whole

temperature range.

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The second heating scan for PP4 (Figure 20) includes a glass transition
and multiple crystallizations and melting transitions in the low temperature range.
However, peaks corresponding to the crystalline phase changes were again not
seen in the cooling scan, similar to the data for P82.

The second DSC heating and cooling scans for polymers PH2, PH3, PH4
and PH5 are plotted in Figures 21, 22, 23 and 24 respectively. In all cases,
glass transitions were observed at low temperatures. The DSC heating scans
for polymers PH2 and PH3 have similar features. Above the glass transition, a
broad crystallization peak is followed by two melting transitions at higher
temperatures. For polymers PH4 and PH5, there were multiple crystallization
and melting peaks. Usually a crystalline phase formed and melted, followed by
formation and melting of another crystalline phase as the temperature increased.

Finally, DSC thermograms for P02 (Figure 25) show adjacent twin
melting peaks in the heating scan and a sharp crystallizing peak in the cooling
scan. In Figure 26, P04 with a longer ethylene oxide segment possesses one
broad melting transition in heating scan and a sharp crystallizing peak in the
cooling scan.

The characteristics of the thermal transitions for the unsaturated polymers
are summarized in Table 6. Values of the melting transition temperature, Tm,
were taken as the temperature at the peak of the melting transitions in second
heating scans, and the crystallization temperature, Tc, was taken as the

temperature at the peak of the crystallization transitions in the second cooling

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Table 6. Thermal Transition of the Unsaturated Polymers

64

 

 

Polymer Tg (°C) Tm 3 (°C) Tc b (°C) Tg/T m °
P82 -72 -9, 0 0.74
PP2 -79
PP3 -77
PP4 -75 -36, -19, -14 0.76
PH2 -81 -10, -4 -38 0.71
PH3 ~79 -8, 4 -39 0.70
PH4 -77 -32, -5 -29 0.73
PH5 -74 -20, 7 -31 0.71
P02 18, 25 0
P04 -78 3 -17 0.71

 

3 Taken as the temperature of the peak of the melting endotherm.

” Taken as the temperature of the peak of the crystallization exotherm in the

DSC cooling scans.

° Calculated using absolute temperature values.

65

scans. Each Tg/T m value was calculated as the ratio of Tg to the highest Tm for

that polymer sample, where T is expressed in Kelvin (K)-

66

Ill. Alternating (A8)" Copolymers from Unsaturated Polymers

1. Reduction of the unsaturated polymers

Four unsaturated polymers, PH2, PH3, PH4 and PH5, were reduced to
form hydrogenated polymers, PHZH, PH3H, PH4H, and PH5H respectively, as
outlined in Scheme 20. The reduction reaction involved the hydrogenation of
the carbon-carbon double bonds in the unsaturated polymers with p-
toluenesulfonhydrazide, which was believed to decompose and form diimide as
an intermediate during the reaction”79 Diimide is very reactive and reduces
symmetrical double bonds readily by neutral hydrogen atom transfer to the

substrate.

Scheme 20. Hydrogenation of the unsaturated polymers

+(CH2)4—0(C HQCH20)n—(CH2)4—C H20 H11;

TsNHNH2 (excess)

toluene, BHT, Ar

reflux, 12 h

 

I

+0(CH2CH20)n—(CH2)10‘}; + H30+302H + N2

(n = 2, 3, 4, and 5)

67

The hydrogenation reaction was carried out smoothly in refluxing toluene
for 12 h and the reducing reagent was employed in large excess to ensure a
complete reduction of all carbon-carbon double bonds. The 1H and 13C NMR
spectra of the hydrogenated polymers provided spectroscopic evidence that
complete reduction was achieved in all four polymers. As an example, Figure
27 displays the 1H NMR spectrum of hydrogenated polymer PH5H. In this figure,
the multiple peaks between 3.63 and 3.54 ppm belong to the protons on the
ethylene oxide units. Their position and pattern are unchanged from PH5 to
PH5H. The multiplet peak at 5.35 ppm that corresponded to proton on the
internal double bond, however, is absent, indicating double bonds no longer exist
in this hydrogenated polymer. The structural change from PH5 to PH5H is
reflected in the 13C NMR spectrum (Figure 28) as well. The adjacent peaks at
130.24 and 129.74 ppm characteristic of internal trans and cis double bonds can
not be detected in the spectrum. NMR data proved that perfectly alternating
polyethylene/polyethylene oxide (AB)n copolymers were successfully prepared

by the reduction reaction shown in Scheme 20.

2. Physical properties of the hydrogenated polymers
The molecular weights and molecular weight distributions of the
hydrogenated polymers are listed with those of the unsaturated polymers in
Table 7. Interestingly, there was a remarkable decrease in number-average
molecular weight during hydrogenation for each pair. For example, Mn of PH2

was 44,700, but after reduction, Mn of PH2H dropped to

68

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70

24,800. Since the molecular weights were measured relative to monodisperse
polystyrene standards by GPC, each molecular weight is not an absolute value
of the true molecular weight but a relative one reflecting the coil sphere size of
macromolecules in dilute solution. From the chemical structure, the absolute
molecular weight change of each polymer before and after reduction of the
double bonds is negligible. The decrease of relative molecular weight may be a

sign of decrease of coil sphere size for the saturated polymers.

Table 7. GPC Data Comparison Between the Hydrogenated Polymers and

Their Unsaturated Precursors

+0“: H2’C H20)n—(C H2)10‘}7

 

 

 

Unsaturated Polymer Hydrogenated Polymer
n Mn PDI Mn PDI
2 44,700 2.74 24,800 2.09
3 32,200 2.12 24,900 2.00
4 28,100 2.16 13,100 2.06
5 31,500 2.01 18,400 1.81

 

The saturated polymers PH2H, PH3H, PH4H and PH5H show a number
of notable properties, some of which differentiate them from the original

unsaturated polymers. Unlike the unsaturated polymers that have a greenish

71

brown color, these polymers appear to be opaque with a white color. The
remnants of the molybdenum catalyst may have been removed from the
polymers after the reduction reaction and work-up procedure. Because the
polarity of the saturated polymers is not significantly altered, they exhibit the
same good solubility in a variety of organic solvents that dissolve the unsaturated
precursors, such as toluene, tetrahydrofuran, methylene chloride, chloroform,
carbon tetrachloride, and acetonitrile. The hydrogenated polymers are

hygroscopic and tend to gradually absorb moisture from environment.

3. Thermal behavior of the hydrogenated polymers

The thermal properties of the four hydrogenated polymers were studied by
DSC analysis in the same way as for the unsaturated polymers. The second
DSC heating and cooling scans of PH2H is displayed in Figure 29. In contrast
to the unsaturated polymers, the glass transition of PH2H is not clearly defined in
this plot. Following a minor melting peak and a minor crystallization peak, a
major melting transition was seen with a peak melting temperature of 46 °C in
the heating scan. This transition confirms that PH2H is a crystalline polymer at
room temperature. When the sample was cooled, a sharp crystallization peak
was observed at 29 °C.

Similarly, the Tg of PH3H was not detected in its DSC thermograms
(Figure 30). A melting transition appeared at 37 °C in the heating scan, followed
by a minor second melting peak. In the cooling scan a well-defined

crystallization transition was observed at 22 °C. Both Tm and Tc of PH3H are

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lower than corresponding Tm and To of PH2H, which has one less ethylene oxide
unit in the repeating unit.

The T9 of PH4H was not seen in its DSC thermograms (Figure 31).
Compared with corresponding unsaturated polymer PH4 (Figure 23), the
thermal transitions of PH4H show a strikingly similar pattern in its heating scan,
though the transition temperatures are higher. After a melting peak followed by
a crystallizing peak, the main melting transition appeared at 29 °C. The cooling
curve for PH4H is much simpler, showing only one crystallizing peak at 4 °C.

In the second heating scan of PH5H (Figure 32), the hydrogenated
polymer exhibits multiple melting and crystallizing transitions in the heating scan,
with the major melting peak at the same temperature as the Tm of PH4H. lts
crystallizing temperature measured during cooling is also close to that of PH4H.

The DSC study proves that all hydrogenated polymers are crystalline at
room temperature. The absence of observable Tg’s for the polymers probably
reflects the high crystallinity in these materials. The thermal transition

temperatures of the hydrogenated polymers are summarized in Table 8.

75

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8% 229882.

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Ill-0?... 1

v-v“vo

 

 

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76

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M“ QC=OOU .......
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77

Table 8. Thermal Transition Temperatures for the Hydrogenated Polymers.

 

 

Polymer Tg (°C) Tm (°C)b Tc (°C)c
PH2H NDa 46 29
PH3H ND3 37 22
PH4H NDa 29 4
PH5H ND3 29 5

 

a Not detected.

" Taken as the temperature at the peak of the major melting transition
in the second heating scan.

° Taken as the temperature at the peak of the major crystallization

transition in the second cooling scan.

4. Morphology of the hydrogenated polymers
The crystalline phase in the hydrogenated polymers was directly observed
by polarized optical microscopy. After being melted and hot pressed between
two glass slides, the hydrogenated polymer films were allowed to cool. At room
temperature, crystalline regions were seen to form slowly in the thin polymer
films. As the polarized light optical micrograph of PH2H shows in Figure 33, this
hydrogenated polymer consisted of scattered crystalline domains after extended

cooling at room temperature. The typical Maltese cross pattern

78

 

Figure 33. Polarized light optical micrograph of PH2H.

79

 

Figure 34. Polarized light optical micrograph of PH3H.

W i

w?

80

was observed, indicating the formation of spherulites in the crystalline polymer.
The cross pattern is more easily seen in the micrograph of PH3H (Figure 34),
which showed better developed spherulites. The same characteristics were also

seen in the micrographs of PH4H and PH5H.

81

IV. Polymer Electrolytes Based on the Unsaturated Polymers

Polymer electrolytes formed from the unsaturated polymers PP2, PP3,
PP4, PH3, PH4 and PH5 with various LiCIO4 contents were studied. Thermal
properties of these polymer electrolytes were examined by DSC analysis, and
their ionic conductivities were measured by impedance spectroscopy over the

temperature range of 20 to 100 °C.

1. Thermal behavior of the polymer electrolytes

DSC analysis of the polymer electrolytes was performed in the same way
as for the unsaturated polymers. The second heating scans of PP2 and its
LiClC)4 salt complexes at different salt concentrations are compiled in Figure 35.
The DSC curves show a glass transition for each sample that increases with
increasing salt concentration in the sample (Figure 36). No other thermal
transition was observed for these samples, indicating PP2—salt complexes are
amorphous in the salt concentration range studied.

The DSC curves recorded for amorphous polymer PP3 and its salt
complexes are shown in Figure 37. Similar to polymer electrolytes from PP2,
the glass transition was the only thermal transition observed for electrolytes from
PP3. These polymer-salt complexes exhibited higher Tg's for higher salt

contents (Figure 38).

82

 

 

Endo

32

 

 

pure

fw/

-1OO -50 O 50 100
Temperature (°C)

 

 

 

Figure 35. 2nd heating DSC scans of PP2 and its LiClO4 salt complexes at
different salt concentrations. Numbers refer to molar O:Li ratios for each

sample. Heating rate is 10 °Clmin,

83

 

-45

T9 (°C)
>

-65

 

 

 

0.00 0.05 0.10 0.15

Xsalt (molar fraction)

Figure 36 T9 as a function of the salt molar fraction for PP2-salt complexes.

84

 

 

 

 

 

/ 15

32

..f’ .4

pure

Endo

 

 

 

“fr”!

-100 -50 0 50 100
Temperature (°C)

 

 

 

Figure 37. 2nd heating DSC scans of PP3 and its LiCIO4 salt complexes at

different salt concentrations. Numbers refer to molar O:Li ratios for each

sample. Heating rate is 10 °Clmin.

85

 

10

-10

T9 (°C)

-50 A

 

 

 

0:00 0.05 0.10 0.15 0.20 0.25

X53" (molar fraction)

Figure 38 Tg as a function of the salt molar fraction for PP3-salt complexes.

86

Figure 39 depicts the second heating DSC scans of polymer PP4 and
PP4- LiCIO4 salt complexes. As for PP2 and PP3, polymer electrolytes from PP4
displayed increasing Tgs as the salt concentration increased (Figure 40). PP4
displayed interesting multiple melting and crystallization transitions above its Tg,
however, none of these thermal transitions appeared in the DSC measurements
of salt complexes from PP4. Even the PP4-salt complex with an O:Li ratio of 64
is amorphous, suggesting the crystalline phase present in the pure polymer at
low temperature can easily be eliminated by dissolving a small amount of salt in
the polymer.

The second DSC heating scans of PH3 and its salt complexes are
displayed in Figure 41. As increasing amounts of salt are dissolved in the
complexes, their Tg values increase accordingly (Figure 42), the same trend
seen in previous cases. Pure PH3 shows a crystallization transition peak
followed by two melting peaks. The thermal behavior of its salt complex (O:Li =
64), however, was affected by the presence of salt. Compared with PH3, the
crystallization peak shifted to a higher temperature, while the peak intensity
lowered, indicating increased difficulty for crystallization and a decreased overall
crystallinity. The melting peaks decreased as well, but the corresponding
temperatures stayed the same, suggesting that the crystalline phase was pure
PH3. When the molar O:Li ratio is 32 in the salt complex, only small bumps
corresponding to crystallization and melting were seen in the DSC heating scan.
The complexes become totally amorphous and free of crystallization and melting

transitions when the O:Li ratio is 16 and lower.

87

 

Endo

 

\

 

32

64

pure

 

 

-1 00 -50 0
Temperature (°C)

50

100

Figure 39. 2nd heating DSC scans of PP4 and its LiClO4 salt complexes at

different salt concentrations. Numbers refer to molar O:Li ratios for each

sample. Heating rate is 10 °Clmin.

88

 

T9 (°C)

 

 

~90
0.00 0.05 0.10 0.15 0.20 0.25

Xsalt (molar fraction)

 

Figure 40. Tg as a function of the salt molar fraction for PP4-salt complexes.

89

 

12

 

32

N4 6.

pure

 

Endo

 

 

 

 

-100 -50 0 50 100

Temperature (°C)

Figure 41. 2nd heating DSC scans of PH3 and its LiCIO4 salt complexes at
different salt concentrations. Numbers refer to molar O:Li ratios for each

sample. Heating rate is 10 °Clmin.

90

 

T9 (°C)
('11
o

-70

 

 

 

0.00 0.05 0.10 0.15 0.20 0.25

X53" (molar fraction)

Figure 42. Tg as a function of the salt molar fraction for PH3-salt complexes.

91

Figure 43 includes the second heating DSC curves of PH4 and polymer
electrolytes from PH4 at various salt concentrations. The common feature
observed in the other polymer electrolytes is also seen in this figure: an
increasing Tg for polymer electrolytes with higher salt content (Figure 44). In
addition, the multiple crystallization and melting transitions seen in PH4 were
also found for PH4-salt complexes with O:Li ratios of 64, 48, and 32. The
crystallization following the glass transition also moved to noticeably higher
temperatures as the salt content increased. While the temperature at which the
melting peaks appeared did not change appreciably, the intensity of the peaks
decreased with decreasing O:Li ratios. Similar to electrolytes from PH3, the
crystallization and melting transitions of PH4 remained visible in DSC scans to
O:Li ratios of 32, but for O:Li<24, the polymer electrolytes were amorphous and
only glass transitions were observed.

The last polymer electrolytes studied by DSC were those from
unsaturated polymer PH5 and the results were plotted in Figures 45 and 46.
Except for the detailed shapes of the melting and crystallization peaks, the

results mirror those of PH3 and PH4.

92

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

4
‘ 8
f
1 2
————'—‘-'/F— A
16
A ~——-"’
24
u—a—I—‘"/_ v
32
O
'0
C
I.” M/A
mA/A a.
-100 -50 O 50 1 00

Temperature (°C)

Figure 43. 2nd heating DSC scans of PH4 and its LiClO4 salt complexes at

different salt concentrations. Numbers refer to molar O:Li ratios for each sample.

Heating rate is 10 °Clmin.

93

 

T9 (°C)

 

 

 

0.00 0.05 0.10 0.15 0.20 0.25

X5am (molar fraction)

Figure 44. Tg as a function of the salt molar fraction for PH4-salt complexes.

94

 

 

 

 

 

 

 

4
8

— f
12

 

 

32

Endo

64

 

pure

 

 

 

 

-100 -50 0 50 100

Temperature (°C)

Figure 45. 2nd heating DSC scans of PH5 and its LiClO4 salt complexes at

different salt concentrations. Numbers refer to molar O:Li ratios for each

sample. Heating rate is 10 °Clmin.

95

 

-40

T9 (°C)
'a

 

 

 

0.00 0.05 0.10 0.15 0.20 0.25

X55m (molar fraction)

Figure 46. T9 as a function of the salt molar fraction for PH5-salt complexes.

96

2. Impedance spectroscopy of the polymer electrolytes

Impedance spectroscopy measurements were used to measure the ionic
conductivities of the unsaturated polymer electrolytes at different temperatures.
At each temperature, both the real and imaginary components of a sample's
impedance were obtained over the frequency range of 5 Hz to 10 MHz. The plot
of the imaginary impedance vs. the real impedance resulted in a complex
impedance diagram, as exemplified in Figure 47. This complex impedance
diagram, obtained for a PP4-salt complex (O:Li = 4) at 50 °C, is composed of an
arc that describes the complex impedance of the sample cell at high frequencies,
and a linear spike following the arc that corresponds to the impedance at low
frequency. The intercept of that line on the real axis, 7.2 K0, was taken as the
bulk resistance of the electrolyte cell. As the dimensions of the cell were known,
the conductivity of PP4-salt complex (O:Li = 4) at 50 °C could be derived by
simple calculation.

Figure 48 shows the complex impedance diagram for a PH4-salt complex
(O:Li = 32) at 30 °C. The arc in this figure is incomplete near the origin, because
the upper frequency limit of the measurement was too low to obtain the complex
impedance in that region. This phenomenon is usually seen when the bulk
impedance of the sample is small, but it does not affect the extrapolation of the
linear portion of the data. From the intercept on the real axis, a bulk resistance

of 2.2 K!) was obtained for this sample.

97

 

 

 

 

 

10000
8000 ~
E 6000 r
.c
O
f x
[x'] .
4000 — X
l X
~ X
xxxx X x §
2000 f
:{X X
ohllLrtttttitilti 111..¥
0 2000 4000 6000 8000 1 0000
Z'(Ohm)

Figure 47. Complex impedance diagram for PP4-salt complex (O:Li = 4) at 50

°C.

:igl

98

 

 

 

 

’ x
3000 F
7 x
x
... ” x
E 2000 ~ 3.:
5 ~ :1:
,
z x X
1000 x x x
” x
i
0 1 1 1 1 1 1 1 1 1 l 1 1 1 l
0 1000 2000 3000
2' (Ohm)

Figure 48. Complex impedance diagram for PH4—salt complex (O:Li = 32) at 30

°C.

2.0

Incr

and 5C

99

The ionic conductivities of the unsaturated polymer-salt complexes at

various temperatures appear in the Appendix.

3. Conductivity behavior of the polymer electrolytes

The effects of salt concentration and temperature on ionic conductivity of
the unsaturated polymer-LiCIO4 complexes were examined. Figures 49-54
display the results for the PP2, PP3, PP4, PH3, PH4, and PH5 salt complexes.
At each temperature, for example, 20 °C, the conductivity increases as the salt
content in the electrolyte increases. After reaching a maximum, the conductivity
decreases with further increases in salt content. The conductivity also shows
strong dependence on the temperature. The conductivity of all salt
concentrations increases systematically as a result of increased temperature.
The peak conductivity for electrolyte from PP2 (Figure 49) is 7.9x10‘ S/cm at 20
°C, increases to 3.5x10'5 S/cm at 50 °C, and reaches 1.7x10“ S/cm at 100 °C.

For PP3 (Figure 50) the room temperature conductivity maximum of
2.0x10‘5 S/cm was achieved with a molar O:Li ratio of 12. This conductivity
increased to 7.9x10‘5 S/cm at 50 °C, and 4.1x10“ S/cm at 100 °C. Although the
conductivity maximum was obtained at almost the same salt content (O:Li ratio
of 12) for all three temperatures, the peak conductivity shows a tendency of
moving toward higher salt concentration. It is also interesting to see that as the
temperature increases, the conductivity peak becomes broader.

The conductivity of PP4-salt complex as a function of salt content at 20 °C

and 50 °C are shown in Figure 51. The conductivity of an amorphous PEO-

100

 

 

 

 

1.05-03
100°C
V o
9 9
1015-04 ’
Q . 50°C
I
A A A
A A
5 1
‘2’, 1.0E-05 I I . < 20°C
b I
1.0E-06
I
roe-07
o 0.05 0.1 0.15 0.2 0.25

Xsalt (molar fraction)

Figure 49. Conductivity of PP2-LiCIO, complexes as a function of salt content at

20 °C, 50 °C and 100 °C.

101

 

 

 

 

1.0503 ,
. ’ ’ < — 100°C
105-04 . . o
“ A A «mu 50°C
A
9 A
E I I ---.“ 20°C
0
(7) 1.0E-05 1 A I
v I
b
I A
1.0E-06 .
105.07 I
0 0.05 0.1 0.15 0.2 0.25

X33" (molar fraction)

Figure 50. Conductivity of PP3-LiClO4 complexes as a function of salt content at

20 °C, 50 °C and 100 °C.

102

 

1.0E-03
H o. «I—M amorphous PEO at 50 °C
1.0E-04 19 A .
" A A A 4 50°C
0
A b ‘
g l - 20°C
‘2’, 1.0E-05 E . <
o 1 I
I A
1.0E-06 .
I
1.0E-07

 

 

 

0.00 0.05 0.10 0.15 0.20 0.25
X5am (molar fraction)

Figure 51. Conductivity of electrolytes from PP4 and amorphous PEO as a

function of salt content at 20 °C and 50 °C.

103

 

 

 

 

1.0E-03
O . ‘___- 100°C
’ o
1.0E-04 -
O
<———-— 50°C
A A A
O
A ' A
E A .
‘2’, 105-05 1 I I <—~~- 20 C ‘
b I I I
1.0E-06
I
1.0E-07
0 0.05 0.1 0.15 0.2 0.25

xsalt (molar fraction)

Figure 52. Conductivity of PH3-LiCIO4 complexes as a function of salt content at

20 °C, 50 °C and 100 °C.

104

 

 

 

 

105-03 1
l O
- <---——-- 100°C
. .
O O
1-05'04 ~ A <—~—~ 50 °C
. A A
9 A
—.—-- 20 °C
’5 A I I I : A
0
£7; 1.05-05 .
b I
1.0E-06
' I
1.0E-07
0 0.05 0.1 0.15 0.2 0.25

XS,"t (molar fraction)

Figure 53. Conductivity of PH‘twLiCIO4 complexes as a function of salt content at

20 °C, 50 °C and 100 °C.

105

 

 

 

 

1.05-03
. Q 6 <~ 100°C
0 9
1.0504 : .‘ ‘ A ‘4__ 50°C
A
25:
£71 A
b I I I ‘ 20°C ‘
105-05 I
I
I
1.0E-06
0 0.05 0.1 0.15 0.2 0.25

Xsalt (molar fraction)

Figure 54. Conductivity of PH5-LiClO4 complexes as a function c: ‘ salt content at

20 °C, 50 °C and 100 °C.

106

LiClO, complex as a function of salt content at 50 °C is also included in the same
figure. For PP4, the room temperature conductivity maximum was 1.6x10'5 Slcm
at a molar O:Li ratio of 32, and 8.3x10'5 Slcm at 50°C with an O:Li ratio of 16.
The highest conductivity of amorphous PEO electrolytes was reported to be
2.4x10‘ Slcm at 50 °C.9 The conductivity of PP4-salt complexes at 50 °C is
comparable to that of amorphous PEO-LiCIO4 complexes at the same
temperature, but the peak conductivity was achieved at a higher O:Li ratio for
PP4-salt complexes.

The salt concentration-dependent conductivity of PH3-LiCIO4 complexes
is given in Figure 52. The dependence of conductivity on salt concentration
observed for electrolytes from PP2, PP3 and PP4 holds for electrolytes from
PH3. The peak conductivity at room temperature was found to be 1.0x10‘5'S/cm
for the sample with an O:Li ratio of 16. The peak value improved to 3.9x10'5
Slcm with an O:Li ratio of 12 at 50 °C. The highest conductivity for PH3
electrolytes was obtained as 2.3x10“ Slcm at 100 °C with an O:Li ratio of 8.

The relationship between conductivity of electrolytes from PH4 and the
salt concentration was also examined (Figure 53). For example, the peak
conductivity of PH4 electrolytes was determined to be 2.1x10'5 Slcm, 1.0x10“
Slcm and 5.7x10“ Slcm at 20 °C, 50 °C and 100 °C respectively.

As expected, the conductivity of electrolytes from PH5 showed the same
dependence on the salt concentration as observed for other electrolytes in this
research (Figure 54). The conductivity maximum of electrolytes from PH5 was

determined to be 2.3x10’5 Slcm for an O:Li ratio of 32 at 20 °C, 1.2x10“ S/cm for

107

an O:Li ratio of 16 at 50 °C, and 4.9x10" Slcm for an O:Li ratio of 8 at 100 °C

respectively.

4. Temperature dependent conductivity

The VTF equation has been commonly used to model the temperature
dependent conductivity of polymer electrolytes.80 Here we used the VTF
equation to examine the relationship between the structure and conductivity of
the unsaturated polymer-based electrolytes.

Figure 55 shows the VTF plots for PP2-LiClO4 complexes at four salt
concentrations. The O:Li ratios are 32, 16, 12, and 4 respectively. Values of T0
were taken as the Us of the corresponding electrolytes measured in the DSC
studies. At each salt concentration, a linear relationship was well established
between logarithm of the conductivity (Log 0‘) and 1/(T - To), as predicted by the
VTF equation. Although the four lines are not perfectly parallel to each other,
they appear to have similar slopes (same activation energy), suggesting the
conduction mechanism is the same in all samples.

Figures 56-60 give the VTF plots for PP3, PP4, PH3, PH4 and PH5-
LiClO, complexes. All plots of Log 0 vs. 1/(T - T0) are linear, agreeing well with
the VTF equation. In many cases, slopes of the samples from each polymer are

found to have similar values.

108

 

-4.5 »

Log 6 (Slcm)

 

 

 

-5.5
0.000 0.005 0.010 0.015 0.020

1/0 -T.)

 

Figure 55. VTF plots for PP2-LiClO4 complexes with O:Li ratio of 32, 16, 12, and

4.

109

 

 

 

 

 

-3
X
C
O:Li = 16 "up
.4
E O:Li = 32 - m2...
9
b
m
0
_J
—5
O:Li = 64 ->
.5
0.000 0.005 0.010 0.015 0.020

1/(T - To)

Figure 56. VTF plots for PP3-LiClO4 complexes with O:Li ratio of 64, 32, 16, and
12.

110

 

Log 0 (Slcm)

 

 

 

 

0.000 0.005 . 0.010 0.015
1/(T - To)

0.020

Figure 57. VTF plots for PP4-LiCIO4 complexes with O:Li ratio of 64, 32, 16, and
8.

111

 

 

 

 

 

-3.5
O:Li = 32 A
\,
’5‘ -4.5 ‘
2
L”,
o
o:
o
_.|
O:Li = 64 ——.->
-5.5
-6.5 .
0.000 0.005 0.010 0.015 0.020 0.025

1/(T'To)

Figure 58. VTF plots for PH3--LiCIO4 complexes with O:Li ratio of 64, 32, 8, and
4.

112

 

O:Li = 64

Log 6 (Slcm)
c'n

 

 

 

-7
0.000 0.005 0.010 0.015 0.020 0.025
1/(T - To)

 

Figure 59. VTF plots for PH4-LiClO4 complexes with O:Li ratio of 64, 32, and 4.

113

 

Log 0 (Slcm)

.5
<11

O:Li =64 ._ -

 

 

-5.5
0.000 0.005 0.010 0.015

1/(T"To)

 

 

0.020 0.025

Figure 60. VTF plots for PH5-LiCIO4 complexes with O:Li ratio of 64, 32, 8, and
4.

DISCUSSION

l. Scope of ADMET Polymerization in Synthesizing Target Polymers

Three aspects of ADMET polymerization were examined in the present
research: ( 1) the effectiveness of metathesis catalysts in the synthesis of target
polymers; (2) how monomer structure affects the polymerizability of monomers in
ADMET polymerization; and (3) the ease of ADMET polymerization in giving

polymers in the desired molecular weight range.

1. ADMET polymerization catalysts

While ADMET polymerization has proven to be a convenient method to
prepare various unsaturated polymers, only a limited number of metathesis
catalysts are capable of polymerizing acyclic dienes with different functionalities.
In an effort to find a suitable catalyst for the preparation of the target polymers,
the reactivity of both a conventional metathesis catalyst, WCI6/Sn(CH3)4/PrOAC
system, and Schrock’s Mo alkylidene catalyst were tested with oligo(ethylene
oxide) segmented (mo-diene monomers.

It was reported that 1,4-polybutadiene oligomer (Mn = 2,970, PDI = 2.43)
was successfully prepared“ when WCI,,/Sn(CH3)4 mixture was applied to the
hydrocarbon monomer, by introducing a Lewis base, n-propyl acetate, into the

catalyst mixture to quench unwanted side reactions. However, the

114

115

WClelSn(CH3)4/PrOAc system failed to polymerize P3 and H4. The ether
structures in these two monomers were expected to provide additional difficulty
for this Lewis acid catalyst, since the oxygen atoms in monomers P3 and H4 can
easily coordinate to the center W atom. Such interactions may hinder or totally
destroy the metathesis reactivity of the catalyst, and give rise to side reactions.

However, Schrock’s molybdenum alkylidene catalyst was successful in
the synthesis of the target polymers. The use of this Lewis acid free metathesis
catalyst effected a clean and efficient polymerization that generated a variety of
unsaturated ethylene oxide segmented polymers.81 Although Schrock’s Mo
catalyst is a very well designed metathesis catalyst, it has several limitations in
practical applications. First, the preparation of this catalyst requires a multistep
organometallic synthesis in an oxygen and moisture-free environment. As a
result, the cost of this catalyst is high. Second, since it is an extremely oxygen
and moisture-sensitive compound, great care is needed in storing, handling, and
transferring this catalyst. The monomers for ADMET polymerization also must
be dry and of high purity. Third, it is difficult to remove catalyst traces from the
products, and ADMET polymers usually have an undesirable greenish brown
color. Nevertheless, as demonstrated by the work of Wagener et al. and results
in this research, Schrock’s well-defined single-component molybdenum

alkylidene catalyst is an excellent choice for ADMET polymerizations.

116

2. Polymerizability of the monomers

The potential application of the target polymers as solid polymer
electrolytes also requires a good understanding of the structure-property
relationship in the target polymers. The general structure of the target polymers
(shown in Scheme 8) suggested that both the number of methylene units and
the length of ethylene oxide chain could be altered to refine theproperties of the
unsaturated polymers. From the polymer synthesis point of view, this offered
some Challenging questions. First, is there a limit to the number of methylene
units that can be incorporated into a monomer and still lead to a successful
polymerization? If there is, what are structural features that prevent that
monomer from being polymerized by ADMET?

In the synthesis of the unsaturated polymers, it was found that monomers
with 3, 4, and 6 methylene units between the vinyl group and the oligo(ethylene
oxide) segment all polymerized via ADMET. The number of ethylene oxide units
in these monomers ranged from 2 to 5, and had no effect on the polymerizability
of these monomers. This result agreed well with Wagener’s work,"6 which
showed that when two or more methylene groups separate oxygen atoms from
the terminal double bond, ADMET polymerization proceeds and generates high
polymers.

Wagener et al‘6 further found that Schrock’s W catalyst failed to
polymerize di-3-butenyl ether (Scheme 21). Since there were only two
methylene units to separate oxygen atom and the vinyl end group, it was

proposed that an interaction between the carbon-carbon double bond and the

117

oxygen atom with the catalyst metal atom may block the metathesis reaction and

poison the catalyst.

Scheme 21. Failed ADMET polymerization to make an unsaturated
polyether

catalyst

NOW ————> no high polymer

VV//j
? \:O
W

Another possible explanation is suggested by recent work by Grubbs and
coworkers”89 on ring-closing metathesis reactions. Ring—closing metathesis,
outlined in Scheme 22, competes with ADMET polymerization. Instead of
forming an unsaturated linear polymer, an acyclic diene can be cyclized by a
metathesis catalyst. Similar to ADMET polymerization, the mechanism of a ring-
closing reaction (Scheme 23) involves formation of two metallocyclobutane rings
as reactive intermediates. After the first metathesis forms a new carbene
species, the second metallocyclobutane ring forms by reacting with another
double bond from the same diene. Ring-closing reactions are usually carried out

in solution with a low concentration of the acyclic diene, so that the probability

118

Scheme 22. Competition between ring-closing metathesis reaction and

 

ADMET polymerization
ring-closing
metathesis
WXW 7' Z S + CZH4 I

X
l ADMET polymerization

quj + C2H4I

Scheme 23. Mechanism for ring-closing metathesis reaction

 

‘x
LnM=CH2 W—
+ LnM—
WXW
1L] HzC—CHZ
/\ __._
[— x ____ LnM—CH—\

 

119

of metathesis reaction between double bonds on the same diene (intramolecular)
is higher than the reaction between different diene molecules. A favorable ring
size is equally important in a ring-closing reaction; five-, six-, seven- and even
eight-membered carbocyclic and heterocyclic products are most commonly seen.

Various heterocycles, such as cyclic ethers82 and nitrogen-containing
heterocycles,83 were prepared by ring-closing metathesis reaction. A ring-Closing
metathesis reaction example relevant to ADMET polymerization in this research
is given in Scheme 24."2 In the starting diene, one carbon-carbon double bond
was separated from the oxygen atom by one carbon atom, the other double
bond was separated from the oxygen by two. A six-membered cyclic ether was
produced in this metathesis reaction. This example implies that it is possible for
monomers with one or two carbon atoms separating terminal double bond and
oxygen atom to undergo ADMET polymerization, if ring formation can be

suppressed.

Scheme 24. An example of ring-closing metathesis reaction to prepare a

 

cyclic ether
/ Schrock's Mo catalyst
l -
benzene, 20 °C, 15 min, 92%
Me

Me —

120

Even though di-4-butenyl ether could not be polymerized into high
molecular weight polymer, monomer 82, a structurally homologous molecule,
polymerized using Schrock’s Mo catalyst. Compared to di-4—butenyl ether, BZ is
longer by two ethylene oxide units, long enough to inhibit the ring-closing
reaction, which occurs easily with di-4-butenyl ether.

It is now necessary to consider the ADMET polymerization of monomer
A2, which contains only one methylene group between the double bond and
oxygen atom. When catalyst was added to A2, ethylene gas was released, but
the polymerization never yielded oligomer or polymer of reasonable molecular
weight. However, the reasons behind this failed polymerization are complicated.
When the A2 and BZ monomers were purified, they could not be dried with a
sodium mirror, as it was found that monomers with one or two methylene units
between double bond and oxygen atom reacted with sodium metal to give
unknown products. They were only purified by repeated distillation over CaHz,
so they may not be absolutely anhydrous. Other possibilities, such as catalyst
poisoning caused by monomer structure, and a competing ring-closing reaction,
can not be excluded at this time. The polymerizability of monomer A2 needs

further investigation.

3. Controlling molecular weights
ADMET polymerization of P2, P3 and P4 was carried out for 48 h and for

168 h, to gain an understanding about the achievable molecular weight and

121

polymerization rates at high conversion. The GPC data of the six polymers
PP2a, PP2, PP3a, PP3, PP4a and PP4 are listed in Table 4.

When the reaction time for the polymerization of P2 was extended from 48
h to 168 h, higher molecular weight was achieved for PP2 (168 h) than for PP2a
(48 h). The same trend can be seen for polymers PP3 and PP3a, and PP4 and
PP4a. In all cases, longer polymerization time resulted in higher molecular
weights. In a stepwise ADMET polymerization with perfect stochiometry and no
side reactions that lead to chain ends without double bonds, the degree of
polymerization, Xn is given by the Carothers equation

' Xn = 1/(1 - p)

where p is the fractional conversion of terminal vinyl groups to internal double
bonds. Thus, the extension of polymerization time enhanced the ADMET

conversion, and thus increased the molecular weight.

122

ll. Unsaturated Ethylene Oxide-Segmented Polymers

1. Segment length dependent glass transition temperature

The glass transition temperature is a parameter of great importance for
new synthetic polymers, since its value usually defines potential applications for
the polymer. In this project, it is generally desirable to have polymers with low
glass transitions so that polymer chains are mobile, and enhance the
conductivity of polymer electrolytes. Therefore, an understanding of the effect of
chemical structure on T9 in ethylene oxide segmented polymers would help in
the design of improved polymer electrolytes.

The Tg’s of two series of unsaturated polymers are plotted in Figure 61 as
a function of number of ethylene oxide units in the repeating unit. When there
are three methylene units in the polymer structure (m = 3, polymers PP2, PP3
and PP4), the Tg increases about 2 °C per ethylene oxide unit (solid triangles) in
the repeating unit of the polymer.

The same trend can be seen when there are four methylene units in the
structure (m = 4, polymers PH2, PH3, PH4 and PH5). Polymer PH2 has the
lowest T9 (-81 °C), and T9 increases by 2 to 3 °C with each additional ethylene

oxide unit (solid circles) for PH3, PH4 and PH5.

123

 

 

 

 

-72
-74 I
A
-76 n
6
a, A e
o:
I"
-78 r
‘ . . m = 4
'80 - ‘ m = 3
.
-82
1 2 3 4 5 6

number of E0 units (n)

Figure 61. Ethylene oxide segment length dependent Tg in unsaturated

polymers

+(CH2)m——O(CHZCH20)n—(CH2)m—CH=CH%;

The unsaturated polymers PBZ, PP2 and PH2 all have two ethylene oxide
units in their repeating units but a different number of methylene units. Their Tg’s
are plotted as a function of number of methylene units, as shown in Figure 62
(solid squares). In this polymer series, Tg decreases with increasing numbers of

methylene units, from -72 °C for m = 2, to -79 °C for m = 3, to -81 °C for m = 4.

124

The Tg’s of polymers PP4. PH4 and P04 (four ethylene oxide units in the
repeating unit) decrease as the methylene content increases (solid diamonds in

Figure 62), similar to the trend observed for PBZ, PP2 and PH2.

-70

 

-72 I

T9 (°C)
;,
o:

-80

 

 

-82

 

1 2 3 4 5 6
number of methylene units (m)

Figure 62. Methylene unit dependent Tg in several unsaturated, polymers

+(CH2)m—-o(cHzcnzo)n——(CH2)m—CH=CH—}x—

The dependence of the Tg of a one-phase copolymer on the Us of its two

components is given by a simple equation”

125

T9 = w,Tg1 + an2
where w1 and w2 are the weight fractions of components 1 and 2 in the
copolymer respectively, while T91 and T92 are the glass transition temperatures of
homopolymers of component 1 and component 2. This equation was applied to
several unsaturated polymers prepared in this project. For example, polymers
PP2, PP3 and PP4 can be generally regarded as (AB), segmented copolymers,
with the hydrocarbon chain one segment and oligo(ethylene oxide) the other.
The glass transition temperature of PEO is known to be -65 °C, but the Tg of the

unsaturated polyether

+(C H2)3—C H=CH—(C H2)3—O—}T

was not reported in the article that described its synthesis.“ We derived a value
of -88 °C by using the above equation and the T9 of PP2 obtained from DSC
measurements. Based on these data, the Tg’s of PP3 and PP4 were calculated.
In the same way, the T1, of PH3, PH4 and PH5 were obtained.

The experimental and calculated Tg’s of several polymers are listed in
Table 9. Except for PH5, the calculated Tg for each polymer is in good
agreement with the DSC measurements, indicating the equation provides a
reliable Tg prediction for other unsaturated polymers in this project. These
results further confirmed that there is no phase separation in the unsaturated

polymers.

126

Table 9. The Measured and Calculated Tg of Some Unsaturated Polymers

 

 

Polymer Measured Tg (°C) Calculated Tg (°C)
PP3 -77 ~77
PP4 ~75 ~75
PH3 ~79 ~79
PH4 ~77 ~77
PH5 ~74 ~76

 

The equation can also be used to explain qualitatively the segmental
dependence of Tg in the unsaturated polymers. There is a linear relationship
between the T9 of a copolymer and the Us of the homopolymers of the two
components A and B in the copolymer. If the Tg of homopolymer A is higher
than the Tg of homopolymer B, the higher the weight fraction of A, the higher the
Tg of the copolymer. In contrast, the higher the weight fraction of B, the lower
the Tg of the copolymer. Unsaturated polyethers that have no ethylene oxide
units have lower Tg’s than PEO. Therefore, for polymers with the same number
of methylenes in the repeat unit, increasing the number of ethylene oxide units in
a repeating unit gives higher Tg’s, and for a fixed number of ethylene oxide units,

the more methylene units in a repeating unit, the lower the Tg of the polymer.

127

2. Melting transitions
Many of the unsaturated polymers displayed well-defined crystallizing and
melting transitions in their DSC thermograms. As shown in Table 6, the Tg/T m
ratios for these polymers fall between 0.70 to 0.76. These values are close to
2/3, the suggested ratio of Tg/T m for nonsymmetrical crystalline polymers by the

Boyer-Beaman rule.91

'0' “I

 

 

15 I;

10

Tm (°C)
0

~10

 

 

~15

 

1 2 3 4 5 6
number of EO units (n)

Figure 63. Melting temperature as a function number of ethylene oxide units in

unsaturated polymers

+(CH2)4—0(CH2CHzo)n——(CH2)4——CHzCH—I;

128

The melting points for the highest melting phases of polymers PH2, PH3,
PH4 and PH5 are plotted in Figure 63. Polymers with an even number of
ethylene oxide units (PH2 and PH4) have lower melting points than those with
odd number of ethylene oxide units (PH3 and PH5).

The study on the relationship between structure and crystalline transitions
of unsaturated polymers and the hydrogenated polymers is currently undenlvay in

our group.

129

III. Electrolytes from the Unsaturated Polymers

1. Conductivity and E0 content
The highest conductivities obtained for each electrolyte at three
‘ temperatures are compiled in Table 10. The weight fraction of the ethylene
oxide segment in each polymer is also included. Except for the PP4-salt
complex at 20 °C, the conductivity of LiCIO4 salt complexes from PP2, PP3 and
PP4 increases with increasing EO content. Since the hydrocarbon segment in
each polymer acts as a filler and does not contribute to the conductivity, the
conductivity in these three polymers is generally low. Therefore an increase in
E0 segment fraction in the polymers is expected to result in higher conductivity.
A similar trend can be seen for electrolytes from polymers PH3, PH4 and
PH5. Except for conductivity of PH4-salt complex at 100 °C, conductivity of other
samples increases as EO content increases at the same temperature.
As the conductivity of electrolytes from the unsaturated polymers is not
satisfactory at this stage, the dependence of conductivity on the E0 content in
these polymers offers an effective approach to increase the overall conductivity

of the unsaturated polymers.

130

Table 10. Peak Conductivity' of the Unsaturated Polymers

at 20 °C, 50 °C and 100 °C

 

 

speak (Slcm)

Polymer EO (%)b 20 °C 50 °C 100 °C
PP2 49 7.9x10"3 3.5x10'5 1 .7x10“
PP3 57 2.0x10'5 7.9x10'5 4.1x10“
PP4 64 1 .6x10‘5 8.3x10‘5
PH3 52 1.0x10‘5 3.9x10’5 2.2x10“
PH4 58 2.1x10’5 1.0x104 5.7x10“
PH5 63 2.3x10‘5 1 .2x10" 4.9x10"

 

3 Highest conductivity measured for that polymer at a temperature.

° Weight fraction percentage of ethylene oxide segment in a polymer.

2. Parameters in the VTF equation
The parameters A and B for the VTF equation, o(T) = A exp[-B/(T ~ T°)],
were obtained in the polymer-salt complexes with an O:Li ratio of 32 in Table 11.
The values of A for samples from PP2, PP3 and PP4 increase as the E0 fraction
in the polymer increased. This again shows the dependence of conductivity on
the E0 content in the unsaturated polymers. Similarly, A increases for

electrolytes from PH3, PH4 and PH5 with increasing E0 fraction.

131

It is interesting to note that the values of B for all six samples are similar.
Since parameter B in the VTF equation is related to the activation energy for the
ionic conduction, comparable B values for the six electrolytes indicate that they

likely have the same conduction mechanism.

Table 11. The VTF Parameters for Polymer-Salt Complexes

with an O:Li Ratio of 32

 

 

Polymer EO (%)a T, (°C)° A (Slcm) B (K)
PP2 49 ~69 1.2x10'3 549
PP3 57 ~69 1.7x10'3 568
PP4 64 ~65 2.7x10'3 508
PH3 52 -72 0.8x10° 530
PH4 58 ~69 2.6x10’3 525
PH5 63 ~66 3.5x10-° 555

 

a Weight fraction percentage of ethylene oxide segment in a polymer.

° Taken as the Tg of the sample in the DSC measurement.

132

IV. Summary

In this research, the unsaturated ethylene oxide-segmented polymers
were designed and successfully prepared from oligo(ethylene glycol) 01,0)-
dialkenyl ethers via ADMET polymerization with Schrock’s well-defined
molybdenum alkylidene metathesis catalyst. The polymerizations proceeded to
give high molecular weight polymers in good yields (above 92%). Spectroscopic
methods, including 1H and 13C NMR and IR, were used to confirm the structure of
the polymers. Internal double bonds on unsaturated polymer backbone typically
had a trans geometry (among 82 to 86%). Due to the presence of both
hydrophilic and hydrophobic segments in the polymer Chain, the unsaturated
polymers dissolved well in a variety of polar and nonpolar organic solvents.

TGA analysis demonstrated that the unsaturated polymers have good
thermal stability both in air and in nitrogen. No significant thermal degradation
took place for these polymers at 300 °C, but a rapid thermal breakdown followed
at higher temperatures and only traces were left when the temperature reached
500 °C. The unsaturated polymers showed segment length—dependent US from
DSC measurements. Some of the unsaturated polymers are crystalline at low
temperature and interesting multiple crystallization and melting transitions were
observed in their DSC scans.

Four unsaturated polymers were hydrogenated to yield perfectly

alternating polyethylene/p0Iyethylene oxide (AB), copolymers. The

133

hydrogenation reaction was carried out in refluxing toluene using p-
toluenesulfonhydrazide for several hours, and NMR monitoring showed that a full
reduction was achieved. The resulting hydrogenated polymers are crystalline at
room temperature, and their thermal behavior was studied by DSC
measurements.

The polymer-LiCIO, complexes were prepared by combining the
unsaturated polymers and salt in acetonitrile and drying the samples. The Tg of
each of these polymer electrolytes was found to increase with increasing salt
content. The ionic conductivities of the polymer electrolytes were measured in IS
experiments. The conductivity isotherms of the polymer-salt complexes
indicated that the conductivity increased at low salt contents, reached a
maximum and then decreased. The conductivity alsoincreased as the
temperature increased. The temperature-dependent conductivities fit the Vogel-
Tammann-Fulcher (VT F) equation. Finally, electrolytes with higher ethylene

oxide content displayed higher conductivities.

134

V. Suggestions for Further Research

Based on the results in this work, several directions can be taken in future
research. First, a better understanding of relationship between polymerizability
and monomer structure is necessary. Investigation can be carried out on
ADMET polymerization of monomers with one methylene spacer separating the
terminal vinyl group and ethylene oxide segment. Monomers having different
numbers of ethylene oxide units, which can be prepared using the same
preparation for this work, should be considered.

Recent work by Grubbs et al.6365 provided another type of efficient
metathesis catalysts, the ruthenium carbene catalysts. Compared with
Schrock’s molybdenum alkylidene catalsyt, the ruthenium catalysts have several
advantages, such as easier preparation and handling, and tolerance toward
moisture and oxygen. As purification and drying of monomers with longer
ethylene oxide segment is expected to become harder, the ruthenium catalysts
may substitute for Schrock’s catalyst in polymer preparation.

Both unsaturated and hydrogenated ethylene oxide-segmented polymers
displayed interesting segment length-dependent thermal behavior in DSC study.
Efforts can be directed toward the understanding in the molecular level factors
that govern the thermal changes.

The ionic conductivity of the polymer electrolytes prepared from the
unsaturated polymers is still low at room temperature. One approach to improve

the conductivity is suggested by structure-property relationship discovered in the

135

present work. As the conductivity showed a systematic increase as the ethylene
oxide content increased, future unsaturated polymers should be prepared with
longer ethylene oxide chains to enhance overall conducting segment fraction.
Increasing the E0 content in the polymer can also be achieved by attaching EO
side chains to the double bond functionality to make comb-branched polymers

with E0 segments on both backbone and side chains of the material.

EXPERIMENTAL

I. General

Unless otherwise specified, ACS reagent grade starting materials were
used as received from commercial suppliers without further purification. Melting
points and boiling points were uncorrected. Glassware used for ADMET
polymerization was soaked in a potassium hydroxide/ethanol base bath
overnight, thoroughly rinsed with distilled water, and oven dried at 160 °C for one
day.

Proton and carbon nuclear magnetic resonance (‘H and 13C NMR) analyses
of monomers and polymers were carried out at room temperature in deuterated
chloroform (CDCI3) on a Varian Gemini-300 spectrometer, the solvent proton and
carbon signals being used as chemical shift standards respectively. Quantitative
13C NMR spectra used to determine the trans / cis ratio of the internal double
bonds on polymer backbone were obtained on a VXR-300 NMR spectrometer.
Infrared (IR) spectra of both monomers and polymers were recorded as CCI,
solutions under nitrogen at room temperature on a Nicolet lR/42 Fourier
Transform IR spectrometer. The spectrum of each pure compound was obtained
by subtracting the CCI4 spectrum from that of the solution. High resolution mass
spectra of the monomers were measured by the Michigan State University Mass

Spectroscopy Facility, with a heated direct inlet on a JEOL AX-505H double-

136

137

focusing mass spectrometer. Elemental analyses were carried out by the
Microanalysis Laboratory at University of Illinois, Urbana-Champaign, using a
CE440 Carbon, Hydrogen, Nitrogen Analyzer (Exeter Analytical, lnc.). Molecular
weights were determined by gel permeable Chromatography (GPC) using a
PLgel 20m Mixed A column at room temperature with THF as eluting solvent at a
flow rate of 1 mUmin. The concentration of the polymer samples were 2 mg/mL.
Detection was by a Waters R401 Differential Refractometer. The results were
calibrated with monodisperse polystyrene standards. Therrnogravimetric
analyses (T GA) of the polymers were obtained from a Perkin Elmer TGA 7
instrument at a heating rate of 10 °Clmin, usually in the temperature range of 30
to 800 °C. For each polymer, one run was performed in air and one in nitrogen.
Differential scanning calorimetry (DSC) analysis of the polymers and polymer
electrolytes was performed in aluminum pans under a nitrogen/helium
atmosphere on a Perkin Elmer DSC 7 instrument, calibrated with indium.
Coolant for the system was liquid nitrogen. Each run was carried out by heating
from ~100 °C to 100 °C at a rate of 10 °Clmin, quenching immediately to ~100 °C
at a rate of 200 °Clmin, heating to 100 °C at a rate of 10 °Clmin, and cooling
back to ~100 °C at a rate of 10 °Clmin. The glass transition temperature, T9, was
defined as midpoint temperature of the transition, and the melting point was
taken as the temperature at the peak of the melting endotherm. The polymer
samples (2 ~ 4 mg) for microscopy were prepared by heating samples to 80 °C
on a Mettler FP 82 HT hot stage and pressing the sample between two clean

glass slides. Polarized optical microscopy of the hydrogenated polymers PH2H,

 

138

PH3H, PH4H and PH5H was carried out with a Nikon OptiphotZ-Pol Microscope
in polarized light at ambient temperature after the polymers crystallized and
became opaque. Micrographs were taken with a Nikon FX-35DX camera that
was directly connected to the microscope. Polymer electrolyte cells for
impedance spectroscopy (IS) measurements were prepared by sandwiching bulk
electrolytes between two stainless steel electrodes separated by a Teflon O-ring,
and pressing with a Carver Laboratory Press (Model 2112) at 80 °C. The
polymer electrolytes thus prepared typically had a diameter of 1.12 cm and
ranged from 400 to 600 microns in thickness as determined with a Mitutoyo 101~
103 micrometer. The impedance spectra of the polymer/LiCIO4 complexes were
measured using a Hewlett-Packard 4192A LF Impedance Analyzer in a
frequency range of 5 Hz to 10 MHz. Measurements were made from 20 to 100
°C by heating the cells in a VWR Scientific 141OD oven. The thickness and area
of each cell was measured at 20 °C and was not corrected for different operating
temperatures. Data collection and processing were performed through an HPIB
interface using software from this laboratory on a Gateway 2000 4DX2~66V

personal computer.

1. Solvents
Acetonitrile was distilled over phosphorus pentoxide (P205) under nitrogen
and was stored over activated 4 A molecular sieves. Reagent grade diethyl
ether was distilled from sodium benzophenone ketyl under nitrogen. Anhydrous

dimethoxyethane (99.5%) was distilled from sodium benzophenone ketyl under

139

nitrogen. Reagent grade pentane (4 L) was vigorously stirred over concentrated
sulfuric acid (H2804, 300 mL), which was changed every 12 h until the acid
remained colorless. The pentane was then stirred over a 500 mL solution of
potassium permanganate (KMnO4,0.5 M) and H280, (3 M) for one day. After
separation from the aqueous phase, the pentane was washed with distilled water
(4x500 mL), saturated solution of sodium bicarbonate (NaHCOa, 500 mL) and
distilled water (2x500 mL), and dried over anhydrous magnesium sulfate
(M9804). The pentane was filtered and distilled from calcium hydride and then
from sodium benzophenone ketyl under nitrogen. Tetrahydrofuran (THF) was
dried first by distilling from calcium hydride and then from sodium benzophenone
ketyl under nitrogen. Toluene was dried by distilling first from calcium hydride

and then from sodium benzophenone ketyl under nitrogen;

2. Argon

Argon used in air—sensitive reactions was deoxygenated by passing it
through a 60 cm (8 cm in diameter) Mn°lSiO2 column.

Raw column filling material. An acidic manganese nitrate [Mn(N03)2]
solution was prepared by mixing Mn(N03)2(H20),, (500 g), concentrated nitric acid
(HNO3, 50 mL) and distilled water (500 mL). The clear light pink solution was
blended with silica gel (60 ~ 200 mesh, 500 g). The blended silica gel was
transferred into a 2000 mL beaker and the beaker was heated with a silicone oil
bath at 180 °C in a well-ventilated hood for 72 h, with occasional stirring until no

NO and N02 were no longer evolved. The raw filling material was black.

 

140

Column generation/regeneration. The quartz column wrapped with
heating wire and filled with the raw filling material was heated to at least 450 °C
under a flow of hydrogen gas (H2). The color of the filling material turned from
black to brown to green, and moisture was evolved from the column. The
generation process lasted about 10 h and was followed by switching the H2 flow
to argon for 2 h with continued heating. Traces of H20 were removed by
connecting the column to vacuum for 30 min.

After it was used for a period of time, the filling material in the column

turned from green to brown, and the column regeneration process was repeated.

3. Sodium mirror
Sodium mirror coated Schlenk flasks were prepared by heating a piece of
fresh sodium metal (0.2 9) inside a Clean flask with a burner under high vacuum

until the molten sodium vaporized and coated the walls of the flask.

141

II. Preparation of Monomers

1. Diethylene glycol a,m-diallyl ether (A2)

A mixture of sodium hydride powder (6.70 g, 95% purity, 0.265 mol) in dry
THF (450 mL) was placed in a nitrogen filled 1000 mL flask equipped with a
Claisen adapter, a cold water condenser and a dropping funnel. To this stirred
mixture was slowly added a solution of allyl alcohol (12.8 g, 0.221 mol) in THF
(30 mL) over a period of 30 min, while a stream of hydrogen evolved. The
reactionmixture was stirred at room temperature for 12 h. Then a solution of
diethylene glycol di-p-tosylate (43.5 g, 0.105 mol) in THF (150 mL) was added
and the reaction was stirred under reflux for 72 h. The mixture was cooled to
room temperature and was filtered through a coarse fritted funnel with a 2 cm
layer of Celite" to removed insoluble solids. The resulting solution was
concentrated and the product was purified by repeated distillation over CaH2
under vacuum, to yield a clear colorless liquid. Yield: 16.6 g (85.0 %). B.P.: 38.2
- 39.9 °C I<0.05 mm Hg. 1H NMR (300 MHz, CDCIa) 6 (ppm): 5.90 (ddt, J= 17.3,
10.4, 5.7 Hz, 2H), 5.25 (dq, J: 17.2, 1.6 Hz, 2H), 5.16 (dq, J: 10.4, 1.4 Hz, 2H),
4.01 (dt, J: 5.7, 1.4 Hz, 4H), 3.67-3.57 (m, 8H). 13C NMR (300 MHz, CDCI3) 6
(ppm): 134.68, 116.90, 72.11, 70.57, 69.34. IR (CC|,,): cm'1 3083, 3017, 2865,
1647, 1551, 1451, 1420, 1345, 1107, 995, 926, 884, 745. HRMS m/z calc for
C,,,H,,,O3 (M’) 186.1256, found 186.1225; calc for C,,,H,,,O3 (M*+1) 187.1334,

found 187.1320.

 

142

2. Diethylene glycol a,m-di~3-butenyl ether (32)

Monomer 82 was prepared in a similar way as for A2. The reaction of 3-
buten-1-ol (12.5 g, 0.173 mol), NaH (5.68 x 95% g, 0.225 mol), and diethylene
glycol di-p-tosylate (34.2 9, 0.0824 mol) in THF (650 mL) yielded 11.4 g (64.4 %)
of clear colorless product after repeated vacuum distillation over CaHz. B.P.:
46.1 ~ 48.3 °C I<0.05 mm Hg. 1H NMR (300 MHz, 000;) 6 (ppm): 5.80 (ddt, J=
17.1, 10.3, 6.8 Hz, 2H), 5.10-4.99 (m, 4H), 3.65-3.56 (m, 8H), 3.51 (t, J= 6.9 Hz,
4H), 2.33 (qt, J= 6.8, 1.3 Hz, 4H). 1"C NMR (300 MHz, CDCI3) 8 (ppm): 135.08,
116.19, 70.57, 70.53, 70.08, 34.05. IR (CCL): cm'1 3081, 3002, 2980, 2941,
2872, 2838, 1981, 1837, 1642, 1555, 1480, 1456, 1431, 1418, 1325, 1296,
1244, 1138, 1048, 990, 916, 878, 747, 639. HRMS m/z calc for C12H22O3 (M‘)

214.1569, found 214.1543.

3. Diethylene glycol or,w-di-4-pentenyl ether (P2)
5-lodo-1-pentene was prepared from 5-bromo-1-pentene, according to a
literature procedure.92 In a 1000 mL flask with a condenser and a drying tube, a
mixture of 5-bromo-1-pentene (42.8 g, 0.287 mol) and sodium iodide (300 g,
2.00 mol) in acetone (600 mL) was refluxed in darkness. After 20 h, the acetone
solution from the reaction was combined with distilled water (500 mL) to give a
homogeneous solution, which was extracted with ether (3x300 mL). The

combined ether extracts were washed with saturated NaCl solution (3x500 mL)

143

and distilled water (500 mL), and dried over anhydrous M9304. Ether and
MgSO4 were removed and the resulting liquid was distilled. The product was
collected at 144 - 147 °C as a light pink liquid (41.6 g, 74.0%). 1H NMR (300
MHz, CDCI3) 6 (ppm): 5.74 (ddt, J: 17.1, 10.3, 6.7 Hz, 1H), 5.10-4.98 (m, 2H),
3.18 (t, J= 6.9 Hz, 2H), 2.15 (q, J: 7.0 Hz, 2H), 1.89 (q, J: 7.0 Hz, 2H).

To a 500 mL round-bottom flask at room temperature under argon and
Charged with a stirred mixture of sodium hydride (3.79 g, 95% purity, 0.150 mol)
in dry THF (250 mL), was added dropwise a solution of diethylene glycol (5.30 9,
0.0500 mol) in THF (40 mL). After 12 h a solution of 5-iodo-1-pentene (29.4 g,
0.150 mol) in THF (30 mL) was added dropwise. The reaction was heated to
reflux after 6 h and the course of the reaction was followed by 1H NMR. After an
extended time (more than 72 h) the reaction mixture was filtered through a
coarse fritted funnel with a 3 cm layer of Celite‘”. After removal of solvent, the
resulting liquid was distilled over CaH2 in vacuo to yield a clear colorless liquid. It
was further purified by stirring over a fresh sodium mirror in a 50 mL Schlenk
flask, followed by a second vacuum distillation, and was stored in helium filled
drybox for future use. Yield: 7.53 g (62.2%). B.P.: 67.4 ~ 68.5 °C/<0.05 mm Hg.
1H NMR (300 MHz, CDCl,) 6 (ppm): 5.80 (ddt, J: 17.0, 10.2, 6.7 Hz, 2H), 5.04-
4.91 (m, 4H), 3.65-3.55 (m, 8H), 3.45 (t, J= 6.6 Hz, 4H), 2.09 (q, J: 7.2 Hz, 4H),
1.66 (q, J: 7.1 Hz, 4H). 13C NMR (300 MHz, CDCI3) 6 (ppm): 138.28, 114.65,

70.69, 70.62, 70.11, 30.21, 28.75. IR (CCI4): crt'l'1 3081, 2977, 2942, 2927,

144

2869, 1642, 1551, 1451, 1350. 1298, 1250, 1121, 994,914,631. HRMS m/z

calc for C1,,H2603 (M‘) 242.1882, found 242.1884.

4. Triethylene glycol a,m-di-4~pentenyl ether (P3)

An argon-filled 500 mL flask at room temperature was charged with
sodium hydride (3.79 g, 95% purity, 0.150 mol) in dry THF (200 mL). Added
dropwise to the stirred mixture was a solution of triethylene glycol (7.51 9, 0.0500
mol) in dry THF (40 mL). After stirring for 24 h, 5-bromo-1-pentene (25.5 g,
0.171 mol) was added, and the reaction was heated to reflux for 96 h. Following
the same work-up and drying procedure as for diethylene glycol a,w~di-4-
pentenyl ether, triethylene glycol a,m-di-4-pentenyl ether was obtained as a clear
liquid by vacuum distillation at 92.8 ~ 93.4 °C/<0.05 mm Hg. Yield: 10.6 g
(73.8%). It was degassed with four freeze-pump-thaw cycles and then stored in
a helium-filled drybox for future use. 1H NMR (300 MHz, CDCI3) 6 (ppm): 5.79
(ddt, J: 17.1, 10.3, 6.7 Hz, 2H), 5.03-4.91 (m, 4H), 3.64-3.54 (m, 12H), 3.45 (t,
J: 6.7 Hz, 4H), 2.09 (q, J: 7.2 Hz, 4H), 1.66 (q, J: 7.1 Hz, 4H). 13C NMR (300
MHz, CDCI3) 6 (ppm): 138.28, 114.65, 70.68, 70.61, 70.09, 30.21, 28.76. IR
(CCI.): cm" 3081, 2998, 2942, 2917, 2869, 1642, 1451, 1350. 1296, 1246,
1121, 994, 876, 637. HRMS m/z calc for C,6H300,, (M‘) 286.2144, found

286.2138.

145

5. Tetraethylene glycol a,co~di-4~pentenyl ether (P4)

Monomer P4 was prepared as described for diethylene glycol a,a)-di-4~
pentenyl ether using tetraethylene glycol (8.74 g, 0.045 mol) in THF (120 mL),
NaH (3.41 g, 95% purity, 0.135 mol), and 5-bromo-1-pentene (14.9 g, 0.100 mol)
in dry THF (50 mL). The colorless liquid tetraethylene glycol di-4-pentenyl ether
was purified by distillation at 124.1 ~ 125.0 °CI<0.05 mm Hg. Yield: 12.1 g
(81.2%). 1H NMR (300 MHz, CDCI3) 6 (ppm): 5.79 (ddt, J= 17.1, 10.3, 6.7 Hz,
2H), 5.03491 (m, 4H), 3.64-3.54 (m, 16H), 3.45 (t, J= 6.7 Hz, 4H), 2.09 (q, J:
7.2 Hz, 4H), 1.66 (q, J: 7.1 Hz, 4H). 13C NMR (300 MHz, CDCla) 6 (ppm):
138.28, 114.67, 70.69, 70.59, 70.10, 30.21, 28.76. IR (COL): cm" 3081, 2998,
2979, 2942,2919, 2869, 1642, 1451, 1350, 1296, 1246, 1121, 994, 914, 641.

HRMS m/z calc for c,,H,,o, (M’) 330.2406, found 330.2416.

6. Diethylene glycol a,(o-di-5~hexenyl ether (H2)
Diethylene glycol a,w~di~5~hexenyl ether was prepared as described for
A2. After repeated vacuum distillation over CaH2 and a sodium mirror, a clear
colorless liquid was obtained (23.8 g, 84.0%). B.P.: 87.2 - 88.4 °C I<0.05 mm
Hg. 1H NMR (300 MHz, CDCI3) 6 (ppm): 5.78 (ddt, J= 17.0, 10.3, 6.7 Hz, 2H),
5.02-4.90 (m, 4H), 3.65-3.54 (m, 8H), 3.44 (t, J= 6.7 Hz, 4H), 2.04 (q, J= 7.1 Hz,
4H), 1.58 (m, 4H), 1.42 (m, 4H). 13C NMR (300 MHz, CDCIS) 6 (ppm): 138.60,

114.36, 71.12, 70.54, 69.99, 33.43, 28.97, 25.27. IR (CCI4): CM1 3079, 2938,

146

7. Triethylene glycol a,w-di-5-hexenyl ether (H3).
Triethylene glycol a,m-di~5~hexenyl ether was prepared as described for

A2. A clear colorless liquid was obtained after repeated vacuum distillation over
CaH2 and sodium mirrors. Yield: 23.5 g (71.3%). B.P.: 105.5 - 88.4 °C /§0.05
mm Hg. ‘H NMR (300 MHz, CDCI3) 6 (ppm): 5.78 (ddt, J = 17.0, 10.3, 6.7 Hz,
2H), 5.01-4.89 (m, 4H), 3.63-3.54 (m, 12H), 3.44 (t, J = 6.6 Hz, 4H), 2.04 (q, J =
7.1 Hz, 4H), 1.63-1.53 (m, 4H), 1.46-1.36 (m, 4H). 13C NMR (300 MHz, CDCI3) 6
(ppm): 138.58, 114.36, 71.10, 70.48, 69.94, 33.40, 28.94, 25.24. IR (CCl4): cm"
3079, 2938, 2867, 1827, 1642, 1551, 1456, 1441, 1416, 1350, 1323, 1298,
1246, 1121, 1044, 994, 913, 745, 633. HRMS m/z calc for CwHasO. (M*+1)

315.2491, found 315.2506.

8. Tetraethylene glycol a,w-di-5-hexenyl ether (H4)
Tetraethylene glycol a,w-di~5—hexenyl ether was prepared as described for
A2 to give a clear cplorless liquid. Yield: 29.3 g (77.9%). B.P.:132.1 -133.5 °C,
< 0.05 mm Hg. 1H NMR (300 MHz, CDCI3) 6 (ppm): 5.78 (ddt, J= 17.0, 10.2, 6.7
Hz, 2H), 5.02-4.90 (m, 4H), 3.64-3.54 (m, 16H), 3.44 (t, J= 6.6 Hz, 4H), 2.04 (q,
J: 7.1 Hz, 4H), 1.58 (m, 4H), 1.41 (m, 4H). 13C NMR (300 MHz, CDCla) 6 (ppm):
138.55, 114.34, 71.07, 70.45, 69.92, 33.38, 28.92, 25.22. IR (CCI4): cm" 3079,

2938,2867, 1827, 1642, 1551, 1456, 1441, 1350, 1323, 1298, 1246, 1121,

147

1042, 994, 949, 913, 745, 633. HRMS m/z calc for CZOH3,,O5 (M’) 358.2719,

found 358.2737.

9. Pentaethylene glycol a,co-di-5-hexenyl ether (H5)

Using the same procedure used to prepare A2, H5 was obtained as a
clear colorless liquid, after purification by distillation over CaH2 and a Na mirror.
Yield: 28.9 g (68.5%). B.P.: 155.9 - 157.2 °C/<0.05 mm Hg. 1H NMR (300 MHz,
CDCI3) 6 (ppm): 5.79 (ddt, J = 17.1, 10.3, 6.7 Hz, 2H), 5.03-4.91 (m, 4H), 3.64-
3.54 (m, 20H), 3.45 (t, J = 6.7 Hz, 4H), 2.04 (q, J = 7.1 Hz, 4H), 1.64-1.53 (m,
4H), 1.45-1.36 (m, 4H). 13C NMR (300 MHz, CDCI3) 6 (ppm): 138.58, 114.36,
71.10, 70.45, 69.93, 33.40, 28.92, 25.24. IR (CCI4): cm'1 3079, 2938, 2867,
1831, 1642, 1551, 1456, 1416, 1350, 1323, 1298, 1248, 1121, 1042, 994,948.

913, 747. HRMS m/z calc for CZZHQOS (M‘) 402.2981, found 402.2918.

10. Diethylene glycol a,m-di-7-octenyl ether (02)
7-Octen~1~ol, a colorless oil, was prepared by dehydrochlorination of 8-
chloro~1~octanol according to the literature method .93'9‘ To a stirred mixture of
potassium t-butoxide (31.3 g, 95% purity, 0.265 mol) in dry dimethyl sulfoxide
(DMSO, 700 mL) in a 2000 mL flask, was added dropwise a solution of 8~chloro~
1~octanol (29.2 g, 0.177 mol) in DMSO (50 mL) under argon at room
temperature. After 2 h, the reaction mixture was combined with ether (500 mL)

and washed with 1 M acetic acid (300 mL), 2M NaOH solution (300 mL), and

148

distilled water (3 x 500 mL). After filtration and removal of solvent, the crude
product was distilled under vacuum. Yield: 15.3 g (67.5 %). 1H NMR (300 MHz,
CDCIa) 6 (ppm): 5.79 (ddt, J= 17.0, 10.3, 6.7 Hz, 1H), 5.01-4.89 (m, 2H), 3.62 (t,
J= 6.6 Hz, 2H), 2.03 (q, J= 7.0 Hz, 2H), 1.55 (m, 2H), 1.33 (m, 6H), 1.33 (s, 1H).

Diethylene glycol a,co-di-7~octenyl ether was prepared using the method
described for A2 from 7-octen-1-ol and diethylene glycol p-ditosylate as a clear
colorless liquid. Yield: 7.70 g (82.9%). B.P.: 138.2 - 140.5 °C<0.05 mm Hg. 1H
NMR (300 MHz, CDCla) 6 (ppm): 5.78 (ddt, J= 17.0, 10.2, 6.7 Hz, 2H), 5.02-4.88
(m, 4H), 3.64-3.54 (m, 8H), 3.43 (t, J= 6.8 Hz, 4H), 2.02 (q, J= 6.6 Hz, 4H), 1.56
(m, 4H), 1.41-1.31 (m, 12H). 13C NMR (300 MHz, CDCIa) 6 (ppm): 138.95,
114.10, 71.36, 70.57, 70.01, 33.63, 29.50, 28.85, 28.76, 25.86. IR (CCl4): cm'1
3079, 2932, 2881, 1642, 1551, 1456, 1415, 1350, 1323, 1298, 1246, 1121,
1042, 995, 912, 804. HRMS m/z calc for Con;.,,,O3 (M’) 326.2821, found

326.2866.

11. Tetraethylene glycol a,w~di-7~octenyl ether (04)

Monomer 04, a clear colorless liquid, was prepared using the method
described for A2. Yield: 12.0 g (78.4%). B.P.: 174.5 - 177.2 °C<0.05 mm Hg.
1H NMR (300 MHz, CDCla) 6 (ppm): 5.78 (ddt, J: 17.0, 10.2, 6.8 Hz, 2H), 5.02-
4.88 (m, 4H), 3.63-3.54 (m, 16H), 3.43 (t, J= 6.8 Hz, 4H), 2.03 (q, J= 6.7 Hz, 4H),
1.55 (m, 4H), 1.42-1.31 (m, 12H). 13C NMR (300 MHz, CDCI3) 6 (ppm): 138.65,

113.92, 71.10, 70.33, 69.80, 33.41, 29.29, 28.63, 28.54, 25.65. IR (CCI4): cm"1

149

3079, 2932, 2861, 1642, 1549, 1456, 1350, 1324, 1296, 1242, 1119, 1042, 995,

912, 804. HRMS m/z calc for C2,,H4505 (M’) 414.3345, found 414.3343.

 

150

Ill. ADMET Polymerization Catalysts

WCl6/Sn(CH3),/PrOAc was prepared as described by Nubel, Lutman and
Yokelson.54 Mo(CHCMezPh)(NAr)[OMe(CF3)2]2, Schrock’s molybdenum
alkylidene catalyst was prepared starting from M002, using the five-step

synthesis reported in literature procedure.62

151

IV. Synthesis of Unsaturated Ethylene Oxide-Segmented Polymers

1. Polymer from diethylene glycol a,m-di~3~butenyl ether (PBZ)

In a helium filled drybox, monomer BZ (0.500 g, 2.34 x 10'3 mol) was
placed in a 30 mL Schlenk tube with a stir bar. To this was added Schrock’s Mo
catalyst (15 mg) and the mixture was vigorously stirred at room temperature.
The reaction vessel was removed from the drybox and high vacuum (<0.02 mm
Hg) was applied to the system to remove ethylene generated during the
polymerization. After 6 h, the reaction temperature was raised to 50 °C by
heating with a silicone oil bath. When the reaction mixture became too viscous
to stir, toluene (3 mL) and Schrock’s Mo catalyst (3 mg) were added. The
polymerization was terminated after 7 days by exposing it to air. The toluene
solution of the product was filtered through Celite" and polymer PBZ was
precipitated into n-heptane and dried in vacuo at room temperature until constant
weight was reached. Yield: 0.394 g (92.8%). M,, = 15,100, PDI = 1.86. 1H NMR
(300 MHz, CDCIa): 6 (ppm) 5.45 (m, 2H), 3.63-3.54 (m, 8H), 3.44 (t, J = 7.1 Hz,
4H), 2.29-2.23 (m, 4H). 13C NMR (300 MHz, CDCla): 6 (ppm) 128.24, 127.38,
70.97, 70.46, 69.96, 32.89, 27.85. IR (CCl4): cm'1 2867, 1549, 1456, 1350,

1324, 1296, 1242, 1119, 1041, 970, 885, 804.

2. Polymer from diethylene glycol 01,01-di-4-pentenyl ether (PP2)
PP2a. Under helium environment in a drybox, monomer P2 (2.00 g,

8.26x10'3 mol) was placed in a 50 mL Schlenk tube with a magnetic stir bar.

152

After the catalyst (15 mg) was added, the mixture was vigorously stirred at room
temperature for 20 min, and the reaction vessel was connected to high vacuum
(<0.02 mm Hg). As for polymerization of 82, the reaction was heated to 50 °C
after 6 h. When the reaction mixture became too viscous to stir, toluene (10 mL)
and catalyst (5 mg) were added. The polymerization was terminated after 48 h
by exposing it to air. PP2a was purified in the same manner as for PB2. Yield:
1.68 g (95.0 %). M,, = 17,700, PDI = 2.15. 1H NMR (300 MHz, CDCI3): 6 (ppm)
5.38 (m, 2H), 3.64-3.53 (m, 8H), 3.42 (t, J = 6.7 Hz, 4H), 2.09-1.98 (m, 4H), 1.61
(q, J = 7.1 Hz, 4H). 13C NMR (300 MHz, CDCIa): 6 (ppm) 129.94, 129.51, 70.74,
70.54, 70.03, 29.35, 28.94, 23.60. IR (CCl4): cm'1 2940, 2914, 2867, 1555,
1449, 1350, 1294, 1246, 1121, 968, 879, 754. Anal. Calcd. for (C,2H2203),,
(PP2-1): C, 67.25; H, 10.35; 0, 22.40. Found: C, 66.50; H, 10.51; 0, 22.99.
PP2. A 7~day polymerization of P2 (2.00 g, 8.26x10’3 mol), carried out in
the same way as for PP2a, gave 1.73 g (97.8 %) of PP2. M, = 93,900, PDI =
2.29. Anal. Calcd. for (C,2H2203), (PP2): C, 67.25; H, 10.35; 0, 22.40. Found:

C, 67.66; H, 10.91; 0, 21.43.

3. Polymer from triethylene glycol a,w-di-4~pentenyl ether (PP3)
PP3-1a. The polymer was prepared by ADMET polymerization of P3
(2.00 g, 6.99x10'3 mol) with Mo catalyst (15 mg) in the same way as for PP2a.
Yield: 1.72 g (95.3 %). M, = 18,300, PDI = 3.10. 1H NMR (300 MHz, CDCI3): 6

(ppm) 5.38 (m, 2H), 3.64-3.53 (m, 12H), 3.42 (t, J = 6.7 Hz, 4H), 2.09-1.97 (m,

153

4H), 1.61 (q, J = 6.9 Hz, 4H). 13C NMR (300 MHz, 000,): 6 (ppm) 129.96,
129.54, 70.78, 70.55, 70.03, 29.38, 28.96, 23.63. IR (CCI4): cm‘1 2949, 2909.
2869, 1551, 1451, 1350, 1262, 1119, 968, 868, 754. Anal. Calcd. for
(C14H2604),: C, 65.08; H, 10.14; 0, 24.78. Found: C, 65.57; H, 10.60; 0, 23.83.

PP3. A 7-day polymerization of P3, done in the same way as for PP3a,
gave 1.73 g (95.9 %) of PP3. M,, = 55,000, PDI = 2.57. Anal. Calcd. for

(C14H2604),,: C, 65.08; H, 10.14; 0, 24.78. Found: C, 65.22; H, 10.60; 0, 24.18.

4. Polymer from tetraethylene glycol a,m-di-4~pentenyl ether (PP4)
PP4a. The polymer was prepared by ADMET polymerization of P4 (2.00
g, 6.06x10'3 mol) with Mo catalyst (15 mg) in the same way as for PP2a. Yield:
1.77 g (96.7 %). M,, = 37,300, PDI = 2.21. 1H NMR (300 MHz, CDCIa): 6 (ppm)
5.38 (m, 2H), 3.63-3.53 (m, 16H), 3.42 (t, J = 6.7 Hz, 4H), 2.09-1.97 (m, 4H),
1.60 (q, J = 7.1 Hz, 4H). 13C NMR (300 MHz, CDCI3): 6 (ppm) 129.942, 129.50,
70.73, 70.50, 69.99, 29.34, 28.92, 23.59. IR (CCI,): cm'1 2940, 2916, 2869,
1549, 1451, 1350, 1296, 1248, 1121, 968, 874, 744. Anal. Calcd. for
(C,6H3005),: C, 63.54; H, 10.00; 0, 26.46. Found: C, 62.56; H, 10.41; 0, 26.03.
PP4. A 7~day polymerization of P4 (2.00 g, 6.06x10'3 mol), carried out in
the same way as for PP4a, gave 1.79 g (97.8 %) of PP4. M,, = 66,400, PDI =
2.24. Anal. Calcd. for (C,6H3005),: C, 63.54; H, 10.00; 0, 26.46. Found: C,

63.74; H, 10.64; 0, 25.62.

154

5. Polymer from diethylene glycol a,w-di-5~hexenyl ether (PH2)

The polymer was prepared by ADMET polymerization of H2 (6.20 9,
0.0230 mol) with Mo catalyst (30 mg) as described for PBZ. Polymerization time:
7 days. Yield: 5.28 g (95.0 %). M,, = 44,700, PDI = 2.74. 1H NMR (300 MHz,
CDCIa): 6 (ppm) 5.35 (m, 2H), 3.63-3.53 (m, 8H), 3.42 (t, J = 6.7 Hz, 4H), 2.03-
1.92 (m, 4H), 1.60-1.50 (m, 4H), 1.40-1.30 (m, 4H). 13C NMR (300 MHz, CDCIS):
6 (ppm) 130.18, 129.67, 71.26, 70.53, 69.98, 32.26, 29.16 (cis), 29.02, 26.91
(cis), 26.10 (cis), 25.94. IR (CCL): cm‘1 2938,2865, 1549, 1456, 1350, 1299,
1249, 1121, 970, 801. Anal. Calcd. for (C,,H2,o,), : C, 69.39; H, 10.82; 0,

19.79. Found: C, 68.50; H, 10.49; 0, 21.01.

6. Polymer from triethylene glycol a,co-di~5~hexenyl ether (PH3)
The polymer was prepared by ADMET polymerization of H3 ( 12.5 9,
0.0398 mol) with Mo catalyst (30 mg) as described for PBZ. Polymerization time:
7 days. Yield: 11.1 g (97.4 %). M,, = 32,200, PDI = 2.12. 1H NMR (300 MHz,
CDCI3): 6 (ppm) 5.34 (m, 2H), 3.62-3.52 (m, 12H), 3.41 (t, J = 6.7 Hz, 4H), 2.03-
1.92 (m, 4H), 1.59-1.49 (m, 4H), 1.39-1.29 (m, 4H). 13C NMR (300 MHz, CDCI3):
6 (ppm) 130.01, 129.51, 71.07, 70.35, 69.80, 32.09 (trans), 29.00 (cis), 28.85
(trans), 26.75 (cis), 25.94 (cis), 25.78 (trans). IR (CCI4): cm" 2942, 2869, 1549,
1456, 1349, 1249, 1121, 970, 800, 743. Anal. Calcd. for (C,5H3OO,),, : C, 67.09;

H, 10.56; 0, 22.35. Found: C, 66.51; H, 10.66; 0, 22.83.

155

7. Polymer from tetraethylene glycol or,co-di-5-hexenyl ether (PH4)
The polymer was prepared by ADMET polymerization of H4 (15.0 9,
0.0419 mol) with Mo catalyst (30 mg) as described for PBZ. Polymerization time:
7 days. Yield: 13.4 g (97.1 %). M,, = 28,100, PDI = 2.16. 1H NMR (300 MHz,
CDCla): 6 (ppm) 5.38 (m, 2H), 3.63-3.53 (m, 16H), 3.42 (t, J = 6.7 Hz, 4H), 2.04-
1.92 (m, 4H), 1.60-1.50 (m, 4H), 1.40-1.30 (m, 4H). 13C NMR (300 MHz, CDCla):
6 (ppm) 130.01, 129.51, 71.07, 70.33, 69.80, 32.09 (trans), 28.99 (cis), 28.85
(trans), 26.74 (cis), 25.94 (cis), 25.78 (trans). IR (CCI4): cm'1 2937, 2890, 1549,
1456, 1350, 1322, 1299, 1249, 1121, 970, 802. Anal. Calcd. for (C1,,H3405)x : C,

65.47; H, 10.37; 0, 24.22. Found: C, 66.16; H, 10.20; 0, 23.64.

8. Polymer from pentaethylene glycol a,m-di-5-hexenyl ether (PH5)
The polymer was prepared by ADMET polymerization of H5 ( 12.8 9,

0.0318 mol) with Mo catalyst (30 mg) as described for PBZ. Polymerization time:
7 days. Yield: 11.6 g (97.5 %). M, = 31,500, PDI = 2.01. 1H NMR (300 MHz,
CDCI3): 6 (ppm) 5.35 (m, 2H), 3.63-3.53 (m, 20H), 3.42 (t, J = 6.7 Hz, 4H), 2.04~
1.93 (m, 4H), 1.63-1.50 (m, 4H), 1.40-1.30 (m, 4H). 13C NMR (300 MHz, CDCIa):
6 (ppm) 130.24, 129.74, 71.33, 70.53, 70.01, 32.32, 29.22 (cis), 29.08, 26.98
(cis), 26.16 (cis), 26.00. IR (CCI4): cm'1 2946, 2844, 1549, 1456, 1350, 1299,
1241 1121, 970, 802, 742. Anal. Calcd. for (C20H3806), : C, 64.14; H, 10.23; 0,

25.63. Found: C, 64.39; H, 10.50; 0,2511.

156

9. Polymer from diethylene glycol a,m-di-7-octenyl ether (P02)

The polymer was prepared by ADMET polymerization of 02 (5.00 9,
0.0168 mol) with Mo catalyst (15 mg) as described for PBZ. Polymerization time:
4 days. Yield: 4.39 g (96.1 %). M,, = 57,100, PDI = 2.45. 1H NMR (300 MHz,
CDCI3): 6 (ppm) 5.35 (m, 2H), 3.64-3.53 (m, 8H), 3.42 (t, J = 6.8 Hz, 4H), 1.94
(m, 4H), 1.59-1.51 (m, 4H), 1.28 (m, 12H). 13C NMR (300 MHz, CDCI3): 6 (ppm)
130.10, 129.54, 71.37, 70.63, 70.01, 34.89, 29.44, 29.02, 26.95, 25.50, 25.94.
IR (CCL): cm'1 2932, 2859, 1459, 1350, 1324, 1299, 1245, 1121, 1042, 968,

901, 804.

10. Polymer from tetraethylene glycol a,co-di-7-octenyl ether (P04)

The polymer was prepared by ADMET polymerization of 04 (8.50 9,
0.0205 mol) with Mo catalyst (20 mg) as described for PBZ. Polymerization time:
4 days. Yield: 7.53 g (95.0 %). M,, = 35,400, PDI = 2.35. 1H NMR (300 MHz,
CDCI3): 6 (ppm) 5.35 (m, 2H), 3.63-3.53 (m, 16H), 3.43 (t, J = 6.8 Hz, 4H), 1.93
(m, 4H), 1.60-1.50 (m, 4H), 1.28 (m, 12H). 13C NMR (300 MHz, CDCI3): 6 (ppm)
130.17, 129.62, 71.31, 70.55, 69.97, 34.80, 29.41, 29.00, 26.97, 25.53, 25.88.
IR (CCI4): cm'1 2933, 2861, 1458, 1350, 1324, 1296, 1245, 1119, 1042, 968.

901, 804.

157

V. Preparation of Saturated Ethylene Oxide-Segmented Polymers

1. Hydrogenated polymer from PH2 (PH2H)

The hydrogenation of unsaturated polymer PH2 was done according to
the documented procedurem‘79 To a 250 mL Schlenk flask was added a solution
of the unsaturated polymer PH2 (1.00 g) in dry toluene (150 mL), p~
toluenesulfonhydrazide (10 equivalent of the number of the double bonds) and
2,6-di-t-butyl-4-methylphenol (butylated hydroxytoluene, BHT, 0.005 g) as the
radical inhibitor. The mixture was degassed with three freeze-pump-thaw cycles.
Then a cold water condenser with argon inlet and outlet was attached to the
flask under argon environment, and the mixture was heated to reflux in argon
with an oil bath. After 12 h, the mixture was cooled to room temperature and
was filtered through a 60 mL coarse fritted funnel under vacuum. The solution
was washed with 2 M HCI solution (3x150 mL), saturated NaCl solution (3x150
mL) and distilled water (150 mL), and was concentrated with a rotary evaporator.
The resulting polymer was further purified by repeated precipitation into n-
heptane from toluene solution and dried in vacuo until constant weight was
observed. The hydrogenated polymer was then stored in a desiccator for future
Characterization. Yield: 0.427 g (42.7 %). Mn = 24,800, PDI = 2.09. 1H NMR
(300 MHz, CDCIa): 6 (ppm) 3.64-3.54 (m, 8H), 3.42 (t, J = 6.8 Hz, 4H), 1.55 (m,

4H), 1.25 (m, 12H). 13C NMR (300 MHz, CDCI3): 6 (ppm) 71.52, 70.61, 70.04,

158

29.62, 29.53, 29.47, 26.07. IR (CCL): em1 2934, 2863, 1643, 1456, 1349.

1324, 1299, 1249, 1119, 1048, 992, 954, 913, 810, 742..

2. Hydrogenated polymer from PH3 (PH3H)

PH3H was prepared and purified by the same procedure as used for
PH2H. Yield: 0.293 g (29.3 %). Mn = 24,900, PDI = 2.00. 1H NMR (300 MHz,
CDCI3): 6 (ppm) 3.64-3.54 (m, 12H), 3.42 (t, J = 6.7 Hz, 4H), 1.55 (m, 4H), 1.25
(m, 12H). 13C NMR (300 MHz, CDCIa): 6 (ppm) 71.43, 70.50, 69.94, 29.52,
29.44, 29.38, 25.98. IR (CCI,): cm'1 2932,2861, 1455, 1355, 1324, 1292, 1117,

1048, 992, 954, 913, 810, 742.

3. Hydrogenated polymer from PH4 (PH4H)
PH4H was prepared and purified by the same procedure used for PH2H.
Yield: 0.330 g (33.0 %). Mn = 13,100, PDI = 2.06. 1H NMR (300 MHz, CDCla): 6
(ppm) ) 3.63-3.53 (m, 16H), 3.42 (t, J = 6.8 Hz, 4H), 1.55 (m, 4H), 1.25 (m, 12H).
”’0 NMR (300 MHz, CDCIS): 6 (ppm) 71.52, 70.54, 69.99, 29.59, 29.53, 29.46,
26.05. IR (COL): cm‘1 2932,2861, 1732, 1549, 1456, 1350, 1324, 1296, 1249,

1117, 1042, 992, 948, 913, 806, 742.

4. Hydrogenated polymer from PH5 (PH5H)
PH5H was prepared and purified by the same procedure as used for

PH2H. Yield: 0.389 g (38.9 %). M, = 18,400, PDI = 1.81. 1H NMR (300 MHZ,

 

159

CDCIa): 6 (ppm) 3.63-3.54 (m, 20H), 3.42 (t. J = 6.8 Hz, 4H), 1.55 (m, 4H), 1.25
(m, 12H). 13C NMR (300 MHz, CDCI3): 6 (ppm) 71.49, 70.53, 69.99, 29.58,
29.50, 29.43, 26.03. IR (ccr,): cm" 2932,2863, 1456,1350,1324, 1292,1249,

1117,1042,986,947,913,886,823,742.

160

VI. Preparation of Polymer Electrolytes

Polymer electrolytes were prepared from unsaturated polymers and
lithium perchlorate (LiCl04). CH3CN (6 - 8 mL) was added to a vial containing
the polymer sample (usually 0.400 - 0.600 g) and the appropriate amount of
LiCl04. The mixture was stirred until a homogeneous solution was obtained.
The solution was concentrated by solvent evaporation at 70 °C, followed by
drying under high vacuum for 24 h. Sample were further dried under high
vacuum at 120 °C for 2 h. Polymer electrolytes from PP2, PP3, PP4, PH3, PH4
and PH5 were prepared, generally with O:Li ratios of 64:1, 32:1, 16:1, 12:1, 8:1
and 4:1 for each polymer. The polymer electrolytes were stored in a dry and

inert atmosphere.

APPENDIX

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