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Thermal elimination of poly(phenylvinylsulfoxide) and its styrene block copolymers

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Thermal elimination of poly(phenylvinylsulfoxide) and its styrene block copolymers
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Kanga, Rustom Sam
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ix, 135 leaves : ill. ; 28 cm.

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Copolymers ( jstor )
Molecular weight ( jstor )
Monomers ( jstor )
Phenyls ( jstor )
Polymerization ( jstor )
Polymers ( jstor )
Solvents ( jstor )
Styrenes ( jstor )
Sulfenic acids ( jstor )
Sulfoxides ( jstor )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Polyacetylenes ( lcsh )
Polymerization ( lcsh )
Polymers ( lcsh )
Styrene ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (Ph. D.)--University of Florida, 1988.
Bibliography:
Includes bibliographical references.
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Typescript.
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Vita.
Statement of Responsibility:
by Rustom Sam Kanga.

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THERMAL ELIMINATION OF POLY(PHENYLVINYLSULFOXIDE)
AND ITS STYRENE BLOCK COPOLYMERS
B/
RUSTOM SAM KANGA
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1988
F libraries


Dedicated
to
my parents
Sam and Gool Kanga
and to my mentor
the late Mr. J. Elavia


ACKNOWLEDGMENTS
I wish to thank all the members of my supervisory committee: Dr.
George Butler, Dr. Kenneth Wagener, Dr. Merle Battiste, Dr. Russel Drago, Dr.
Christopher Batich and Dr. James Boncella.
Special thanks are given to Dr. Batich for his help and advice in XPS,
to Mr. Richard Crockett for running the XPS spectra of my polymers and to
Dr. King for running the pyrolysis-MS.
I thank Dr. Wagener for his support, encouragement and sagacious
advice, both chemical and non-chemical.
I am gratefully indebted to Dr. Thieo Hogen-Esch for his direction,
guidance, encouragement and best of all patience. He taught me a lesson I
will never forget: avoid mediocrity!
Thanks are offered to Lorraine Williams for her ready smile and
readier help. Thanks and cheers are expressed to all the people on the
polymer floor for having enriched my existence.
Words cannot express my gratitude nor my indebtedness to Pauline
Schneider for her help in preparing this manuscript and for being there at
the most critical point in my life!
in


TABLE OF CONTENTS
Page
ACKNOWLEDGMENTS
KEY TO ABBREVIATIONS
ABSTRACT
CHAPTER
1 INTRODUCTION
Polyacetylene (PA)
Precursor Routes to Polyacetylene
2 EXPERIMENTAL
High Vacuum Anionic Polymerization Techniques
Purification of Solvents, Monomers and Reagents
Purification of Phenylvinylsulfoxide and Ethylphenylsulfoxide..
Purification of Styrene and 1,1-Diphenylethylene
Purification of t-Butyllithium
Preparation of Initiators
Lithium Naphthalide
Triphenylmethyllithium (TPML)
1,1 Diphenylhexyllithium (DPHL)
Triphenylmethylpotassium (TPMK)
1 -Lithio-1 -(Phenylsulfinyl) Ethane (EPSL)
Determination of Concentration of Carbanions
Titration with Fluorene
vi i
v i i i
1
3
5
11
11
12
12
13
16
16
16
18
20
20
20
22
22
IV


Determination of Concentration by UV/Visible Spectroscopy 23
Polymerization of Phenylvinylsulfoxide 24
Copolymerization of Styrene and Phenylvinylsulfoxide 28
A-B Copolymers 28
A-B-A Triblock Copolymers 33
Monomer Conversion Study 34
Thermal Elimination 36
Instrumental Methods 38
Size Exclusion Chromatography (SEC) 38
Capillary Gas Chromatography (GC) 39
Nuclear Magnetic Resonance Spectroscopy (NMR) 39
Infrared Spectroscopy (IR) 40
UV/Visible Spectroscopy 41
Polarimetry 41
Pyrolysis-Mass Spectrometry 41
Thermogravimetric Analysis (TGA) 42
X-Ray Photoelectron Spectroscopy (XPS) 42
Contact Angle of PPVS Homo- and Copolymers 44
3 HOMOPOLYMERIZATION AND COPOLYMERIZATION OF PVS 4 5
Homopolymerization 45
Initiators 47
Nature of the Propagating Carbanion 48
Effect of Temperature 52
Effect of Temperature on Initiation of PVS 54
Effect of Temperature on Polymerization 59
Conversion of () PVS With Time 65
Polymerization and Studies of (+)-PVS 67
v


Copolymerization of Styrene and PVS 67
A-B Copolymers 67
A-B-A Copolymers 76
Proof of Dianion Formation in the Lithium Naphthalide Initiated
Polystyryllithium 79
4 THERMAL ELIMINATION STUDIES 85
Mechanism of Sulfoxide Elimination 85
Use of Sulfoxides as Acetylene Synthons 88
Michael Addition-Elimination 88
Alkylation-Elimination 88
Sulfenylation-Dehydrosulfenylation 91
Diels-Alder Cycloadditions and Elimination 91
1,3 Dipolar Cycloaddition and Elimination 91
Elimination of PPVS and PS-PPVS Copolymers 91
Fate of Phenyl Sulfenic Acid 94
Thermal Methods for Study of Elimination 98
Thermogravimetric Analysis (TGA) 98
Pyrolysis-Mass Spectrometry 106
Studies of the Elimination of PPVS by Spectroscopic Methods 112
X-Ray Photoelectron Spectroscopy (XPS) 11 2
Nuclear Magnetic Resonance (NMR) 116
Infrared (IR) 1 25
REFERENCES. 129
BIOGRAPHICAL SKETCH 135
vi


KEY TO ABBREVIATIONS
PVS phenylvinylsu If oxide
PPVS poly(phenylvinylsulfoxide)
PPVO poly (phenylvinylsu If one)
PA polyacetylene
PS polystyrene
EPS ethylphenylsulfoxide
TPML triphenylmethyllithium
1,1-DPE 1,1-diphenyl ethylene
GC gas chromatography
SEC size exclusion chromatography
MW. molecular weight
Mn number average molecular weight
Mw weight average molecular weight
Mp. peak molecular weight from SEC
XPS X-ray photoelectron spectroscopy
vii


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
THERMAL ELIMINATION OF POLY(PHENYLVINYLSULFOXIDE)
AND ITS STYRENE BLOCK COPOLYMERS
By
Rustom Sam Kanga
December 1988
Chairman: Dr. Thieo E. Hogen-Esch
Major Department: Chemistry
The polymerization of phenyl vinyl sulfoxide (PVS) was carried out
in THF at -78C using various anionic initiators. It was found that
delocalized carbanion initiators such as triphenylmethyllithium are
effective initiators as are methyllithium and the dipole stablilized
1-lithio-1-(phenylsulfinyl) ethane. There was excellent correlation
between the measured molecular weight and the calculated molecular
weight. The molecular weight distribution was found to be narrow (<1.4).
The polymerization reaction was found to be extremely rapid with a half
life time of about 4 seconds. A side reaction at higher temperatures was
observed leading to broadening of the molecular weight distribution. The
effect of counter ion, solvent polarity and temperature on the
polymerization reaction was investigated.
Both A-B and A-B-A block copolymerization were carried out. The
A-B diblock copolymerization was carried out by vapor-phase
viii


polymerization of styrene in THF at -78C using t-butyllithium initiator
followed by capping with 1,1-diphenylethylene. The capped
polystyryllithium was used for initiation of the PVS block. The A-B-A
triblock copolymerization was carried out by reacting two-ended
polystyrene prepared by using lithium naphthalide as initiator with 1,1-
DPE to give a capped stable living dianion of polystyryllithium which
initiated PVS at both ends to give an A-B-A triblock copolymer,
polystyrene being the inner block. The molecular weight distributions of
the block copolymers were, in general, narrower than the homopolymers.
The thermal elimination of the homo and copolymers was studied by
TGA and pyrolysis-MS. The TGA of homopolymers typically show two
degradation stages: one at lower temperatures corresponding to
elimination of phenyl sulfenic acid and one at higher temperatures
corresponding to polyacetylene degradation. Pyrolysis-MS was used for
elucidating the fate of phenyl sulfenic acid formed upon elimination. XPS
was used to monitor the elimination reaction with temperature. Proton
NMR was also used to characterize the elimination process and shows
formation of cis and trans polyenes at high temperatures (>100C). A
change in IR spectra with temperature was observed but gave no useful
information about the polyenes formed.
Preliminary studies carried out elsewhere show a relatively short
conjugation length in the polyacetylene formed. Preliminary conductivity
measurements are in progress.
IX


CHAPTER 1
INTRODUCTION
In the course of previous investigations on the mechanism of anionic
oligomerization and polymerization of phenyl vinyl sulfoxide (PVS) [1, 2] it
was discovered that poly(phenylvinylsulfoxide) (PPVS) upon standing,
either in the solution or the solid state, at room temperature changed color
from white to yellow within 24 hours. The polymer then became red and
finally black within one week. The color change occurred in dark or in the
presence of light. It occurred in air, under vacuum or under an argon
atmosphere. The color change, indicating decomposition of some type, was
suppressed to some extent by storage at freezer temperatures.
These color changes were also observed while warming in a melting
point apparatus and were essentially immediate upon heating the polymer
above 100-150C. Interestingly when PPVS was oxidized to
poly(phenylvinylsulfone) the above color changes were not observed upon
heating. The color changes were consistent with the formation of
polyacetylene through a concerted, cyclic, sigmatropic thermal elimination
of phenyl sulfenic acid from PPVS illustrated in Figure 1-1. The sulfoxide
elimination was first proposed by Kingsbury and Cram [3] and later used as
an acetylene equivalent in a Michael addition-elimination [4-9], and a
Diels-Alder cycloaddition-elimination [10] for introduction of a vinyl group
in organic syntheses. Thus PPVS could be regarded as a soluble
polyacetylene precursor.
1


2
Poly(phenylvinylsu If oxide)
H H
Poly(phenylvinylsulfoxide)
+
Ph-S-O-H
Figure 1-1. Scheme for the elimination of phenyl sulfenic acid from
PPVS.


3
Polvacetvlene (PA)
Polymers with conjugated ^-electron backbones are currently of
intense research interest worldwide [11-20]. This is because this class of
polymers displays unusual electronic properties such as low energy optical
transitions and low ionization potentials. As a result they can be oxidized
or reduced more readily and reversibly than conventional polymers without
conjugation [11]. Therefore an insulating polymer could be converted into
conducting polymers with near metallic conductivity in many cases.
Polyacetylene, the simplest conjugated polymer has become a prototype in
the conducting polymers field and has been the most widely studied of the
conducting polymers.
The main impetus for the study of conducting polymers was provided
when Shirakawa [12] successfully synthesized PA as a coherent free
standing film. They used an unusually high concentration of a Ziegler-type
catalyst system. When acetylene gas was introduced into a vessel
containing Ti(OC4Hg)4 / AI(C2H5)3 (AI:Ti::4:1) in toluene (0.1-0.2 M in Ti)
at -78C, a lustrous film formed at the gas-liquid surface. This polymer
referred as "Shirakawa polyacetylene" had a lustrous, golden appearance
and predominantly cis-geometry and was an insulator. The cis-PA
isomerized to trans at higher temperatures (>150C) or upon doping with
electron acceptors such as iodine or AsFs (called p-doping) or with
electron donors like sodium or potassium naphthalide (called n-doping). In
the pristine form cis-PA is an insulator (o = 10'9 S/cm) whereas trans-PA
is a semi-conductor (o = 105 S/cm). Upon doping, however, conductivities
as high as 103 have been obtained [13]. Recently Naarman in W. Germany
[14] report an improved synthesis of PA with fewer SP3 defects having
conductivity in the range of 1.5 x 103 which is about one-fourth the


4
conductivity of copper by volume and twice the conductivity of copper by
weight!
The doping of conjugated polymers results in high conductivities
primarily by increasing the carrier concentration. The description of this
process as doping is a misnomer since dopant concentrations are
exceptionally high compared to the conventional doping of inorganic semi
conductors. In some cases the dopant constitutes about 50% of the final
weight of the conducting polymer [11]. Thus the system would be more
appropriately described as a conducting charge-transfer complex rather
than a doped polymer. Conductivity in doped polymers may be due to
electron transport through the chain (intramolecular), between chains
(interchain transport) and also through interparticle contact [11].
PA is an inconvenient material for fabrication. It is insoluble in all
solvents and cannot be melt processed. Intractability is the major hurdle
for large scale commercial application of PA. Also PA as synthesized can
undergo oxidation in air fairly readily resulting in a severe drop in
conductivity [13].
Another problem is contamination of the PA sample with catalyst
residues which may influence the detailed outcome of the individual
measurements of conductivities which varies with the details of
preparation, recovery, and the washing technique. PA has a fibrullar mat
morphology in which only one third of the space available is occupied by
the PA fibrils. Generation of alternate morphologies has resulted in little
success. The necessity of producing the film at the interface between a
catalyst solution and acetylene gas limits the physical form in which PA
can be produced and this restricts the utility and applicability of direct
synthesis. Considerations of this kind lead to the conclusion that a two


5
step precursor route to synthesis of PA would be advantageous in
circumventing one or more of the above problems. Thus a soluble precursor
could be generated which on further chemical reaction would yield PA in
the second step.
Precursor Routes to Polvacetvlene
Precursor routes to PA are not unknown [16-20]. Marvel et al. were
the first to consider dehydrohalogenation of polyvinylhalides to from PA
[15]. Unfortunately they found that under the extreme reaction conditions
used (high temperatures in presence of high local concentrations of HX) the
nascent polyene formed undergoes further reactions.
Precursor routes for PA syntheses have been extensively studied by
Feast in Durham, U.K. Their approach is outlined in Figure 1-2 and 1-3. The
precursor polymers are synthesized by a metathesis ring-opening
polymerization of monomers like 7,8-bis(trifluoromethyl) tricyclo
{4.2.2.02<5} deca-3,7,9-triene (Figure 1-2) [17, 18]. These precursor
polymers are obtained as colorless soluble materials by conventional
reprecipitation and films or fibres could be spun from solution. A
1,2-disubstituted benzene is thermally eliminated from the precursor
polymer in a symmetry allowed step to yield PA. Cis-PA is initially
formed which isomerizes to trans-PA at higher temperatures. Under
increasingly applied stress ordered films of PA can be produced. This two
step approach allows a whole range of new morphologies to be prepared and
investigated [16,17],
Recently Grubbs [20] found that ring opening metathesis
polymerization (ROMP) of benzvalene yields poly(benzvalene) which is a
polyacetylene precursor. ROMP of benzvalene was achieved using well-
defined non-Lewis acid tungsten alkylidene metathesis catalysts like


6
7,8-bis(trifluromethyl)
tricyclo-[4.2.2.02,5]
deca-3,7,9-triene
i'
Trans-polyacetylene
Cls-polyacetylene
Figure 1-2. Precursor route -1- to "Durham Polyacetylene.


7
3,6-bis(trifluoromethyl)pentacyclo
[6.2.0.02,4.03,6.057]dec-9-ene
Trans-polyacetylene
A
w
Cis-polyacetylene
Figure 1-3. Precursor route -2- to "Durham polyacetylene.


8
Schrock's catalyst {(RO)2W(N(2,6-(iPr)2Ph))CHC(Me)3} [Figure 1-4].
Poly(benzvalene) isomerizes to PA by the action of transition metal
catalysts like HgCl2, HgBr2, and Ag+ salts in THF. The thermal and
photochemical isomerizations were unsuccessful.
The SEC studies of poly(benzvalene) reveals a very broad molecular
weight distribution ranging from 1000 to 600,000 with average molecular
weight approximately 20,000 (relative to polystyrene standards). The
conductivities of the doped PA was 1 S/Cm [20] which was comparable to
Durham PA but is much lower than Shirakawa and Narmann PAs. This may
be due to the amorphous morphology formed during the isomerization.
The synthesis of PA from PPVS in our case has potential advantages.
Firstly the polymerizations of PVS proceeds through stable carbanions
(Chapter 3) so that the molecular weight distribution is expected to be
narrow (unlike those of the Durham and Grubb precursors). Moreover the
control of molecular weight through the ratio of monomer to initiator is
quite good and thus formation of high molecular weight PPVS is possible.
As a result a series of monodisperse PAs of known molecular weights is
possible. Unlike the previous precursor routes which use exotic and
difficult chemistry, the anionic polymerization of PVS is simple and uses
readily available reagents and well-known techniques.
A second advantage of the sulfoxide precursor route to PA is the
formation of A-B and A-B-A type copolymers with monomers like styrene,
butadiene, isoprene etc which are accessible through living anionic
polymerizations. These may then be subjected to elimination to form block
copolymers of styrene (or other monomers) and PA. Previous attempts to
make block copolymers of PA have been known [21-24], There have been
two different approaches to make PA block copolymers. Aldissi [21-22]


9
Polyacetylene
Figure 1-4. Ring opening metathesis polymerization of benzvalene
to polybenzvalene, a polyacetylene precursor.


10
had proposed an "anionic to Ziegler-Natta catalyst" approach wherein the
styrene, isoprene etc have been polymerized anionically followed by
addition to a Ziegler-Natta catalyst like Ti(OBu)4 which exchanges one of
the ligands with the anionically growing polymer chain. Acetylene gas was
then introduced to make the soluble block copolymer. Baker and Bates have
used a similar approach to make both block and graft copolymers [23].
Stowell et al. [24] on the other hand used the "anionic to metathesis
catalyst" approach to make block copolymers of PA. They react the growing
polystyryllithium with a co-ordination catalyst like WCI6 and polymerize
acetylene with the WCl6/polystyryllithium catalyst. Our approach to make
block copolymers would be one using the traditional anionic block
copolymerization technique where styrene is first polymerized using
alkyllithium initiator followed by capping with 1,1-diphenylethylene and
the capped polystyryllithium would be used to polymerize PVS. The
copolymer could then be subjected to thermolysis to make the
poly (sty rene-b-acety lene).
Thus the purpose of the present study was twofold: (i) to synthesize
and characterize PVS homopolymers and its block copolymers with styrene
(both A-B and A-B-A) and (ii) to demonstrate the thermal elimination of
phenyl sulfenic acid from the homo- and copolymers to form PA and its
block copolymers.


CHAPTER 2
EXPERIMENTAL
High Vacuum Anionic Polymerization Techniques
Anionic polymerizations are extremely sensitive to trace amounts of
electrophilic impurities. Thus rigorous techniques for purification of
reagents and solvents were found to be necessary. Also most of the
reagents, solvent transfers, etc. were carried out under high vacuum (10~6
Torr).
High vacuum line techniques have been well known for decades
[25,26,27] and routinely used in our group. The vacuum system consists of
a rotary oil pump in conjunction with a mercury or oil diffusion pump. The
vacuum line was custom made in our glass shop, constructed entirely of
pyrex glass. High vacuum pyrex ground glass joints (Eck & Krebs) were
used at various junctions in the line to permit evacuation of reaction
vessels and distillation of solvents from one part to another. A mercury
McCleod gage attached to the manifold was used to monitor the pressure in
the system.
The reaction vessels used in most of the reactions were made from
pyrex and were self built by use of a hand-held gas and oxygen torch. The
manipulations required for various reactions like addition, transfer of
reagents etc. were performed in vacuo using the breakseal technique
[25,26]. The glassware used was scrupulously cleaned using in order: KOH
/ isopropanol (15% W/V), 1% HF, rinsed with water and acetone and dried
before attaching it to the line. Once attached to the line the whole system
11


12
was evacuated and flamed thoroughly with a torch to remove traces of
adsorbed water vapor and oxygen from the surface of the glass. The system
was then checked for the presence of pinholes using a Tesla coil. Reactions
were carried out only after confirming "sticking vacuum" (<10'6 Torr) as
registered on the McCleod gage.
Purification of Solvents. Monomers and Reagents
All polymerizations and other reactions were carried out under high
vacuum in THF. Since anionic polymerizations involve reactive
intermediates, it was found necessary to use highly purified and dry
reagents and solvents. THF was purified by refluxing over a
sodium/potassium alloy for 24 hrs., followed by distillation onto fresh
alloy in a round bottom flask which was then flushed with argon and
connected to a vacuum line equipped with a water-jacketed condenser. A
small amount of benzophenone was added as an indicator. The THF was
evacuated and degassed several times. The color turned purple which
indicates formation of the benzophenone dianion and absence of protic
impurities and oxygen.
Purification of Phenvlvinvlsulfoxide and Ethvlphenvlsulfoxide
Phenylvinylsulfoxide (Aldrich) in the crude form is a dark brown high
boiling liquid. The crude phenylvinylsulfoxide was stirred over calcium
hydride for 24 hrs., followed by distillation in a Vigreux distillation
apparatus at 100-110C / 0 mm Hg onto fresh calcium hydride. This
procedure was repeated thrice. The colorless distillate from the last
distillation was collected in a break-seal equipped ampule and further
divided as needed. Care was taken while sealing to make sure that none of
the high boiling monomer remains at the site being sealed and which might
degrade forming undesirable impurities.


13
Other purifying agents were tried but did not work. The monomer
became black within minutes when stirred over potassium mirror. McGrath
[28-29] has advocated the use of triethylaluminum for the purification of
acrylate and methacrylate monomers. The trialkylaluminum forms a
colored charge-transfer complex with the carbonyls of the monomer and
hence is self-indicating in the titration. We tried using triethylaluminum
once with disastrous results! There was a strong exothermic reaction
between PVS and triethylaluminum and ultimately an explosion!
The monomer was characterized by GC (>99% pure) and by proton and
carbon-13 NMR.
1H NMR (CDCI3, 200 MHz, 9 in PPM): d at 5.85 (1H), d at 6.15 (1H), d
of d at 6.6-6.8 (1H), 7.45 (3H),7.6 (2H)
13C NMR (CDCI3, 50 MHz, 9 in PPM): 121 (vinyl methylene), 125
(ortho aromatic carbons), 131.5 (para carbon), 143 (vinyl methine), 143.5
(substituted quarternary aromatic).
(+) Poly(phenylvinylsulfoxide) was synthesized by M. Buese [2]. It
was purified by distilling twice over calcium hydride. The optical
rotation, [a]D20, was found to be 358.5.
Ethylphenylsulfoxide (ICN Pharmaceuticals, INC.) was purified in a
similar manner.
1H NMR (CDCI3, 200 MHz, 9 in PPM): t at 1.1 (3H), q at 2.75 (2H), m at
7.6 (5H).
13c NMR (CDCI3, 50 MHz, 9 in PPM): 10 (methyl), 52 (methylene),
126,131,132,147(aromatics).
Purification of Stvrene and 1.1-Diphenvlethvlene
Styrene (Fisher) was purified by stirring over calcium hydride for 24
hrs. followed by fractional distillation under vacuum (75C / 95 mm Hg).


14
The middle fraction was collected in an ampule. The ampule was further
attached to an apparatus shown in Figure 2-1 and evacuated. The side arm
contained freshly cut potassium metal which was heated gently with a
torch to form a shiny mirror in the main container. Styrene was then added
onto the mirror and allowed to stir gently for 30 minutes. After degassing
it was distilled into the side flask provided with a break-seal and
carefully sealed off from the main apparatus. The extremely pure and dry
styrene was stored in the freezer and used as needed. Styrene-d8 (Aldrich)
was purified by distilling twice over calcium hydride in vacuo.
Styrene: 1h NMR (CDCI3i 200 MHz,3 in PPM): d at 5.11 (1H), d at 5.59
(1H), d of d at 6.59 (1H), 7-7.5 (5H)
Styrene: 13q nmr (CDCI3, 50 MHz, 3 in PPM): 113 (vinyl methylene),
126 (ortho aromatics), 127.8 (para aromatic), 128.5 (meta), 137 (vinyl
methine), 138 (substituted quarternary). Styrene-d8: 1H NMR (neat with
TMS, 200 MHz, 3 in PPM): t at 5.0 (1H), t at 5.5 (1H), d at 6.5 (1H), s at 7.0
(para 1H), s at 7.1 (meta 2H), s at 7.25 (ortho 2H).
13c NMR (neat with 1% CDCI3, 50 MHz, 3 in PPM): pentet at 112.5
(vinyl methylene CD2), t at 125.6 (aromatic ortho CD), t at 126.9 (aromatic
para CD), t at 127.7 (aromatic meta CD), t at 136.2 (vinyl methine CD), s at
137.1 (substituted aromatic quarternary C). All assignments made from
non-deuterated styrene in Sadtler.
1,1-Diphenylethylene was purified in a similar manner. 1H (200 MHz,
CDCI3, 3 in PPM): s at 5.4 (2H), m at 7.2 (10H)
13C (50 MHz, CDCI3, 3 in PPM): 114 (=CH2), 127.5 (ortho aromatic),
128.1 (m and p aromatic), 141.5 (ipso aromatic), 150 (>C=).


15
Figure 2-1. Apparatus used for purification of styrene.


16
Purification of t-Butvllithium
It was found that the crude t-butyllithium (Aldrich) contained
undesirable impurities like lithium t-butoxide, lithium hydroxide etc. It
was thus found desirable to further purify t-butyllithium by sublimation of
the crude product [30]. The apparatus shown in Figure 2-2 was used.
Crude t-butyllithium was introduced in "a" under a constant flow of
argon. The solvent was pumped off into the trap and the side arm sealed.
Crushed dry ice was put in the cork ring on the flask "b" to trap the
subliming t-butyllithium. The lower part of the apparatus was immersed
in a hot water bath (85C) and the combination of heat and dynamic vacuum
was used to sublime highly pure t-butyllithium which was trapped in b"
while the impurities remained unaffected in "a." The flask containing the
t-butyllithium was sealed off from "a" at the constriction "S1" and from
the line at "S2." Extreme care was taken to see that none of the
t-butyllithium remained at the sites "S1" and "S2" which might form
undesirable decomposition products and might also create pinholes. The
shiny white solid t-butyllithium was then dissolved in Na/K dried hexane
and further subdivided as needed.
Preparation of Initiators
Lithium Naphthalide
Lithium wire (Mallinckrodt) was cleaned by dipping successively in
methanol, hexane, and finally THF. A THF solution of naphthalene (Aldrich,
Gold label) was prepared in vacuo in a break-seal equipped ampule. An
excess of naphthalene was used to avoid formation of the naphthalene
dianion [31, 32]. The lithium metal was introduced in the reaction vessel
under a constant flow of argon. After evacuation more THF was distilled
in. The naphthalene solution was then added in. A noticeable color change


17
Figure 2-2. Apparatus used for purification of t-butyllithium by
sublimation.


18
was observed upon reaction of naphthalene with lithium metal. The
reaction was allowed to proceed at 25C for 12 hrs. At the end of 12 hrs. a
dark green solution was obtained which was filtered through a course frit
into various ampules. The concentration of the initiator was determined as
described later.
Triphenvlmethllithium (TPMU
TPML was made as described in reference 33. A THF solution of
triphenylmethane (TPM) was prepared in vacuo and attached to an apparatus
illustrated in Figure 2-3. The apparatus was attached to the line,
evacuated and flame degassed. Argon was then charged into it and
n-butyllithium was injected through the serum cap. Both argon and the
solvent were removed by distillation into the cold trap leaving behind the
viscous yellow n-butyllithium. The apparatus was cooled to -78C using a
dry ice/isopropanol bath and the serum cap was sealed from the apparatus.
THF was then distilled into the n-butyllithium and the TPM solution was
added from the ampule through the breakseal. The solution started turning
red almost immediately and was allowed to stir at room temperature for
8-10 hrs. THF was then distilled from the solution into the trap leaving
behind the dark red TPML. The apparatus was then cooled to -78C and
dried hexane was distilled into the flask (THF:Hexane approximately 1:15).
The apparatus was sealed from the line and the recrystallized TPML was
washed with the hexane. This was accomplished by pouring the hexane
from the main body of the apparatus into the wash ampule and distilling
back into the main body. After repeating this procedure several times the
hexane was removed from the main body in the wash ampule.
The apparatus was reattached to the line and THF was distilled in to
dissolve the TPML salt. The TPML solution was poured into a separate


19
Figure 2-3. Apparatus used for the preparation of TPML.


20
ampule and sealed off from the main body. The initiator was stored at
-20C and was further divided as needed. The concentration of the
initiator was determined as described later.
1,1 Diphenvlhexvllithium (DPH
DPHL [33] was prepared by reaction of equimolar amounts of
1,1-diphenylethylene and n-butyllithium in THF at room temperature for 12
hrs. The reddish orange salt was purified by washing with hexane as
described for TPML. The THF solution of DPHL was stored at -20C and
divided as needed. The concentration of the initiator was determined as
described later.
Triphenvlmethylpotassium (TPMK)
TPMK was synthesized by reaction of a 1.1-molar excess of a
solution of TPM in THF with a solution of oligomeric dianions of
a-methylstyrylpotassium (aMSK) in THF prepared by reaction of
alphamethylstyrene in THF with potassium metal for 24 hrs at 25C [34].
A THF solution of TPM was prepared in vacuo in a breakseal equipped
ampule. The red solution was filtered through a frit and divided into
ampules. The THF solutions of TPM and aMSK were reacted with each other
in vacuo at room temperature for 2 hrs. After the reaction the TPMK
solution was sealed from the line and divided into various ampules. The
concentration of the TPMK solution was measured as described later.
1-Lithio-1-(Phenvlsulfinvh Ethane (EPSU
EPSL [1, 2] was synthesized by a reaction of a 1.1 excess of
ethylphenylsulfoxide with methyllithium in THF at -78C. The apparatus
used for the synthesis is illustrated in Figure 2-4. The apparatus was
attached to the line and evacuated. Argon was then charged into it through
the line and methyllithium was injected through the serum cap. The


21
Figure 2-4. Apparatus used for the synthesis of EPSL.


22
solvent was carefully removed by distillation into the trap as the solution
tended to bump in the apparatus. The serum cap was sealed off and THF
was distilled to make a solution of methyllithium. The solution was then
cooled to -78C and ethylphenylsulfoxide was added from the ampule
through the breakseal. The solution started becoming yellowish as the
methyllithium reacted with ethylphenylsulfoxide to form the carbanion.
The solution was degassed several times to remove the methane gas and
was stirred at -78C until no more methane gas evolved (as evidenced by
the bubbling of the solution upon degassing and the characteristic pump
noise). The yellowish-green solution was sealed from the line and poured
into a side ampule which was sealed off. The initiator was stored at -20C
and divided as needed. The concentration of the initiator was determined
as described below.
Determination of Concentration of Carbanions
For polymerization reactions concentration determination of metal
alkyls and the delocalized carbanion salts was necessary. Thus, for anionic
polymerizations in the absence of terminating impurities the number
average molecular weight can in principle be predicted if the accurate
concentration of the initiator is known. Also for two-ended carbanions the
accurate determination of the concentration was imperative in order to
prove the "two-endedness of the system. Two methods were used for
determination of concentration of initiators. The agreement between the
two methods was found to be excellent (5%).
Titration with Fluorene
The fluorene (Aldrich) used in titrations of the carbanion solutions
was purified by crystallization from ethyl alcohol and pumped on the


23
vacuum line for several days to get rid of the traces of alcohol. Purity was
better than 99% by GC.
The carbanion solutions in THF are reacted with a known excess of
fluorene in THF at -78C. In most cases the reaction of the carbanions
with fluorene was instantaneous as seen by an immediate color change of
the solution to yellowish-orange, the characteristic color of
fluorenyllithium. The fluorenyllithium was then reacted with an excess of
methyl iodide to form 9-methylfluorene and the ratio of fluorene to
9-methylfluorene was determined by capillary GC.
Determination of Concentration bv UV/Visible Spectroscopy
UV/Vis was found to be an excellent method for concentration
determination since most delocalized carbanions have distinct and strong
absorptions in the visible region.
All of the absorbance measurements were carried out under high
vacuum using an apparatus equipped with a UV cell. The absorbance of the
unknown carbanion was measured followed by a reaction with an excess of
fluorene. The absorbance of the fluorenyl carbanion thus formed was
measured. Comparison of the two absorbances and the molar absorptivity
of the fluorenyl carbanion from the literature [35, 36, 37] provided the
molar absorptivity and hence the concentration of the unknown carbanion
solution. This technique was found to be most convenient for solutions of
living polystyryllithium capped with 1,1-diphenylethylene. The capped
solutions are quite stable at room temperature during the time of
spectroscopic determination and it also avoids the problem associated
with the entrapment of fluorene and 9-methylfluorene in the polymer
matrix during precipitation of the polystyrene in methanol (Method I).


24
The ampule containing the carbanion solution was attached to an
apparatus which was provided with a quartz cell having a 2 mm path
length, in conjunction with a 1.9 mm spacer. The whole system was
attached to the line, evacuated, flamed and sealed off the line. The
carbanion solution was introduced in the cell from the ampule through the
breakseal and scanned in the visible and near UV regions. The fluorene was
then introduced. A change in color was noted as the carbanion reacted with
the fluorene to form fluorenyllithium. After all the carbanion reacted the
fluorenyllithium was scanned in the UV region.
Assuming Beer's law to be applicable to both the carbanion solutions
[25] one can write the following equations:
Ax = ex Cx 1 2 -1
Ay = £y Cy 1 2-2
Cy =Ay £X CX / AX £y 2-3
where x refers to the unknown carbanion solution and y to the
fluorenyllithium, A = absorbance, e = molar absorptivity, C = concentration
of the absorbing species, I = path length, determined using a known
standard solution of Potassium Chromate (e372nm = 4815) [37],
Since Cx = Cy (assuming no inadvertent protonation of the carbanion during
the reaction) we get ex = Ax/Ay ey. Knowing ex one can calculate the molar
concentration of the unknown carbanion solution using the equation 2-3.
Polymerization of Phenvlvinvlsulfoxide
The homopolymerization of phenylvinylsulfoxide (PVS) was carried
out using the apparatus illustrated in Figure 2-5. The system consists of
two round bottom flasks "a" and "b (100 ccs and 50 ccs respectively)
joined together. The ampules containing the initiator (TPML, methyl
lithium, DPHL etc) and the terminating agent (usually methanol) were


25
Initiator
Figure 2-5 Apparatus used for the homo- and copolymerization of
PVS.


26
attached to "a" along with a ground glass joint to hook it to the vacuum
line. The monomer ampule is attached to the smaller flask ("b").
The apparatus was hooked to the vacuum line, evacuated and flamed
thoroughly. The initiator solution was introduced into flask "a" through the
break seal. The ampule was "washed" with the solvent using a cold cotton
dauber in order to remove all of the initiator solution. Dried THF was then
distilled in "a" to dilute the carbanion solution and the carbanion solution
was thoroughly cooled to -78C. The apparatus was then carefully sealed
from the line at S1. The monomer breakseal was then broken and the
monomer was introduced in the flask b." THF was distilled into b" from
the carbanion solution. Care was taken to see that the initiator solution
did not bump during the distillation. After sufficient dilution of the
monomer both the initiator and the monomer solutions were cooled to
-78C as was the tube connecting the two flasks. The solutions were then
rapidly mixed by pouring "b" into "a." An immediate change in color is
usually seen, in the case of TPML from dark red to yellowish-green. This
indicated that the initiation of PVS is quite rapid. After a few minutes
more monomer is added. This procedure is repeated several times until all
the monomer is consumed. The time of polymerization varied from 15
minutes to 12 hours. The yellowish-green color of the living
a-phenylsulfinyl carbanion persists throughout the polymerization. The
chain terminating electrophile (usually methanol) was then added to the
polymerizing solution resulting in an immediate discharge of the
yellowish-green color.
The solvent from the polymerization reaction was rotovaped down
and the polymer was precipitated by pouring into a ten times excess
diethylether solvent. The yield of poly(phenylvinylsulfoxide) (PPVS) was
i


27
determined by weighing and the polymer was characterized further by NMR,
SEC etc. The PPVS was found to be thermally unstable and starts becoming
yellow within a matter of days. It was thus found necessary to store the
polymer in the freezer under argon.
Poly(phenylvinylsulfoxide): 1H NMR (CDCI3, 200 MHz, 3 in PPM):
1.1-2.1 (2H), 2.5-3.5 (1H), 7.2-8 (5H)
Poly(phenylvinylsulfoxide): 13C NMR (CDCI3, 50 MHz, 3 in PPM): 26-
32 (methylene in the chain), 56-60 (methine), 123-126, 128-130, 131,
140-142 (aromatic carbons)
(+) Poly(phenylvinylsulfoxide) [alpha]D20= 408: 1H NMR (CDCI3, 200
MHz, 3 in PPM): 1.3-2.3 (2H), 2.7-3.6 (1H), 67-7.7 (5H)
(+) Poly(phenylvinylsulfoxide): 13C NMR (CDCI3, 50 MHz, 3 in PPM):
55-57 (methylene), 23-26 (methine), 123-126 (aromatic meta carbons),
128-130 (aromatic ortho carbon), 130-132 (aromatic para carbon), 140
(substituted aromatic quarternary carbon).
PPVS upon oxidation to poly(phenylvinylsulfone) (PPVO) becomes
stable to air (or thermal) degradation. PPVS was oxidized to PPVO by
hydrogen peroxide [1, 2, 38]. The polymer was dissolved in glacial acetic
acid. An excess of 30% hydrogen peroxide was added. The polymer solution
was allowed to stir at room temperature for 12 hrs. A bright white ppt
was formed upon completion of the oxidation. The resulting PPVO was
found to be insoluble in most solvents and partially soluble in chloroform
and THF. Oxidation of the sulfoxide to the sulfone was seen to be
quantitative by IR measurements and also by XPS (see Chapter 4).


28
CoDolvmerization of Stvrene and Phenvlvinvlsulfoxide
A-B Copolymers
A-B copolymerization of styrene and PVS was carried out in two
steps: (a) Polymerization of styrene was first carried out at -78C in THF
initiated by t-butyllithium [25] followed by capping with
1,1-diphenylethylene (1,1-DPE) followed by division of the capped living
polystyryllithium into various ampules, (b) Polymerization of various
amounts of phenyl vinyl sulfoxide was then carried out bousing the capped
living polystyryllithium as the initiator.
Polymerization of styrene was carried out in an apparatus
illustrated in Figure 2-6. Once again the basic apparatus consists of 2
round bottom flasks "a" and "b" (500 ml and 50 ml respectively). The
ampules containing the initiator (t-butyllithium) and the capping agent
(1,1-DPE) are attached to flask "a." The monomer (styrene) ampule is
attached to flask "b. The flask "b" is connected to "a" with a tube which
extends into "a" at the top forming a lip. Additionally there are 2 ampules
A1 and A2 equipped with breakseals having volumes 10 ml and 100 ml
respectively.
Once the apparatus was assembled it was attached to the vacuum
line through the ground glass joint, evacuated, checked for pinholes and
flamed. The initiator was added from the ampule through the breakseal
into flask "a" and washed down using a cold dauber. THF was then distilled
into the initiator solution by cooling flask "a." The color of t-butyllithium
turned yellow upon distillation of THF. This was probably due to
deaggregation of the t-butyllithium in going from hexane to THF. It is also
known that t- butyllithium reacts with THF at 25C to form various
alkoxides [25]. However the yellow color observed was probably not due to


29
Figure 2-6. Apparatus used for the polymerization of styrene.


30
this reaction since the solution was kept at -78C at all times. Several
precautions were taken before styrene was distilled in; the level of the
isopropanol/dry ice bath was kept below the level of the initiator and the
path between the flasks "a" and "b" was kept warm using an air dryer.
These precautions were warranted to make sure of a uniform vapor phase
distillation of styrene into the rapidly stirring initiator solution and to
avoid any local concentration of the monomer which is undesirable. The
excellent molecular weight distributions bear testimony to the correctness
of this technique (see Chapter 3). The breakseal of the styrene ampule was
broken and styrene was slowly distilled from the flask "b" which was
cooled to -20C. The color of the t-butyllithium solution turned cherry red
instantaneously. After all the styrene was distilled into "a" the solution
was further stirred for 10 to 15 minutes. 1,1 -DPE was then added to the
living polystyryllithium solution. The cherry red solution turned dark red
upon reaction. The apparatus was sealed off the line at S1. The solution
was allowed to warm up and was then carefully poured into the side
ampules. The constrictions S2 and S3 were washed using a cold dauber and
the ampules were sealed off the main body.
Ampule A1 was used for the detection of the concentration of the
living carbanions by UVA/isible spectroscopy and terminated by an
electrophile like fluorene or methanol. The polystyrene was precipitated in
an excess of methanol nonsolvent and characterized using SEC and NMR.
1 H NMR (CDCI3, 200 MHz, d in PPM): 0.6 (d, t-butyl), 1.2-1.8 (2H),
1.6-2.3 (1H), 6.3-6.9 (2H), 6.8-7.3 (3H).
13C NMR (CDCI3, 50 MHz, d in PPM): 40-41 (methylene), 42-48
(methine), 125.8 (para aromatic), 127 (ortho aromatic), 128 (meta
aromatic), 145 (substituted quarternary).


31
Ampule A2 was further attached to a divider (Figure 2-7), thoroughly
evacuated, flame degassed and sealed from the line. The carbanion solution
was introduced into the apparatus and was carefully divided into the
various ampules. After washing the constriction of each ampule the
divider was cooled in a large dewar to -78C and each arm was carefully
sealed off.
The polymerization of phenylvinylsulfoxide initiated by the living
DPE capped polystyryllithium was carried out as described before for
homopolymerization. The length of the styrene block was kept constant
whereas the length of the poly(phenylvinylsulfoxide) was varied. The
composition of the block copolymer was calculated from the moles of
styrene and PVS used for each polymerization. The mole ratio of phenyl
vinyl sulfoxide / styrene was varied between 0.26 to 8.0. The apparatus
was the same as that for the homopolymerization of PVS (Figure 2-5).
Once again a color change from dark red to yellowish-green was noticed
upon addition of the monomer to the initiator and the living copolymer
turned colorless upon termination with methanol. The copolymer was
purified by precipitation in a solvent system comprised of ethyl ether and
methanol (75/25 v/v).
1 H NMR (CDCI3, 200 MHz, d in PPM): 0.6 (t-butyl), 1.2-1.8 (methylene
of both polystyrene and poly(phenylvinylsulfoxide) blocks), 1.5-2.4
(methine of polystyrene block), 2.5-3.5 (methine of
poly(phenylvinylsulfoxide) block), 6.3-6.9 (2H, ortho aromatic of
polystyrene block), 6.7-7.5 (3H, meta and para aromatic of polystyrene
block), 7-8 (5H, poly(phenylvinylsulfoxide) block)
The copolymer was stored in the freezer and characterized by SEC
and by NMR. Conditions for oxidation of the copolymer were the same as


32
Figure 2-7.
into several
Apparatus employed for division of a carbamon solution
smaller ampules.


that for the homopolymer using an excess of 30% hydrogen peroxide for 24
hrs, yielding the thermally stable poly(styrene-b-phenylvinylsulfone).
A-B-A Triblock Copolymers
The A-B-A copolymers of styrene and phenylvinylsulfoxide like the
AB copolymers were prepared in two steps: (a) formation of living two-
ended polystyryllithium using lithium naphthalide initiator [39] followed
by capping with 1,1-DPE and division of the capped living polystyryllithium
into various ampules and (b) polymerization of various amounts of PVS
using DPE capped two-ended polystyryllithium.
Living two-ended polystyryllithium was prepared in a manner similar
to the polymerization of styrene using t-butyllithium described before.
Lithium naphthalide was employed as the initiator. After assembling the
apparatus (Figure 2-6) it was attached to the vacuum line, evacuated,
checked for pinholes and flame degassed. The initiator solution was
introduced into Mb" and cooled to -20C. The usual precautions were taken
during distillation of styrene in the polymerization solution as described
before. An immediate color change from dark green to cherry red was seen
upon addition of styrene. After all of the styrene was distilled the
solution was further stirred at -78C for 15 minutes. 1,1-DPE was then
added to the living polystyryllithium. The cherry red color changed to dark
red upon reaction with 1,1-DPE. The apparatus was sealed from the line
and the solution was divided into two ampules as described earlier. The
determination of concentration and workup were similar to that of the
one-ended system.
The second step in the triblock copolymerization was identical to the
diblock. Once again the styrene block length was kept constant whereas
the phenylvinylsulfoxide block length was varied depending on the moles of


34
styrene used and the ratio of phenylvinylsulfoxide to styrene desired.
Workup of the triblock copolymer was same as that of the diblock.
Monomer Conversion Study
It was found necessary to roughly determine the conversion of
monomer with time, so as to have a rough idea of the kinetics of the
polymerization reaction. Since aliquots of the polymerization mixture
were withdrawn at various times during the polymerization, the
polymerization had to be carried out under rigorously dried argon.
Naphthalene was employed as an internal standard in order to
monitor the consumption of monomer with time. Several factors were
considered for using naphthalene as an internal standard. Naphthalene and
PVS have retention times in GC which are quite different and measurable.
A calibration curve of ratio of moles of phenylvinylsulfoxide to
naphthalene versus the GC ratio of the areas of PVS to naphthalene (Table
2-1) gave a straight line with an excellent correlation coefficient (Figure
2-8). Also naphthalene is inert in presence of living the PPVS carbanions.
The apparatus used during the above polymerization was similar to
Figure 2-5 and consisted of 2 bulbs "a" and "bH joined together. The
initiator ampule was attached to "a" along with a high vacuum stop-cock.
To the flask Mb" was attached a monomer ampule and a short outlet with a
rubber septum for aliquot withdrawals. The apparatus was attached to the
vacuum line and the absence of pinholes was checked. Purified argon was
charged to the apparatus and a known amount of naphthalene was added to
flask "b" which was then evacuated again. Care was taken to see that none
of the naphthalene sublimed to the trap under the high vacuum. The
initiator was introduced in flask "a" and the contents of the ampule were
washed down. Additional THF was distilled into the initiator solution


Table 2-1. Calibration for the determination of phenylvinylsulfoxide in the
presence of naphthalene as an internal standard.
mol PVS
x 104
mol NPH
x 104
mol PVS/mol NPH
A PVS/A NPH
6.1
1.7
3.6
2.56
5.7
4.3
1.3
0.96
7.7
7.7
1.0
0.68
5.9
9.7
0.61
0.39
5.7
12.2
0.47
0.33
6.5
15.3
0.42
0.31
Figure 2-8. Graph of ratio of moles of PVS to Naphthalene versus ratio of
areas (in GC) of PVS to Naphthalene.


36
through the vacuum line. The monomer was then introduced into "b", and
diluted with THF by distillation from the initiator. Both "a" and "b" were
cooled to -78C. Argon was charged into the apparatus, through the line.
The argon had to be rigorously dried, which was accomplished by using a
solid KOH and drierite traps followed by a cold (-78C) trap. The stopcock
S between the line and the apparatus was closed off and the apparatus
detached from the line Both the flasks were then cooled to -78C. The
initiator solution was introduced into flask "b" by tilting the apparatus.
Aliquots of the polymerization solution were withdrawn at various times
during the polymerization through the rubber septum using a syringe and
were quenched in methanol. The quenched solution was added to an excess
of diethyl ether to precipitate the polymer, which was filtered and the
filtrate was rotovaped and analyzed by GC so that the change in
concentration of monomer with time could be determined. The polymer was
dissolved in THF and analyzed by SEC for the change in polymer molecular
weight with time.
Thermal Elimination
Thermal elimination of the homo- and copolymers in the solid state
was carried out using a Thermolyne tube furnace with a suitably equipped
pyrolysis tube (Figure 2-9). The polymer was dissolved in a minimum
amount of THF or chloroform. The solution of the polymer was introduced
into the section "a" using a pipette. The tube was attached to a rotovap in a
horizontal position and was evaporated with a gradual application of
vacuum. The application of vacuum and slow rotation ensured a thin
uniform film surface in the section "a." The tube was then inserted into
the Thermolyne furnace and hooked to the vacuum line. A cold (-78C) trap
was used between the line and the tube to trap any condensables.


3 7
a
Figure 2-9. Pyrolysis tube used for the thermal eliminations of the
homo- and copolymers in the Thermolyne tube furnace.


Elimination was carried out by gradually increasing the temperature to
180-200C and under high vacuum (10* torr) for 1.5 hrs. The polymer
after heating became dark black and shiny and was handled under argon
(glove bag) at all times. The eliminated products obtained from the side of
the tube outside the furnace were analyzed by MS, GC, and NMR.
Instrumental Methods
Size Exclusion Chromatography (SEC1
SEC was carried out on a Waters 6000-A liquid chromatograph
Phenomenex (Rancho Palos Verdes, CA) TSK Gel G-3000H and G-5000H
columns were employed in series (column dimensions: 75mm x 30cm). The
columns were packed with spherical, crosslinked poly(styrene divinyl
benzene) particles having pore sizes 10 and 10 for G3000H and
G5000H respectively. The molecular weight limits for G3000H were 600
to 60,000 and that for G5000H were 10,000 to 10. Polystyrene standards
were supplied by Scientific Polymer Products, Polysciences INC., Pressure
Chemical Co. and Waters Associates. The standards ranged from a
molecular weight of 2000 to 2,00,000. All polymer solutions injected in
the columns were filtered through a 0.5 p PTFE filter ("Alltech", II.).
The eluting solvent was HPLC grade THF filtered through a 0.5 p
filter. The flow rate was usually 1 ml/minute. The model 6000A solvent
delivery system by "Waters Associate" was utilized. Injection into the
column was achieved by a Waters Associate Model U6K universal liquid
chromatograph injector which allowed loading and injecting samples at a
pressure of up to 600 psi without interruption of the solvent flow. A
Perkin-Elmer LC-75 spectrophotometric UV detector set at 254 nm was
used for detection of the eluting polymer. The detector was interfaced
with a Zenith PC-100 personal computer equipped with a MS-DOS Dascon-1


data collecting program operating at a rate of 1 Hz. The Basic programs
used for data acquisition, molecular weight calibration, computation of
molecular weight averages and distributions were written by W. Toreki in
our group [40]. The Basic program for the conversion of the data into a high
resolution graphics display was written by the author with help from Dr.
Gardiner Myers. Explanations of these Basic programs and the relevant
analytical chemistry involved with it are described elsewhere [40].
A calibration curve was created by injecting various polystyrene
standards and using a correction factor to account for band broadening. The
retention volume of PPVS was then compared to the calibration curve and
an apparent molecular weight for our system was determined. In the
absence of suitable PPVS standards this method was found to be quite
accurate for determination of apparent molecular weight and molecular
weight distribution of PPVS homopolymers and its copolymers with
styrene.
Capillary Gas Chromatography,.(QC)
Routine analyses of monomers and reagents were done by GC. A
Hewlett-Packard 5880A gas chromatograph was used for this purpose. The
system consisted of a 50 meter (G. E. Co. SE-54) fused silica capillary
column (0.2mm ID) coated with a 0.11 pM film of silicone gum, a
microprocessor capable of automation, a temperature programmable oven
and a flame ionization detector. Helium was used as the carrier gas. A
stepwise gradient temperature program was used so that the oven
temperature increased at a controlled rate for higher resolution.
Nuclear Magnetic Resonance Spectroscopy (NMR)
Proton and Carbon-13 NMR spectroscopy was used as an extensive
tool for structure determination, determination of purity of reagents, for


40
characterizing the microstructure in the copolymers and also for
monitoring the change in the structures of the homo- and copolymers upon
heating. Most of the NMR spectra were recorded on a Varan FT-NMR XL 200
spectrometer featuring distributed microcomputer control and a flexible,
high-storage-capacity memory capable of high resolution Fourier
transform. Deuterated chloroform was used as a solvent in most monomer
and polymer studies. The chemical shifts were reported in PPM using TMS
as a reference.
High temperature NMR was done on a Varan XL-300 NMR
spectrometer featuring the same software as the XL-200. Acetic acid-D4
was used as a solvent. A heavy-walled 5 mm tube was employed and the
polymer solution was sealed under a partial pressure under argon. The
spectra were recorded at room temperature and the temperature was
increased in steps of 20C. A nitrogen atmosphere was used in the probe.
Spectra were recorded at 60, 80, 100, 120, 140, and 150C.
Infrared Spectroscopy (IR)
Infrared spectroscopy was used for additional structure
determination of the polymers, determination of oxidation of sulfoxide to
sulfone and monitoring of the thermal degradation of PPVS. Routine
measurements were carried out using a Perkin-Elmer 281 IR
spectrophotometer using a pressed KCI pellet or a NaCI window coated with
the polymer. Spectra were also recorded on a Nicolet 5DXB FT-IR
spectrophotometer using NaCI windows under a nitrogen atmosphere. High
temperature IR runs were carried out by Ms. Jennifer Lin in the materials
science department. Spectra were recorded on a Nicolet 60SX FT-IR
spectrophotometer equipped with an "Omega" temperature controller. The
polymer was mixed in diamond powder, mounted and heated under nitrogen


41
atmosphere. The temperature was increased to 200C over a period of time
at a heating rate of 5C/min and the spectra were recorded continuously.
UV/Visible Spectroscopy
UV/VIS spectroscopy was used for determination of concentration of
carbanions. A Perkin-Elmer Lambda-9 UV/VIS/NIR spectrophotometer was
employed. Quartz cells having a 2 mm path length were used in conjunction
with a quartz spacer. The path length was calibrated using a known
standard solution of potassium chromate. The cells were usually attached
to the reaction vessel and the spectra recorded under high vacuum. A
special spectrometer cover was made by the chemistry department
machine shop designed to prevent extraneous light to interfere with the
measurement. The spectra were usually scanned from 700 nm to 300nm.
THF was the solvent in most cases. The response time was 1 second, scan
speed 120 nm/min, peak threshold 0.02 , cycles/time 1/0.05 min, using an
automatic lamp.
Polarimetrv
The optical activity of the optically active monomer and polymer
was measured using a Rudolph Research Autopol III automatic polarimeter.
Py.cQlysJs-Mass 5pectrQmetry
Pyrolysis-MS was used as a technique for characterizing the thermal
elimination on the homo- and copolymers. It was carried out by Dr. King in
the mass spectrometry laboratory. The mass spectrometer used for this
purpose was the AEI MS-30.
The polymer was inserted using a direct insertion probe. A gradient
temperature from 100 to 500C was employed. Spectra were recorded
continuously at various temperatures and processed by a "Kratos" data
system.


42
Thermogravimetric Analysis (TGA)
TGA was carried out on a Perkin-Elmer TGA7 thermogravimetric
system. The system consists of the TGA7 thermogravimetric analyzer
controlled by the TAC7 thermal analysis instrument controller. The
analyzer permits the measurement of weight changes in a sample material
resulting from chemical reactions, decomposition, eliminations etc as a
function of either temperature or time.
The heart of the thermal analysis system is the 32 bit PE-7500
professional microcomputer which allows for totally computerized control
of the TGA7 analyzer. Thus the TGA7 can be programmed to scan a
temperature range by changing at a linear rate over several temperature
ramps or it can analyze data at isothermal temperatures to measure weight
loss/gain with time.
The TGA7 analyzer is made up of 2 major components: a sensitive
ultramicrobalance and a furnace element. Other components of the system
include the GSA-7 gas selector accessory and the graphics plotter.
Before each session the analyzer balance and the furnace were
calibrated over the temperature range used. A curie point temperature
calibration was also carried out using 2 standards: Alumel (163C) and
Perkalloy (596C). The polymers were usually scanned under a nitrogen
sample purge (50 ml/min) from 50C to 900C at a heating rate 10C/min.
X-Rav Photoelectron Spectroscopy (XPS)
XPS (also known as Electron Spectroscopy for Chemical Analysis or
ESCA) was used for the determination of the surface composition of the
homo- and copolymers, the determination of oxidation of sulfoxide to
sulfone, and the observation of changes on the surface of the polymers upon
thermal treatment. A Kratos XSM-800 x-ray photoelectron


spectrophotometer was employed for the measurements. All the
measurements were done by Mr. Richard Crockett in the material science
department. The instrument consisted of 2 chambers: (i) sample
treatment chamber and (ii) sample analysis chamber.
The sample was mounted as a film on a 10-sample carousel.
Automation allowed analysis of 10 consecutive samples during a run. Once
the sample is mounted the sample treatment chamber is evacuated. A
rotary oil pump in conjunction with a turbomechanical pump and a cold trap
makes it possible to attain vacuum in the order of 10*8 Torr routinely. The
sample is transferred into the sample analysis chamber only after a
vacuum of 10*8 Torr is attained in both of the chambers.
The sample is irradiated with a low energy Mg K-alpha (1253.6 eV)
X-ray photoelectrons. The kinetic energy of the electron emitted due to the
interaction of the X-rays with the atomic orbital electron is measured and
the binding energy of the electron is calculated. The binding energies of
the various elements are standardized using the C-|S peak (285 eV) as the
reference. The instrument is occasionally calibrated using a thin silver
foil (Ag3S 368 eV).
High temperature XPS was carried out using a fast insertion
stainless steel probe mounted on a copper block. The polymer was mounted
on the copper block, introduced in the sample treatment chamber and
evacuated. The sample was scanned at room temperature and heated in the
sample treatment chamber to 100C for 0.5 hrs. The thermocouple was
standardized to the sample temperature (50C differential). After all the
condensables were removed as registered by the vacuum in the chamber
(10*7 to 10*8 Torr) the sample was introduced in the analysis chamber and
scanned. A similar procedure was followed at 200C and 300C.


44
Contact Angle of PPVS Homo- and Copolymers
Contact angle is a measure of the surface free energy of PPVS homo-
and copolymers. Measurement of the contact angle was carried out by the
captive air bubble method. The polymer was dissolved in chloroform,
coated on a glass slide and was thoroughly pumped in the vacuum oven to
get rid of residual solvent. The coated slide was immersed in water and
constant volume air bubbles were delivered between the polymer film and
the water surface using a 5 ^1 syringe. The contact angle of the air bubble
between the polymer film and the water surface was measured after 30 s.
A number of observations were made and the mean of the values was taken.
The contact angle is inversely proportional to the surface free energy.
Thus the higher the contact angle the lower is the surface free energy.


CHAPTER 3
HOMOPOLYMERIZATION AND COPOLYMERIZATION OF PVS
Homopolvmerization
The polymerization of phenylvinylsulfoxide (PVS) was investigated.
Most of the polymerization studies were carried out on the racemic
monomer. However the optically active monomer was also investigated
albeit not as thoroughly.
Attempts were made by Mulvaney and Ottaviani to polymerize R-(+)-
isopropenyl p-tolyl sulfoxide using various anionic and radical initiators
which were unsuccessful [41]. Homopolymerization of R-(+)-p-
tolylvinylsulfoxide was also attempted using initiators such as benzoyl
peroxide, azobisisobutyronitrile, n-butyllithium and boron trifluoride
etherate. Once again their attempts failed. n-Butyllithium most likely
attacked the sulfur displacing the aryl group [42] and thus failed to
polymerize the monomer. Kunieda et al. [43,44] tried polymerization of
optically active p-tolylvinylsulfoxide using n-butylmagnesium bromide as
initiator. This gave an optically active polymer of a molecular weight of
2400. However they obtained very poor yields (10%). The successful
polymerization of PVS has recently been carried out using methyllithium as
initiator in THF at -78C [2].
In the present work the polymerization of PVS was carried out by
mixing a solution of the initiator and monomer in THF in vacuo at -78C.
Various initiators were tried initially for the polymerization and are
summarized in Table 3-1.


46
Table 3-1. Homopolymerization of PVS Using Various Anionic Initiators in
THF at -78C.
Initiator
Apparent
Weights (
Mw
Molecular
Exptl)a
Mn
Mn
Calcdb
Mw / Mn
Yield
(%)
TPML
2679
2066
1979
1.33
95
2747
2469
3200
1.11
60
5945
4219
5328
1.41
92
33100
24600

1.34
90
TPMLC
4502
3310
3970
1.36
90
TPMK
8060
6063
12500
1.33
95
DPHL
1240
1171
6089
1.1
>70
Methyl-
3025
2605
6241
1.16
94
lithium
10309
7423
7537
1.39
95
11261
7698
6729
1.46
90
17811
12349
12177
1.44
84
18384
15515
19976
1.18
75
EPSL
9751
7497
11873
1.3
70
14418
11982
11720
1.2
86
LiNph
18982
14594
15222d
1.3
90
a. From GPC using polystyrene standards
b. Mn Caled. = [monomer] converted/[initiator] x Mm0nomer
c. solvent system 1:1 ::THF:toluene
d. Mn Caled. = [monomer]/[initiator] x 2 x Mm0nomer


It is seen from the Table 3-1 that the delocalized carbanions viz
triphenylmethyllithium (TPML), triphenylmethylpotassium (TPMK) and
diphenylhexyllithium (DPHL) are excellent initiators. TPML was, in fact,
the initiator of choice and most of the studies of the polymerization of
PVS (kinetics, temperature effects, etc.) were carried out using this
initiator. There were several reasons for the choice. TPML is very easy to
synthesize (Chapter 2) from a quantitative reaction of triphenylmethane
(which itself is a solid and easy to purify and handle) with n-butyllithium.
The carbanion salt is extremely stable even at R.T. in vacuo (although we
always stored it in the freezer). The solutions of TPML have an intense
absorption in the visible region (e at 500 nm = 31,000) so that their
concentrations can be accurately measured by UV/VIS spectrometry. The
intense color also helps in monitoring visually the initiation process since
a dramatic change in color is seen in going from the TPML carbanion to the
a-lithiosulfinyl carbanion (dark red to yellowish green). Also TPML is not
nucleophilic enough to attack the sulfur atom in the monomer causing side
reactions (at least at -78C).
Methyllithium was the only alkyllithium successfully employed as
the initiator [1, 2]. n-Butyl and t-butyllithium, interestingly, attack the
sulfur atom causing an SN2 displacement of the aryl group [42, 45-48].
This has also been documented [44, 47] in alkyl aryl sulfoxides where the
alkyllithiums other than methyllithium prefer nucleophilic attack on the
sulfur of the sulfinyl rather than proton abstraction.
Electron transfer initiators like lithium naphthalide were also
employed for initiation. A two-ended polymerization of PVS was thus


48
achieved similar to conventional monomers like styrene [25]. Thus the
initiation of polymerization of PVS appears to be similar to the
conventional anionic polymerization for instance of styrene.
The dipole stabilized initiator 1 -lithio-1 -(phenylsulfinyl) ethane
(EPSL) which is a carbanion analogous to that of the growing chain was
also found to be an effective initiator giving polymers of controlled
molecular weight and narrow molecular weight distribution. As will be
discussed later polymeric initiators, both one-ended and two-ended can
also be used as initiators to give block copolymers.
The initiation of PVS is instantaneous as seen from an immediate
change in color from dark red (for the delocalized carbanion) to yellowish-
green color of the growing a-lithiosulfoxide carbanion (Figure 3-1).
Nature of the Propagating Carbanion
The living a-sufinyl carbanion has been shown to be a dipole
stabilized ion pair in THF [2], For instance the U.V. spectrum of
ethylphenylsulfoxide (EPS) and the carbanion derived from it show almost
no difference in the absorption maxima [2]. Also the 13C NMR signals for
the carbanion are almost the same as those of the parent hydrocarbon.
Since delocalization of the negative charge into the aromatic ring would
generally result in an upfield shift of the para carbon due to shielding [49-
SI], there appears to be little or no delocalization of the negative charge
into the aromatic ring. Also the IR spectra of the carbanion of EPS and the
parent hydrocarbon exhibit the same absorption wavelength for the S=0
stretch [2], All of these observations indicate the absence of
delocalization of the negative charge into the S=0 bond.
The bond moment of the S-0 bond has been determined to be 4.76 D
[51]. From the x-ray structure the S-0 bond length in EPS was found to be


C(Ph)3Li + Ch2 = CH S Ph
II
(Red)
-78C,
O
THF
C(Ph)3CH2CH Li +
S=0
I
Ph
Initiation
(Yellowish-Green)
n CH2= CH S Ph
II
O
C(Ph)3 (CHj- CH -)tp CH2 CH Li+
S=0
1
s=o
1
Propagation
1
Ph
1
Ph
1
r MeOH
C(Ph)3-
-(CH2-CH^-CH2
-ch2
i
1
s=o
1
1
S^O
1
Termination
1
Ph
(colorless)
1
Ph
Figure 3-1. Homopolymerization of PVS.


50
1.47 [2], Using the equation: n. = e d, where |i is the dipole moment in
debye, e is the magnitude of charge in ESU and d is the bond length. The
magnitude of the apparent charges on oxygen and sulfur was thus found to
be 0.67 electrons. Thus the S-0 bond can be best described as a bond with
substantial ionic character.
Elegant 13C NMR studies by Marquet et al. [49-51] reveal that the
A1Jc-H in the a-lithio sulfoxide shows a large increase (+16.5 Hz) in 13C
NMR upon metalation of the a-carbon of methyl phenyl sulfoxide. Thus the
carbon bearing the negative charge was shown to have a high sp2 character
similar to that found in Ph2CHLi. In methyl phenyl sulfoxide it was found
that the 13C-1H coupling constant decreases in the cryptated potassium
salt as compared to the uncryptated complex. Thus the carbanion becomes
more pyramidal (or the sp3 character increases) upon cryptation. This
suggests that the planar sp2 configuration is stabilized by interaction with
the cation. It is therefore reasonable to assume a chelated structure
(Figure 3-2) possible because of the high charge density present on the
oxygen in the S-0 bond. This internal chelate interaction is strong even for
very polar solvents and is disrupted only upon using a very powerful
chelating agent such as a cryptand [51].
The chelated structure is possible even for potassium which is
expected to have a looser interaction with the anion. The a-potassio
sulfoxide would be expected to have similar properties as the a-lithio
sulfoxide. This is in fact what we find by using TPMK as initiator (Table
3-1). The molecular weight distribution which is a good indication of the
efficiency of the initiation is similar to that for TPML. The effect of
decreasing the solvent polarity from 100% THF to 1:1 THF: toluene would be
expected to increase the anion-cation interaction. However we see little


51
Figure 3-2. Chelated ion pair structure of a-sulfinyl carbanions with
lithium as counter ion.


52
change in the SEC of the polymerization product in going to a less polar
medium (Table 3-1).
Effect of Temperature
The effect of temperature in both the initiation and in the
propagation reaction was found to be dramatic. A series of experiments
were performed to explore the effect of temperature on the initiation and
polymerization. The results of these experiments are summarized in Table
3-2.
In runs 1 and 2 two parallel polymerizations were carried out having
similar concentrations of initiator and monomer. One of the
polymerizations was initiated at -85C and was allowed to propagate at
-85C using a mixture of dry ice and ethylether. The other was initiated at
-25C and kept at -25C using a mixture of dry ice and carbon
tetrachloride. Runs 3 and 4 were carried out by initiation and propagation
at -78C and 25C (room temperature) respectively.
Run 5 was carried out in an apparatus which was provided with a
side bulb connected through a high vacuum teflon stopcock. The reaction
was initiated at 25C and the solution was then immediately divided into
two portions by pouring half of the reaction mixture in the side bulb
through the high vacuum teflon stopcock. The stopcock was then closed off
and the solution in the side bulb was quickly cooled to -78C. The solution
in the main body, however, was kept at 25C. In this way one can see the
effect of initiation at 25C and propagation at -78C and 25C
respectively.
Run #6 was similarly initiated at -78C and divided into two
portions; one was allowed to proceed at -78C while the other was warmed
up to 25C. Run #7 was simply a repeat of run #6.


Table 3-2. Effect of Temperature on Polymerization of PVS. Initiated by
TPMLinTHF.
Run #
Tia
C
Tpb
C
Mw
Mn
Mn
Calcdc
Mw/Mn
Distribution
1
-85
-85
10810
7595
19025
1.42
unimodal
2
-25
-25
11012
7127
19025
1.55
unimodal
3
-78
-78
5945
4219
5328
1.41
unimodal
4
25
25
8495
3751
4892
2.26
bimodal
5
25
-78
9178
3671
4033
2.5
bimodal
25
25
8805
3108
4033
2.83
bimodal
6
-78
-78
6947
4533
4652
1.53
unimodal
-78
25
6829
3949
4652
1.73
unimodal
7
-78
-78
4795
3138
4567
1.53
unimodal
.zZS
AMI
2M2
4567
unimodal
a. Temperature of initiation.
b. Temperature of polymerization.
c. Mn Caled. =[monomer]/[initiator] x Mmonomer


54
Effect of Temperature of Initiation of PVS
It was seen that during initiation of PVS at 25C the color changed
from dark red (TPML) to yellowish-green, characteristic of the a-sulfinyl
carbanion, and then once again to red within minutes. The color
progressively became darker with time and did not discharge when the
carbanion solution was reacted with methanol. An attempt made to
monitor the formation of the colored side products using UV/VIS
spectroscopy failed. Only a tail was seen in the visible region which gave
no useful information as to the identity of the colored products.
The effect of temperature during initiation by TPML was of interest.
It was seen that initiation at low temperatures (<-25C) led to a unimodal
distribution in the SEC chromatogram. However, initiation at 25C gave
rise to a bimodal distribution (Figure 3-3) even when the solution is cooled
down to -78C immediately after initiation (Figure 3-4).
This leads us to believe that at low temperatures the initiation
process forms only one propagating species. However, at higher
temperatures two distinct propagating or initiating species may be
present: a major giving rise to the high molecular weight peak in SEC with
a minor giving rise to the low molecular weight peak (Figures 3-3 and 3-4).
Obviously the high molecular weight (major) initiating species propagates
or initiates faster than the low molecular weight (minor) one.
It is seen from Table 3-1 that there is excellent agreement between
the calculated and experimental Mn in most runs. This indicates that the
"living" nature of the polymerization is similar to that of a conventional
anionic polymerization for instance of styrene.


5 5
Figure 3-3. SEC chromatogram of PPVS initiated by TPML at 25C and
polymerized at 25C in THF. Eluting solvent: THF. Flow rate: 1 ml/min.
h
pol


56
Figure 3-4. SEC chromatogram of PPVS initiated by TPML at 25C and
polymerized at -78C in THF. Eluting solvent: THF. Flow rate: 1 ml/min.


5 7
Reactions of alkyllithium with sulfoxides having an a-proton have
been well-studied [44-47], Methyllithium and LDA mainly abstract the
a-proton. n-Butyllithium and t-butyllithium, on the other hand, attack the
sulfur causing a ligand exchange on the sulfoxide. Jacobus and Mislow [44]
report the racemization and cleavage of optically active aryl methyl
sulfoxides with methyl and phenyllithium. According to their mechanism
racemization of the sulfoxide and exchange of the alkyl group takes place
via a sulfine intermediate (Figure 3-5). They also proposed a sulfurane
adduct to account for the exchange of the aryl group (Figure 3-6).
Durst et al. [47] have disagreed with the above mechanisms. They
found two competing reactions when various sulfoxides were reacted with
alkyllithiums: a) abstraction of an a-hydrogen to give a-lithio sulfoxide
and b) carbon-sulfur bond cleavage according to the equation
O O
>1 II
S R2 + R3-Li R1 S R3 + R 2" L i
They propose a simple SN2 displacement at sulfur and considered the
sulfurane as a transition state not an intermediate. In our system
displacement of the phenyl group by TPML at -78C is unlikely because
TPML is less basic and more sterically hindered compared with
alkyllithium. The nature of the side reaction is possibly associated with
the presence of chelated stereoisomers some of which propagates faster
than others. A true side reaction, therefore may not be present.
We found the polymerization of PVS to be extremely rapid even at
-78C. Thus at 25C the polymerization is expected to be even more rapid.
The two initiating or propagating species (slow and rapid) that are seen


58
Ph
O
ti
R ¡ CHo
ch3u
Jo
R CH2Li
RLi + [CH2=S=0]
racemization ligand exchange
Figure 3-5. Sulfine intermediate formed during racemization of
sulfoxides.
O
CH,
Ph
O
ll
Figure 3-6. Sulfurane intermediate formed during ligand
exchange in phenylmethylsulfoxide.


5 9
would be expected to form and propagate in the first few seconds of the
polymerization. Thus cooling the reaction mixture after initiation at 25C
does not have much effect on the distribution and we still see the bimodal
nature of the chromatogram (Figure 3-4) (Run 5 in Table 3-2).
The total absence of bimodal distributions for the samples initiated
at -78C suggests that at -78C we form only one initiating species which
propagates further. Warming the solution up to 25C after initiating at
-78C does not give rise to bimodal distribution (Runs 6 and 7 in Table
3-2). However, the molecular weight distribution of the sample was
considerably broadened when it was warmed up to 25C. This indicates a
different effect of temperature on the polymerization as compared to the
initiation (see below).
Also from Table 3-2 it is seen that lower the polymerization
temperature narrower the MW distribution. The difference in molecular
weight distributions observed at the same temperature (-78C) for
different runs (Tables 3-1 and 3-2) for the same initiator is probably due
to the difference in the purity of monomer from batch to batch. Also this
small variation may be due to changes in the SEC conditions. Although all
the SEC runs were carried out as much as possible under identical
conditions and although the calibration curves were recalibrated from
month to month there would still be the some experimental error involved
with the system (i.e. change in flow rate due to wear and tear of the pump,
leakage in the system, difference in the injection conditions, difference in
the concentration of the solution injected, etc.).
Effect of Temperature on Polymerization
It was noticed that warming the polymerization mixture to 25C
resulted in a change in color from yellowish-green to red which


60
progressively became darker with time. The dark red color did not
discharge when terminated with methanol. Furthermore the molecular
weight distributions of the polymers were found to broaden considerably at
higher temperatures (Table 3-2). This was an indication that
polymerization side reactions played an important role at ambient
temperatures. As mentioned before efforts to determine the colored side
products by UV/VIS spectometry failed due to the strong absorption of the
sulfoxide group in UV (Xmax 253 nm).
The side reactions are seen to be present even at -78C. Thus a
tailing effect in the SEC chromatograms were usually observed (Figure
3-7), which was always in the low molecular weight region. The tailing
and consequent worsening of the molecular weight distribution was more
prominent for longer reaction times. Even at -78C, after termination,
there was usually a yellowish tinge in the solution which was not due to
the living carbanions.
During the initial stages of our investigation of this system we
attributed the tailing due to our inability to completely purify PVS to
anionic polymerization standards. As mentioned in Chapter 2 the
importance of rigorous purification of solvents and reagents during anionic
polymerization cannot be overemphasized. The presence of parts per
million of electrophilic impurities could be disastrous especially for the
preparation of high molecular weight polymers [25, 26]. Sulfoxides are
known to form strong hydrogen bonds so that hydrogen bonds may have
formed with electrophiles such as water. PVS is probably synthesized
from a Grignard reaction of vinyl magnesium bromide with
ethylbenzenesulfinate [2]. It is conceivable that some of the reactants may


61
Figure 3-7. SEC chromatogram of PPVS initiated by TPML in THF at -78C
and polymerized at -78C for 33 hours. Eluting solvent: THF. Flow rate: 1
ml/min.


62
have been left behind which may have very close boiling points and thus
cannot be completely removed through distillation.
Another possibility is the decomposition of the monomer during
distillation at high temperatures. Mislow did extensive studies on the
thermal racemization of alkyl aryl sulfoxides [52, 53]. They estimated the
bond dissociation energy of cleavage of C-S bonds in alkyls and aryls to be
about 56-69 kcals/mole whereas the activation energy of the pyramidal
inversion was estimated to be about 36 kcal/mole [52], Thus they
discounted the homolytic cleavage-recombination mechanism for
racemization except in case of benzyl p-tolylsulfoxide which gives rise to
benzyl and p-toluenesulfinyl radicals upon cleavage of the benzylic C-S
bond [53]. Another possibility is a five-center pyrolytic cis-elimination
mechanism for sulfoxides having a [5-hydrogen (Figure 3-8) [3, 54]. A
detailed discussion of this elimination will be given in Chapter 4.
The absence of detectable impurities in GC leads us to believe that
the tailing effect in the low molecular weight side in polymerizations
carried out at -78C may be due to factors other than impurities in the
monomer. It was noticed that the side reactions were more prominent in
polymerizations with long reaction times so that the growing polymer
chain is somehow deactivated during the polymerization. Several
explanations are possible since we have a number of sites in the polymer
chain which could be attacked by a carbanion leading to various side
products. Apparently these side reactions are strongly temperature
dependent and lead to broad molecular weight distribution (Table 3-2).
Probable deactivation reactions could be
i. E2 elimination of phenyl sulfenic acid in the polymer chain by a growing
carbanion [55, 56] to form polyene linkages in the chain


63
¡i. Deprotonation of an a proton in the chain to form a dipole stabilized
carbanion [44-48]
iii. Attack on the sulfinyl of a polymer chain by the growing a-lithio
sulfoxide [47]
The pKa of LDA [57] is very similar to that of the a-lithio sulfinyl
carbanions [48]. Thus it was decided to investigate the effect of LDA on
PPVS. LDA was prepared in vacuo by a reaction of diisopropyl amine and


64
Figure 3-8. Possible elimination reaction in phenylvinylsulfoxide at high
temperatures.


65
methyllithium. The ratio of LDA:sulfoxide was about 1:1. The THF solution
of PPVS was then added to the THF solution of LDA at -78C. It was seen
that the polymer solution turned dark red (similar to that of the solution of
polymerization at 25C ). After about 15 minutes methanol was added to
quench any LDA left behind and the polymer was purified by precipitation in
ether. The polymer was not completely soluble in THF. The SEC of the
soluble polymer showed a decrease in molecular weight as compared to the
starting polymer. Thus a cleavage of chains by LDA at -78C may have
occurred. The change in color upon reaction of LDA with PPVS may be due
to the formation of low MW polyenes in the polymer due to a p elimination
of phenyl sulfenic acid as discussed above.
Conversion of () PVS With Time
A rough idea of the conversion of monomer with time and the
kinetics was highly desirable. This would give us the half life of the
polymerization reaction and would help us decide when to terminate the
polymerization so as to obtain reasonable yields without the side reactions
associated with long reaction times.
A polymerization reaction was carried out at -78C under rigorously
dried argon and aliquots of the polymerizing solution were withdrawn by
syringe at various times. Naphthalene was employed as an internal
standard to monitor the concentration of the monomer at various times
during polymerization (Chapter 2). The polymer was also characterized by
SEC. The results of one of the runs are summarized in Table 3-3.
Surprisingly the variation in molecular weight was negligible from 5
minutes to 3 hours. Also no detectable monomer was found by GC even
after just a few minutes of reaction. This indicated that the
polymerization of PVS was extremely rapid even at -78C.


66
Table 3-3. SEC Results of the Conversion of Monomer with Time. Initiated
by TPML in THF at -78C under Argon.
TIME
minutes
Mpa
SEC
Mw
Mnb
Mw / Mp
5
5859
6559
3772
1.74
15
6215
7209
4096
1.76
60
6691
7852
4708
1.67
1 20
6790
7515
4001
1.88
1 80
6891
7907
4053
1.95
a. With reference to polystyrene standards.
b. Mn Calculated = 2854.
Since stop-flow techniques were not available, an experiment was
devised wherein the polymerization reaction was terminated at incomplete
conversion. The time of reaction was 21 seconds after which the
polymerizing solution was quenched with methanol. The polymer was
precipitated as usual in excess of ether and the concentration of monomer
in the filtrate was determined by GC.
The rate constant for the pseudo-1st order polymerization reaction
(at a concentration of living polymer chains of approximately 10'3 M)
determined in this way was found to be 0.17 sec'1 with a half life of 4.1
seconds. Thus the polymerization reaction is seen to be extremely rapid.
Several factors must be considered before accepting the above value
of the rate constant. There could be errors involved in the determination of
the time of polymerization. Also the rate of polymerization may not
necessarily be pseudo-1st order (i.e., the assumption that the
concentration of the living ends is constant may not be true).


6 7
Polymerization and Studies of (+1-PVS
Optically active (+)-PVS {[a]ci20 = 358.5} was polymerized using a
procedure similar to that used for the racemic monomer using TPML in THF
at -78C. The polymer shows some unique properties.
It was found that the optically active monomer does not lose its
optical activity upon polymerization. This is expected since sulfoxide
sulfur does not epimerize under the polymerization conditions (1, 2], As
seen from the 13c NMR (Figure 3-9) all of the signals from the optically
active polymer are considerably sharper than the corresponding ones of the
racemic PPVS (Figure 3-10). This suggests a highly stereoregular
structure of (+)-PPVS as compared to the racemic polymer. The (+)-PPVS
would be expected to be isotactic as suggested by the broad methylene
absorption in NMR and by the stereochemistry of the dimers and trimers
studied extensively by Buese and Hogen-Esch [1, 2). The polymer was found
to be only partially soluble in THF and chloroform both of which are
excellent solvents for racemic PPVS. The polymer is soluble in glacial
acetic acid. The decrease in solubility of (+)-PPVS also points to a more
regular structure. The polymer was found to be monodisperse (Mn = 1359,
Mn Calculated = 2920, Mw/Mn = 1.19).
Cooolvmerization of Stvrene and PVS
Both A-B and A-B-A type of copolymers were synthesized as
described in the experimental section.
A-B Copolymers
Figure 3-11 illustrates the various steps in A-B block
copolymerization and Table 3-4 summarizes the SEC data of various A-B
f'9
copolymerizations.


68
Figure 3-9. 50 MHz 13C NMR of (+)-PPVS in CDCI3 at room temperature.


6 9
Figure 3-10. 50 MHz 13C NMR of racemic PPVS in CDCI3 at room
temperature.


Table 3-4. A-B Diblock Copolymerization of Styrene and PVS in THF at -78C
Sample
Moles
Polyst
yrene Block
Moles
Moles
A
B Diblock
Yield
PPVS
Styrene
Mn
Mp
Myy/Mn
DPP3
PVS
Mn
Mp
Mw/Mn
%e
%f
x10-3
Calc'd3
SEC
x10-3
Added
Calc'dC
SECd
x10i2
AB21
8.76
3,432
2,713
1.10
0.360
2.25
3,664
3,979
1.16
98.6
21.32
AB53
6.13
3,432
2,713
1.10
0.250
6.75
6,790
7,954
1.22
97.0
47.08
AB66
7.00
3,432
2,713
1.10
0.288
14.30
10,271
11,245
1.27
96.9
66.82
AB85
6.13
3,432
2,713
1.10
0.252
35.00
16,920
17,101
1.24
68.1
74.85
AB90
1.93
3,432
2,713
1.10
0.079
15.80
19,055
19,252
1.41
54.3
78.37
PSPVS
28.40
8,687
9118
1.04
0.250
23.00
16,647
13,120
1.09
56.2
47.42
ABd89
10.00
2,359
3,341
1.09
0.440
2.25
4,121
3,733
1.18
95.6

a. Mn Calculated = moles styrene / moles t-butyllithium x 104.
b. DDPL = Polystyryllithium capped with DPE. Measured by UV/Vis.
c. Mn Calculated = moles PVS converted / moles DPPL x 152.22 + Mn polystyrene block.
d. Mp SEC with reference to polystyrene standards.
e. % Yield = gs of polymer / gs of monomer x 100.
f. % PPVS calculated from the ratio of aromatic absorptions of sulfoxide phenyl (3=7.4 PPM) and polystyrene
phenyl (3=7.0 PPM {meta and para protons} and 3=6.5 PPM{ortho protons}).
g. Diblock using styrene-d8.


71
(GHgJgC Li -P nCH2 CH-Ph
-78C/THF
(CH3)3C-CH2 CH(CH2 CH)n Li+
Ph Ph
living polystyryllithium (cherry- red)
Ph
CH2-C^
Ph
(CH3)3C- (CH2- CH)n CH2 C(Ph)2Li+
Ph
capped living polystyryllithium (dark red)
mCH2= CH SPh
II
O
(CH3)3C- (CH2- CH)n CH2 C(Ph)2- (CH2 CH)
r.w\mLi+
Ph
(yellowish green)
MeOH
S O
i
Ph
(CH3)3 C- (CH2 CH)n CH2 C(Ph)2- (CH2 CH) H
I I
Ph
(colorless)
S = 0
Ph
Figure 3-11. A-B copolymerization of styrene and PVS.


72
Styrene was polymerized by a slow vapor phase addition of the
monomer onto a rapidly stirred initiator solution at -78C in vacuo [25,
26]. Several initiators like methyllithium, s-butyllithium, etc. were tried.
However we found purified t-butyllithium to be the most efficient. This
initiator gave polymers with reproducible molecular weights and narrow
molecular weight distributions.
As can be seen from Table 3-4 the Mn calculated from the
concentrations of monomer and initiator (determined by UV) was quite
close to the one determined by SEC. Also the molecular weight distribution
for the styrene block was narrow (<1.1) which indicates negligible killing
of the growing polystyryllithium chains. Thus the DPE capped
polystyryllithium was seen to be an excellent initiator for PVS. The
molecular weight distributions were also better than for homopolymers of
PVS which is expected since we start out with polymeric initiators of
narrow molecular weight distribution. However at high PVS concentrations
considerable termination during polymerization was observed as seen from
the worsening molecular weight distribution and lower yields (entries 4
and 5 in Table 3-4).
Figure 3-12 shows a typical SEC chromatogram of the polystyrene
homopolymer (i) and styrene-PVS copolymer (ii). The PPVS content in the
copolymer was calculated from the 1 H aromatic absorptions of the
polystyrene phenyls (3 = 7.0 PPM {meta and para} and 3 = 6.5 PPM {ortho})
and the sulfoxide phenyls (3 = 7.5 PPM). Figure 3-13 is a 200 MHz 1H NMR
of a styrene-PVS A-B diblock copolymer and Figure 3-14 is the
corresponding 200 MHz 1H NMR of poly(phenylvinylsulfoxide) initiated by
TPML in THF at -78C. The ortho protons in polystyrene are seen to be


73
Figure 3-12. SEC chromatograms of i) Polystyrene homopolymer (Mp =
8200, Mw/Mn = 1.09) and ¡i) A-B copolymer of styrene and PVS (Mp =
13,120, Mw/Mn = 1.09). Eluting solvent: THF at 1 ml/min.


7 4
Figure 3-13. 200 MHz 1H NMR of poly(styrene-b-PVS) copolymer in CDCI3
at room temperature.


7 5
Figure 3-14. 200 MHz 1H NMR of PPVS (initiated by TPML in THF at -78C)
in CDCI3 at room temperature.


shifted upfield relative to the meta and para. This is due to the shielding
of the ortho protons being in the anisotropic field of the rc-electron current
of the neighboring ring [58],
In the runs 1-5 the polystyrene block was kept constant (Mp SEC =
2,713) whereas the sulfoxide content was varied. There was a good
correlation between the sulfoxide content calculated (from the ratio of
moles of styrene to moles of PVS) (21%, 53% and 66%) and that observed
from 1H NMR (21%, 47% and 67% respectively) for the first three runs.
However, a large variation was seen for runs 4 and 5 (85% and 90%
calculated and 75% and 78% observed). This also indicates substantial
killing during runs 4 and 5, where the concentration of PVS was high.
Run 7 was carried out using styrene-d8 and the corresponding
copolymer was used for the structure determination of the thermal
elimination product.
A-B-A Cooolvmers
Figure 3-15 illustrates the various steps in the A-B-A block
copolymerization and Table 3-5 summarizes the SEC data of the A-B-A
runs.
Lithium naphthalide was employed as the initiator for the two-ended
polymerization of styrene [39]. As is well known [25, 26] lithium
naphthalide initiates polymerization of styrene by electron transfer to
form the radical anion of the monomer which then immediately couples and
forms the dimer with two anions on either end. This dimer can further
propagate in both directions to give a two-ended polystyryllithium.
Excellent results were obtained when lithium naphthalide was
prepared using excess of naphthalene (Table 3-5) (Figure 3-16). However,
when lithium naphthalide was prepared by using an excess of lithium metal


77
(dark green)
7
CH2=CH Ph
-78C/THF
Li+ CH CH2CH2CM Li+
Ph
(cherry red)
Ph
2mCH2=CH Ph
Li^CH CH2) CH CH2 CH2CH (CH2CH)mLi+
Ph
Ph
(dark red)
Ph
Ph
L^CH CH2)
AAA^A/VW
+ 2n CH2= CHS-Ph
O
(CH2 CH)nLi+
s=o s=o
pti ph/
(yellowish-green)
MeOH
PPVS-PS-PPVS triblock copolymer
(colorless)
j
Figure 3-15
A-B-A copolymerization of styrene and PVS.


Table 3-5. A-B-A triblock copolymerization of Styrene and PVS in THF at -78C
Sample
Moles
Styrene
x10'3
Polyst
Mn
Calc'd3
yrene Bk
Mp
SEC
)ck
Mw/Mn
Moles
DDPPLb
x10'3
Moles
PVS
Added
x10i2
A-B-
Mn
Calc'dc
A Tribloc
Mp
SECd
k
Mw/Mn
Yield
%e
PPVS
%f
ABA30
6.35
11,960
11,393
1.07
0.132
2.7
14,506
18,152
1.14
97.9
41.80
ABA50
6.10
11,960
11,393
1.07
0.127
6.1
18,668
21,201
1.23
96.6
49.86
ABA78
5.55
11,960
11,393
1.07
0.116
19.7
29,967
30,601
1.33
74.3
65.50
ABA90
2.96
11,960
11,393
1.07
0.062
26.0
33,357
28,117
1.51
35.4
69.79
ABASO
19.0
55,000
59,520
1.08
0.079
15.0
79,233
79,060
1.12
90.5
29.46
ABAS1
25.0
26,666
29,750
1.04
0.169
15.0
43,672
48,078
1.10
98.2
35.53
ABAd89
9.60
9,793
10,553
1.08
0.188
3.8
13,597
14,921
1.10
95.0

a. Mn Calculated = moles styrene / moles lithium naphthalide x 2 x 104.
b. DDPPL = Dianion of DPE capped polystyryllithium. Concentration measured by UV/Vis.
c. Mn Calculated = moles PVS converted / moles DDPPL x 152.22 + Mn polystyrene block.
d. Mp SEC with reference to polystyrene standards.
e. % Yield = gs of polymer / gs of monomer x 100.
f. % PPVS calculated from the ratio of aromatic absorptions of sulfoxide phenyl (3=7.4 PPM) and polystyrene
phenyl (3=7.0 PPM (meta and para protons} and 3=6.5 PPM{ortho protons}).
g. Triblock using styrene-d8.


79
we ended up with a bimodal distribution in the SEC chromatogram (Figure
3-17). When lithium naphthalide is prepared using excess of lithium metal
one also gets the formation of naphthalene dianion alongwith the radical
anion [31]. The dianion itself may initiate styrene and a naphthalene group
may thus be incorporated in the middle of the chain [59]. In absence of
more extensive experimental evidence we will not attempt to interpret in
detail these anomalous results.
Table 3-5 once again shows that the dianion of polystyryllithium is
an excellent initiator for PVS. Again the molecular weight distribution of
the copolymer increases with increasing content of sulfoxide. This
indicates some termination when larger amounts of PVS are used.
Proof of Pianion Formation in the Lithium Naphthalide Initiated
Polvstvrvllithium
The "two-endedness" of the DPE capped living polystyryllithium
initiated by lithium naphthalide was proved in the following manner.
Styrene was independently initiated by lithium naphthalide in THF at -78C
and capped with 1,1-DPE. The concentration of the carbanions was
measured using UV/VIS spectrometry (Table 3-6). The carbanion solution
was attached to an apparatus equipped with a quartz cell and a quartz
spacer. An excess of fluorene in a break-seal was also attached to the
apparatus. This was then evacuated and the carbanion solution was poured
in the cell through the break-seal and the absorbance of the red carbanion
solution was measured at its .max (500 nm, Table 3-6). The living
carbanion was then reacted with fluorene. An immediate change in the
color of the solution was noticed on formation of the fluorenyllithium from
dark red to yellow. The absorbance of the solution of fluorenyllithium was
measured at its Xmax (373 nm) (Table 3-6). The extinction coefficient of


80
¡¡ i
Figure 3-16. SEC chromatograms of i) Polystyrene homopolymer (Mp =
10,553, Mw/Mn = 1.08) and ii) A-B-A copolymer of styrene and PVS (Mp =
14,921, Mw/Mn = 1.1). Polystyrene block initiated by lithium naphthalide
prepared by using an excess of naphthalene. Eluting solvent: THF at 1
ml/min.


81
ii i
13
Figure 3-17. SEC chromatograms of i) Polystyrene homopolymer and ¡I)
A-B-A copolymer of styrene and PVS. Polystyrene block initiated by
lithium naphthalide prepared by using an excess of lithium metal. Eluting
solvent: THF at 1 ml/min.


82
Table 3-6. UV/Visible data for various carbanion initiators in THF at 25C.
CARBANIONS
*max
nm
MOL4R
EXTINCTION
COEFFICIENT (z)
TPML
500
30,980
TPMK
486
26,420
Lithium Naphthalide
367
10,263
326
22,350
292
32,550
aMS-22Li+
342
19,700
Polystyryllithium capped with
1,1-DPE, dianion
501
56,000
Fluorenyllithium3
373
9,600
Fluorenylpotassiumb
362
11,500
Potassium Chromate3
372
4815
a. From references 35-37.
b. Estimated from e of fluorenylsodium (Xmax 356 nm) =10,800 and
fluorenylcesium (Xmax 364 nm) = 12,000 [37],


83
the carbanion was thus calculated (e at Xmax = 28,000) from that of
fluorenyllithium which is well-known (e at X max = 9,600) [35-37], Hence
the concentration of the dianion of diphenyl polystyryllithium was
determined (moles of the carbanion solution = 3.03 x 10*6).
The terminated polystyrene was purified by precipitation in excess
of methanol and injected in SEC (Mw = 9199, Mn = 8633, Mw/Mn = 1.07, Mn
calculated = 9591). The polymer was weighed and hence the number of
moles of polymer was calculated from Mn (Moles of polymer = 1.48 x 10*4
moles.). Thus the ratio of moles of carbanion / moles of polymer was found
to be 2.05. This confirms that there are two moles of carbanion for every
mole of the polymer (i.e., two carbanions per growing polymer chain).
In conclusion, it is seen that homo- and copolymerization of PVS can
be carried out using conventional anionic polymerization techniques. A
variety of initiators could be employed but it was seen that delocalized
carbanions like TPML are excellent initiators. Electron transfer initiators
could also be employed to achieve two ended polymerization of PVS. There
was an excellent correlation between the calculated Mn and the
experimental Mn determined by SEC and 1H NMR. The molecular weight
distribution in most homopolymers was found to be narrow (<1.4). The
effect of temperature on initiation and propagation was seen to be
dramatic. In general lower temperatures resulted in well-defined and
narrow molecular weight distribution polymers. Initiation at -78C led to
unimodal distribution indicating one initiating species whereas initiation
at 25C led to a bimodal distribution due to the possible presence of two
initiating species. The polymerization of ()-PVS was seen to be
extremely rapid with a pseudo-first order rate constant of 0.17 sec*1 and


84
a half-life of 4.1 seconds. Optically active (+)-PVS was also polymerized
and the resulting polymer was found to be stereoregular in structure.
Both A-B and A-B-A block copolymers of styrene and PVS were
synthesized. The A-B diblock copolymerization was carried out by vapor-
phase polymerization of styrene in THF at -78C using t-butyllithium as
initiator followed by capping with 1,1-DPE. The capped polystyryllithium
was used for initiation of the PVS block. The A-B-A triblock
copolymerization was carried out by reacting two-ended polystyrene
prepared by using lithium naphthalide as initiator with 1,1-DPE to give a
capped stable living dianion of polystyryllithium which initiated PVS at
both ends to give an A-B-A triblock copolymer, polystyrene being the inner
block. The molecular weight distributions of the block copolymers were, in
general, narrower than the homopolymers.


CHAPTER 4
THERMAL ELIMINATION STUDIES
The thermal instability of sulfoxides has been recognized for more
than a century [60]. However, the synthetic utility of sulfoxides in organic
chemistry and the detailed mechanism of elimination of sulfoxides was
pioneered by Kingsbury and Cram [3]. They demonstrated the facile
elimination of phenyl sulfenic acid from 1,2-diphenyl-1-
phenylsulfinylpropane to give the isomeric 1,2-diphenylpropene. The
mechanism they proposed involved a stereospecific cis elimination similar
to the E¡ Cope elimination in amine oxides [61] and elimination in
selenoxides [62].
Mechanism of Sulfoxide Elimination
The mechanism of sulfoxide elimination proposed by Kingsbury and
Cram [3] is accepted even today. The mechanism they proposed is similar
to the classical mechanism for the internal elimination reaction. The
leaving group (Ph-S-O) abstracts a hydrogen from the [3-carbon (Figure 4-
1). The elimination is stereospecific; the erythro (1R, 2R or 1S, 2S)
sulfoxide gives trans-1,2-diphenylpropene whereas the threo (1S, 2R or 1R,
2S) gives cis-1,2-diphenylpropene at least at low temperatures.
At higher temperatures the reaction is less stereospecific. Thus at
higher temperatures a C-S homolytic bond cleavage was proposed to form a
sulfinyl and a benzyl radical pair without the radicals ever leaving the
solvent cage [3] (Figure 4-2). Other workers in this field [7, 65, 66, 67]
have accepted the above mechanism with some changes. Block [77]
85


86
\
(1 R, 2S)-1,2-diphenyl
propane
1 -phenylsulfinyl
CH3
Ph
C
C
H
Ph
Cis 1,2-diphenylpropene
Figure 4-1. Thermal eliminations in (1R, 2S)-1,2 -diphenyl
1-phenylsulfinyl propane at low temperatures.


87
H
Ph
ch3
n1' C"
/
H
Ph
SO'
Ph^ \
O
CPU''
Ph
H
I
, C-
/
(1 R, 2S)-1,2-dipheny 1-1 phenylsulfinyl
propane
Ph
+
C 'ii /
Ph
H
ch3
Ph
C=C
*>
Trans ,2-diphenylpropene
Figure 4-2. Thermal eliminations in (1R, 2S)-1,2-diphenyl
1-phenylsulfinylpropane at high temperatures.


88
considered the sulfoxide elimination analogous to that of the amine oxides,
involving a five-membered six-electron transition state (4 electrons from
the C-S and C-H a bonds and 2 electrons as a lone pair on oxygen) and
termed it as a a2s + o2s +co2s sigmatropic elimination.
Kwart et al. [54] carried out a detailed comparison of the sulfoxide
and amine oxide thermolysis. A temperature dependence of the kinetic
deuterium isotope effect was found for the deuterated sulfoxides. This
result was apparently in keeping with what has been established for a
planar, concerted, pericyclic transition state. In contrast the amine oxide
elimination was indicative of a bent, cyclic transition state.
Use of Sulfoxides as Acetylene Svnthons
Vinyl sulfoxides have been extensively used in synthetic organic
chemistry as acetylene equivalents. It would serve us well to know a little
about the synthetic value of sulfoxides to introduce a vinyl group in a
molecule.
Michael Addition-Elimination.
Vinyl sulfoxides react with certain nucleophiles to give Michael-type
addition [4-9]. This Michael-adduct could then be subjected to thermolysis
to introduce a vinyl group. Thus vinyl sulfoxides were shown to be
acetylene synthons in Michael addition. This is illustrated in Figure 4-3 [4,
5] and Figure 4-4 [6]. The Michael adduct could also be subjected to
reductive desulfurization [9].
Alkylation-Elimination.
Trost [63, 69] carried out a series of synthetic reactions involving
the alkylation of a-sulfinyl carbanions and eliminations of the resulting
sulfoxides to give a-p unsaturated olefins (Figure 4-5).


8 9
X H + CHo =
Base/THF
CH S Ar
II
O
XCHo CH S Ar
II
O
H+
X CH=CH2 +
Ar-S-O-H
X CHp CHo- S A r
II
O
Figure 4-3. Michael addition-elimination of vinyl sulfoxides.
1)NaH/THF
2) H+
O
II
C-0-CH2-CH3
CH2-CH2-S-Ph
O
(50%)
Figure 4-4. PVS as a vinyl synthon.


90
-CH2-Ph
O
1) LiNR^DME
2) Ph-CH2-Br
Ph
Ph-^-CH-CH2-Ph
O
A
Ph-CH=CH-Ph
Trans-stilbene (79%)
Figure 4-5. Alkylative eliminations.
R-i CH2 CH2 C R 1) Base
O
2) R2-S-S-R2 r
/CH2\
CH
O
II
/c\
R
S-R;
O
R1-CH=CH-C-R
A
-r2soh
[O]
o
h2n cn
R1 CH r
I
o=s-r2
Figure 4-6. Sulfenylation-dehydrosulfenylation route to unsaturated
ketones and esters.


Full Text

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81,9(56,7< 2) )/25,'$





THERMAL ELIMINATION OF POLY(PHENYLVINYLSULFOXIDE)
AND ITS STYRENE BLOCK COPOLYMERS
Of
RUSTOM SAM KANGA
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1988
yOF F LIBRARIES

Dedicated
to
my parents
Sam and Gool Kanga
and to my mentor
the late Mr. J. Elavia

ACKNOWLEDGMENTS
I wish to thank all the members of my supervisory committee: Dr.
George Butler, Dr. Kenneth Wagener, Dr. Merle Battiste, Dr. Russel Drago, Dr.
Christopher Batich and Dr. James Boncella.
Special thanks are given to Dr. Batich for his help and advice in XPS,
to Mr. Richard Crockett for running the XPS spectra of my polymers and to
Dr. King for running the pyrolysis-MS.
I thank Dr. Wagener for his support, encouragement and sagacious
advice, both chemical and non-chemical.
I am gratefully indebted to Dr. Thieo Hogen-Esch for his direction,
guidance, encouragement and best of all patience. He taught me a lesson I
will never forget: avoid mediocrity!
Thanks are offered to Lorraine Williams for her ready smile and
readier help. Thanks and cheers are expressed to all the people on the
polymer floor for having enriched my existence.
Words cannot express my gratitude nor my indebtedness to Pauline
Schneider for her help in preparing this manuscript and for being there at
the most critical point in my life!
in

TABLE OF CONTENTS
Page
ACKNOWLEDGMENTS
KEY TO ABBREVIATIONS
ABSTRACT
CHAPTER
1 INTRODUCTION
Polyacetylene (PA)
Precursor Routes to Polyacetylene
2 EXPERIMENTAL
High Vacuum Anionic Polymerization Techniques
Purification of Solvents, Monomers and Reagents
Purification of Phenylvinylsulfoxide and Ethylphenylsulfoxide..
Purification of Styrene and 1,1-Diphenylethylene
Purification of t-Butyllithium
Preparation of Initiators
Lithium Naphthalide
Triphenylmethyllithium (TPML)
1,1 Diphenylhexyllithium (DPHL)
Triphenylmethylpotassium (TPMK)
1-Lithio-1-(Phenylsulfinyl) Ethane (EPSL)
Determination of Concentration of Carbanions
Titration with Fluorene
vi i
v i i i
1
3
5
1 1
11
12
12
13
16
16
16
18
20
20
20
22
22
IV

Determination of Concentration by UV/Visible Spectroscopy 23
Polymerization of Phenylvinylsulfoxide 24
Copolymerization of Styrene and Phenylvinylsulfoxide 28
A-B Copolymers 28
A-B-A Triblock Copolymers 33
Monomer Conversion Study 34
Thermal Elimination 36
Instrumental Methods 38
Size Exclusion Chromatography (SEC) 38
Capillary Gas Chromatography (GC) 39
Nuclear Magnetic Resonance Spectroscopy (NMR) 39
Infrared Spectroscopy (IR) 40
UV/Visible Spectroscopy 41
Polarimetry 41
Pyrolysis-Mass Spectrometry 41
Thermogravimetric Analysis (TGA) 42
X-Ray Photoelectron Spectroscopy (XPS) 42
Contact Angle of PPVS Homo- and Copolymers 44
3 HOMOPOLYMERIZATION AND COPOLYMERIZATION OF PVS 4 5
Homopolymerization 45
Initiators 47
Nature of the Propagating Carbanion 48
Effect of Temperature 52
Effect of Temperature on Initiation of PVS 54
Effect of Temperature on Polymerization 59
Conversion of (±) PVS With Time 65
Polymerization and Studies of (+)-PVS 67
v

Copolymerization of Styrene and PVS 67
A-B Copolymers 67
A-B-A Copolymers 76
Proof of Dianion Formation in the Lithium Naphthalide Initiated
Polystyryllithium 79
4 THERMAL ELIMINATION STUDIES 85
Mechanism of Sulfoxide Elimination 85
Use of Sulfoxides as Acetylene Synthons 88
Michael Addition-Elimination 88
Alkylation-Elimination 88
Sulfenylation-Dehydrosulfenylation 91
Diels-Alder Cycloadditions and Elimination 91
1,3 Dipolar Cycloaddition and Elimination 91
Elimination of PPVS and PS-PPVS Copolymers 91
Fate of Phenyl Sulfenic Acid 94
Thermal Methods for Study of Elimination 98
Thermogravimetric Analysis (TGA) 98
Pyrolysis-Mass Spectrometry 106
Studies of the Elimination of PPVS by Spectroscopic Methods 112
X-Ray Photoelectron Spectroscopy (XPS) 11 2
Nuclear Magnetic Resonance (NMR) 116
Infrared (IR) 1 25
REFERENCES. 129
BIOGRAPHICAL SKETCH 135
vi

KEY TO ABBREVIATIONS
PVS phenylvinylsu If oxide
PPVS poly(phenylvinylsulfoxide)
PPVO poly (phenylvinylsu If one)
PA polyacetylene
PS polystyrene
EPS ethylphenylsulfoxide
TPML triphenylmethyllithium
1,1-DPE 1,1-diphenyl ethylene
GC gas chromatography
SEC size exclusion chromatography
MW. molecular weight
Mn number average molecular weight
Mw weight average molecular weight
Mp. peak molecular weight from SEC
XPS X-ray photoelectron spectroscopy
vii

Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
THERMAL ELIMINATION OF POLY(PHENYLVINYLSULFOXIDE)
AND ITS STYRENE BLOCK COPOLYMERS
By
Rustom Sam Kanga
December 1988
Chairman: Dr. Thieo E. Hogen-Esch
Major Department: Chemistry
The polymerization of phenyl vinyl sulfoxide (PVS) was carried out
in THF at -78°C using various anionic initiators. It was found that
delocalized carbanion initiators such as triphenylmethyllithium are
effective initiators as are methyllithium and the dipole stablilized
1-lithio-1-(phenylsulfinyl) ethane. There was excellent correlation
between the measured molecular weight and the calculated molecular
weight. The molecular weight distribution was found to be narrow (<1.4).
The polymerization reaction was found to be extremely rapid with a half
life time of about 4 seconds. A side reaction at higher temperatures was
observed leading to broadening of the molecular weight distribution. The
effect of counter ion, solvent polarity and temperature on the
polymerization reaction was investigated.
Both A-B and A-B-A block copolymerization were carried out. The
A-B diblock copolymerization was carried out by vapor-phase
viii

polymerization of styrene in THF at -78°C using t-butyllithium initiator
followed by capping with 1,1-diphenylethylene. The capped
polystyryllithium was used for initiation of the PVS block. The A-B-A
triblock copolymerization was carried out by reacting two-ended
polystyrene prepared by using lithium naphthalide as initiator with 1,1-
DPE to give a capped stable living dianion of polystyryllithium which
initiated PVS at both ends to give an A-B-A triblock copolymer,
polystyrene being the inner block. The molecular weight distributions of
the block copolymers were, in general, narrower than the homopolymers.
The thermal elimination of the homo and copolymers was studied by
TGA and pyrolysis-MS. The TGA of homopolymers typically show two
degradation stages: one at lower temperatures corresponding to
elimination of phenyl sulfenic acid and one at higher temperatures
corresponding to polyacetylene degradation. Pyrolysis-MS was used for
elucidating the fate of phenyl sulfenic acid formed upon elimination. XPS
was used to monitor the elimination reaction with temperature. Proton
NMR was also used to characterize the elimination process and shows
formation of cis and trans polyenes at high temperatures (>100°C). A
change in IR spectra with temperature was observed but gave no useful
information about the polyenes formed.
Preliminary studies carried out elsewhere show a relatively short
conjugation length in the polyacetylene formed. Preliminary conductivity
measurements are in progress.
IX

CHAPTER 1
INTRODUCTION
In the course of previous investigations on the mechanism of anionic
oligomerization and polymerization of phenyl vinyl sulfoxide (PVS) [1, 2] it
was discovered that poly(phenylvinylsulfoxide) (PPVS) upon standing,
either in the solution or the solid state, at room temperature changed color
from white to yellow within 24 hours. The polymer then became red and
finally black within one week. The color change occurred in dark or in the
presence of light. It occurred in air, under vacuum or under an argon
atmosphere. The color change, indicating decomposition of some type, was
suppressed to some extent by storage at freezer temperatures.
These color changes were also observed while warming in a melting
point apparatus and were essentially immediate upon heating the polymer
above 100-150°C. Interestingly when PPVS was oxidized to
poly(phenylvinylsulfone) the above color changes were not observed upon
heating. The color changes were consistent with the formation of
polyacetylene through a concerted, cyclic, sigmatropic thermal elimination
of phenyl sulfenic acid from PPVS illustrated in Figure 1-1. The sulfoxide
elimination was first proposed by Kingsbury and Cram [3] and later used as
an acetylene equivalent in a Michael addition-elimination [4-9], and a
Diels-Alder cycloaddition-elimination [10] for introduction of a vinyl group
in organic syntheses. Thus PPVS could be regarded as a soluble
polyacetylene precursor.
1

2
Poly(phenylvinylsu If oxide)
H H
Poly(phenylvinylsulfoxide)
+
Ph-S-O-H
Figure 1-1. Scheme for the elimination of phenyl sulfenic acid from
PPVS.

3
Polvacetvlene (PA)
Polymers with conjugated rc-electron backbones are currently of
intense research interest worldwide [11-20]. This is because this class of
polymers displays unusual electronic properties such as low energy optical
transitions and low ionization potentials. As a result they can be oxidized
or reduced more readily and reversibly than conventional polymers without
conjugation [11]. Therefore an insulating polymer could be converted into
conducting polymers with near metallic conductivity in many cases.
Polyacetylene, the simplest conjugated polymer has become a prototype in
the conducting polymers field and has been the most widely studied of the
conducting polymers.
The main impetus for the study of conducting polymers was provided
when Shirakawa [12] successfully synthesized PA as a coherent free
standing film. They used an unusually high concentration of a Ziegler-type
catalyst system. When acetylene gas was introduced into a vessel
containing Ti(OC4Hg)4 / AI(C2H5)3 (AI:Ti::4:1) in toluene (0.1-0.2 M in Ti)
at -78°C, a lustrous film formed at the gas-liquid surface. This polymer
referred as "Shirakawa polyacetylene" had a lustrous, golden appearance
and predominantly cis-geometry and was an insulator. The cis-PA
isomerized to trans at higher temperatures (>150°C) or upon doping with
electron acceptors such as iodine or AsFs (called p-doping) or with
electron donors like sodium or potassium naphthalide (called n-doping). In
the pristine form cis-PA is an insulator (o = 10'9 S/cm) whereas trans-PA
is a semi-conductor (o = 10‘5 S/cm). Upon doping, however, conductivities
as high as 103 have been obtained [13]. Recently Naarman in W. Germany
[14] report an improved synthesis of PA with fewer SP3 defects having
conductivity in the range of 1.5 x 103 which is about one-fourth the

4
conductivity of copper by volume and twice the conductivity of copper by
weight!
The doping of conjugated polymers results in high conductivities
primarily by increasing the carrier concentration. The description of this
process as doping is a misnomer since dopant concentrations are
exceptionally high compared to the conventional doping of inorganic semi¬
conductors. In some cases the dopant constitutes about 50% of the final
weight of the conducting polymer [11]. Thus the system would be more
appropriately described as a conducting charge-transfer complex rather
than a doped polymer. Conductivity in doped polymers may be due to
electron transport through the chain (intramolecular), between chains
(interchain transport) and also through interparticle contact [11].
PA is an inconvenient material for fabrication. It is insoluble in all
solvents and cannot be melt processed. Intractability is the major hurdle
for large scale commercial application of PA. Also PA as synthesized can
undergo oxidation in air fairly readily resulting in a severe drop in
conductivity [13].
Another problem is contamination of the PA sample with catalyst
residues which may influence the detailed outcome of the individual
measurements of conductivities which varies with the details of
preparation, recovery, and the washing technique. PA has a fibrullar mat
morphology in which only one third of the space available is occupied by
the PA fibrils. Generation of alternate morphologies has resulted in little
success. The necessity of producing the film at the interface between a
catalyst solution and acetylene gas limits the physical form in which PA
can be produced and this restricts the utility and applicability of direct
synthesis. Considerations of this kind lead to the conclusion that a two

5
step precursor route to synthesis of PA would be advantageous in
circumventing one or more of the above problems. Thus a soluble precursor
could be generated which on further chemical reaction would yield PA in
the second step.
Precursor Routes to Polvacetvlene
Precursor routes to PA are not unknown [16-20]. Marvel et al. were
the first to consider dehydrohalogenation of polyvinylhalides to from PA
[15]. Unfortunately they found that under the extreme reaction conditions
used (high temperatures in presence of high local concentrations of HX) the
nascent polyene formed undergoes further reactions.
Precursor routes for PA syntheses have been extensively studied by
Feast in Durham, U.K. Their approach is outlined in Figure 1-2 and 1-3. The
precursor polymers are synthesized by a metathesis ring-opening
polymerization of monomers like 7,8-bis(trifluoromethyl) tricyclo
{4.2.2.02<5} deca-3,7,9-triene (Figure 1-2) [17, 18]. These precursor
polymers are obtained as colorless soluble materials by conventional
reprecipitation and films or fibres could be spun from solution. A
1,2-disubstituted benzene is thermally eliminated from the precursor
polymer in a symmetry allowed step to yield PA. Cis-PA is initially
formed which isomerizes to trans-PA at higher temperatures. Under
increasingly applied stress ordered films of PA can be produced. This two
step approach allows a whole range of new morphologies to be prepared and
investigated [16,17],
Recently Grubbs [20] found that ring opening metathesis
polymerization (ROMP) of benzvalene yields poly(benzvalene) which is a
polyacetylene precursor. ROMP of benzvalene was achieved using well-
defined non-Lewis acid tungsten alkylidene metathesis catalysts like

6
7,8-bis(trifluromethyl)
tricyclo-[4.2.2.02,5]
deca-3,7,9-triene
i'
Trans-polyacetylene
Cls-polyacetylene
Figure 1-2. Precursor route -1- to "Durham Polyacetylene.

7
3,6-bis(trifluoromethyl)pentacyclo
[6.2.0.02,4.03,6.05’7]dec-9-ene
Trans-polyacetylene
A
w
Cis-polyacetylene
Figure 1-3. Precursor route -2- to "Durham polyacetylene.

8
Schrock's catalyst {(RO)2W(N(2,6-(iPr)2Ph))CHC(Me)3} [Figure 1-4].
Poly(benzvalene) isomerizes to PA by the action of transition metal
catalysts like HgCl2, HgBr2, and Ag+ salts in THF. The thermal and
photochemical isomerizations were unsuccessful.
The SEC studies of poly(benzvalene) reveals a very broad molecular
weight distribution ranging from 1000 to 600,000 with average molecular
weight approximately 20,000 (relative to polystyrene standards). The
conductivities of the doped PA was 1 S/Cm [20] which was comparable to
Durham PA but is much lower than Shirakawa and Narmann PAs. This may
be due to the amorphous morphology formed during the isomerization.
The synthesis of PA from PPVS in our case has potential advantages.
Firstly the polymerizations of PVS proceeds through stable carbanions
(Chapter 3) so that the molecular weight distribution is expected to be
narrow (unlike those of the Durham and Grubb precursors). Moreover the
control of molecular weight through the ratio of monomer to initiator is
quite good and thus formation of high molecular weight PPVS is possible.
As a result a series of monodisperse PAs of known molecular weights is
possible. Unlike the previous precursor routes which use exotic and
difficult chemistry, the anionic polymerization of PVS is simple and uses
readily available reagents and well-known techniques.
A second advantage of the sulfoxide precursor route to PA is the
formation of A-B and A-B-A type copolymers with monomers like styrene,
butadiene, isoprene etc which are accessible through living anionic
polymerizations. These may then be subjected to elimination to form block
copolymers of styrene (or other monomers) and PA. Previous attempts to
make block copolymers of PA have been known [21-24], There have been
two different approaches to make PA block copolymers. Aldissi [21-22]

9
Polyacetylene
Figure 1-4. Ring opening metathesis polymerization of benzvalene
to polybenzvalene, a polyacetylene precursor.

10
had proposed an "anionic to Ziegler-Natta catalyst" approach wherein the
styrene, isoprene etc have been polymerized anionically followed by
addition to a Ziegler-Natta catalyst like Ti(OBu)4 which exchanges one of
the ligands with the anionically growing polymer chain. Acetylene gas was
then introduced to make the soluble block copolymer. Baker and Bates have
used a similar approach to make both block and graft copolymers [23].
Stowell et al. [24] on the other hand used the "anionic to metathesis
catalyst" approach to make block copolymers of PA. They react the growing
polystyryllithium with a co-ordination catalyst like WCI6 and polymerize
acetylene with the WCl6/polystyryllithium catalyst. Our approach to make
block copolymers would be one using the traditional anionic block
copolymerization technique where styrene is first polymerized using
alkyllithium initiator followed by capping with 1,1-diphenylethylene and
the capped polystyryllithium would be used to polymerize PVS. The
copolymer could then be subjected to thermolysis to make the
poly (sty rene-b-acety lene).
Thus the purpose of the present study was twofold: (i) to synthesize
and characterize PVS homopolymers and its block copolymers with styrene
(both A-B and A-B-A) and (ii) to demonstrate the thermal elimination of
phenyl sulfenic acid from the homo- and copolymers to form PA and its
block copolymers.

CHAPTER 2
EXPERIMENTAL
High Vacuum Anionic Polymerization Techniques
Anionic polymerizations are extremely sensitive to trace amounts of
electrophilic impurities. Thus rigorous techniques for purification of
reagents and solvents were found to be necessary. Also most of the
reagents, solvent transfers, etc. were carried out under high vacuum (10~6
Torr).
High vacuum line techniques have been well known for decades
[25,26,27] and routinely used in our group. The vacuum system consists of
a rotary oil pump in conjunction with a mercury or oil diffusion pump. The
vacuum line was custom made in our glass shop, constructed entirely of
pyrex glass. High vacuum pyrex ground glass joints (Eck & Krebs) were
used at various junctions in the line to permit evacuation of reaction
vessels and distillation of solvents from one part to another. A mercury
McCleod gage attached to the manifold was used to monitor the pressure in
the system.
The reaction vessels used in most of the reactions were made from
pyrex and were self built by use of a hand-held gas and oxygen torch. The
manipulations required for various reactions like addition, transfer of
reagents etc. were performed in vacuo using the breakseal technique
[25,26]. The glassware used was scrupulously cleaned using in order: KOH
/ isopropanol (15% W/V), 1% HF, rinsed with water and acetone and dried
before attaching it to the line. Once attached to the line the whole system
11

12
was evacuated and flamed thoroughly with a torch to remove traces of
adsorbed water vapor and oxygen from the surface of the glass. The system
was then checked for the presence of pinholes using a Tesla coil. Reactions
were carried out only after confirming "sticking vacuum" (<10'6 Torr) as
registered on the McCleod gage.
Purification of Solvents. Monomers and Reagents
All polymerizations and other reactions were carried out under high
vacuum in THF. Since anionic polymerizations involve reactive
intermediates, it was found necessary to use highly purified and dry
reagents and solvents. THF was purified by refluxing over a
sodium/potassium alloy for 24 hrs., followed by distillation onto fresh
alloy in a round bottom flask which was then flushed with argon and
connected to a vacuum line equipped with a water-jacketed condenser. A
small amount of benzophenone was added as an indicator. The THF was
evacuated and degassed several times. The color turned purple which
indicates formation of the benzophenone dianion and absence of protic
impurities and oxygen.
Purification of Phenvlvinvlsulfoxide and Ethvlphenvlsulfoxide
Phenylvinylsulfoxide (Aldrich) in the crude form is a dark brown high
boiling liquid. The crude phenylvinylsulfoxide was stirred over calcium
hydride for 24 hrs., followed by distillation in a Vigreux distillation
apparatus at 100-110°C / 0 mm Hg onto fresh calcium hydride. This
procedure was repeated thrice. The colorless distillate from the last
distillation was collected in a break-seal equipped ampule and further
divided as needed. Care was taken while sealing to make sure that none of
the high boiling monomer remains at the site being sealed and which might
degrade forming undesirable impurities.

13
Other purifying agents were tried but did not work. The monomer
became black within minutes when stirred over potassium mirror. McGrath
[28-29] has advocated the use of triethylaluminum for the purification of
acrylate and methacrylate monomers. The trialkylaluminum forms a
colored charge-transfer complex with the carbonyls of the monomer and
hence is self-indicating in the titration. We tried using triethylaluminum
once with disastrous results! There was a strong exothermic reaction
between PVS and triethylaluminum and ultimately an explosion!
The monomer was characterized by GC (>99% pure) and by proton and
carbon-13 NMR.
1H NMR (CDCI3, 200 MHz, 9 in PPM): d at 5.85 (1H), d at 6.15 (1H), d
of d at 6.6-6.8 (1H), 7.45 (3H),7.6 (2H)
13C NMR (CDCI3, 50 MHz, 9 in PPM): 121 (vinyl methylene), 125
(ortho aromatic carbons), 131.5 (para carbon), 143 (vinyl methine), 143.5
(substituted quarternary aromatic).
(+) Poly(phenylvinylsulfoxide) was synthesized by M. Buese [2]. It
was purified by distilling twice over calcium hydride. The optical
rotation, [a]D20, was found to be 358.5°.
Ethylphenylsulfoxide (ICN Pharmaceuticals, INC.) was purified in a
similar manner.
1H NMR (CDCI3, 200 MHz, 9 in PPM): t at 1.1 (3H), q at 2.75 (2H), m at
7.6 (5H).
13c NMR (CDCI3, 50 MHz, 9 in PPM): 10 (methyl), 52 (methylene),
126,131,132,147(aromatics).
Purification of Stvrene and 1.1-Diphenvlethvlene
Styrene (Fisher) was purified by stirring over calcium hydride for 24
hrs. followed by fractional distillation under vacuum (75°C / 95 mm Hg).

14
The middle fraction was collected in an ampule. The ampule was further
attached to an apparatus shown in Figure 2-1 and evacuated. The side arm
contained freshly cut potassium metal which was heated gently with a
torch to form a shiny mirror in the main container. Styrene was then added
onto the mirror and allowed to stir gently for 30 minutes. After degassing
it was distilled into the side flask provided with a break-seal and
carefully sealed off from the main apparatus. The extremely pure and dry
styrene was stored in the freezer and used as needed. Styrene-d8 (Aldrich)
was purified by distilling twice over calcium hydride in vacuo.
Styrene: 1h NMR (CDCI3i 200 MHz,3 in PPM): d at 5.11 (1H), d at 5.59
(1H), d of d at 6.59 (1H), 7-7.5 (5H)
Styrene: 13q nmr (CDCI3, 50 MHz, 3 in PPM): 113 (vinyl methylene),
126 (ortho aromatics), 127.8 (para aromatic), 128.5 (meta), 137 (vinyl
methine), 138 (substituted quarternary). Styrene-d8: 1H NMR (neat with
TMS, 200 MHz, 3 in PPM): t at 5.0 (1H), t at 5.5 (1H), d at 6.5 (1H), s at 7.0
(para 1H), s at 7.1 (meta 2H), s at 7.25 (ortho 2H).
13c NMR (neat with 1% CDCI3, 50 MHz, 3 in PPM): pentet at 112.5
(vinyl methylene CD2), t at 125.6 (aromatic ortho CD), t at 126.9 (aromatic
para CD), t at 127.7 (aromatic meta CD), t at 136.2 (vinyl methine CD), s at
137.1 (substituted aromatic quarternary C). All assignments made from
non-deuterated styrene in Sadtler.
1,1-Diphenylethylene was purified in a similar manner. 1H (200 MHz,
CDCI3, 3 in PPM): s at 5.4 (2H), m at 7.2 (10H)
13C (50 MHz, CDCI3, 3 in PPM): 114 (=CH2), 127.5 (ortho aromatic),
128.1 (m and p aromatic), 141.5 (ipso aromatic), 150 (>C=).

15
Figure 2-1. Apparatus used for purification of styrene.

16
Purification of t-Butvllithium
It was found that the crude t-butyllithium (Aldrich) contained
undesirable impurities like lithium t-butoxide, lithium hydroxide etc. It
was thus found desirable to further purify t-butyllithium by sublimation of
the crude product [30]. The apparatus shown in Figure 2-2 was used.
Crude t-butyllithium was introduced in "a" under a constant flow of
argon. The solvent was pumped off into the trap and the side arm sealed.
Crushed dry ice was put in the cork ring on the flask "b" to trap the
subliming t-butyllithium. The lower part of the apparatus was immersed
in a hot water bath (85°C) and the combination of heat and dynamic vacuum
was used to sublime highly pure t-butyllithium which was trapped in ”b"
while the impurities remained unaffected in "a." The flask containing the
t-butyllithium was sealed off from "a" at the constriction "S1" and from
the line at "S2." Extreme care was taken to see that none of the
t-butyllithium remained at the sites "S1" and "S2" which might form
undesirable decomposition products and might also create pinholes. The
shiny white solid t-butyllithium was then dissolved in Na/K dried hexane
and further subdivided as needed.
Preparation of Initiators
Lithium Naphthalide
Lithium wire (Mallinckrodt) was cleaned by dipping successively in
methanol, hexane, and finally THF. A THF solution of naphthalene (Aldrich,
Gold label) was prepared in vacuo in a break-seal equipped ampule. An
excess of naphthalene was used to avoid formation of the naphthalene
dianion [31, 32]. The lithium metal was introduced in the reaction vessel
under a constant flow of argon. After evacuation more THF was distilled
in. The naphthalene solution was then added in. A noticeable color change

17
Figure 2-2. Apparatus used for purification of t-butyllithium by
sublimation.

18
was observed upon reaction of naphthalene with lithium metal. The
reaction was allowed to proceed at 25°C for 12 hrs. At the end of 12 hrs. a
dark green solution was obtained which was filtered through a course frit
into various ampules. The concentration of the initiator was determined as
described later.
Triphenvlmethllithium (TPMD
TPML was made as described in reference 33. A THF solution of
triphenylmethane (TPM) was prepared in vacuo and attached to an apparatus
illustrated in Figure 2-3. The apparatus was attached to the line,
evacuated and flame degassed. Argon was then charged into it and
n-butyllithium was injected through the serum cap. Both argon and the
solvent were removed by distillation into the cold trap leaving behind the
viscous yellow n-butyllithium. The apparatus was cooled to -78°C using a
dry ice/isopropanol bath and the serum cap was sealed from the apparatus.
THF was then distilled into the n-butyllithium and the TPM solution was
added from the ampule through the breakseal. The solution started turning
red almost immediately and was allowed to stir at room temperature for
8-10 hrs. THF was then distilled from the solution into the trap leaving
behind the dark red TPML. The apparatus was then cooled to -78°C and
dried hexane was distilled into the flask (THF:Hexane approximately 1:15).
The apparatus was sealed from the line and the recrystallized TPML was
washed with the hexane. This was accomplished by pouring the hexane
from the main body of the apparatus into the wash ampule and distilling
back into the main body. After repeating this procedure several times the
hexane was removed from the main body in the wash ampule.
The apparatus was reattached to the line and THF was distilled in to
dissolve the TPML salt. The TPML solution was poured into a separate

19
Figure 2-3. Apparatus used for the preparation of TPML.

20
ampule and sealed off from the main body. The initiator was stored at
-20°C and was further divided as needed. The concentration of the
initiator was determined as described later.
1,1 Diphenvlhexvllithium (DPHÜ
DPHL [33] was prepared by reaction of equimolar amounts of
1,1-diphenylethylene and n-butyllithium in THF at room temperature for 12
hrs. The reddish orange salt was purified by washing with hexane as
described for TPML. The THF solution of DPHL was stored at -20°C and
divided as needed. The concentration of the initiator was determined as
described later.
Triphenvlmethylpotassium (TPMK)
TPMK was synthesized by reaction of a 1.1-molar excess of a
solution of TPM in THF with a solution of oligomeric dianions of
a-methylstyrylpotassium (aMSK) in THF prepared by reaction of
alphamethylstyrene in THF with potassium metal for 24 hrs at 25°C [34].
A THF solution of TPM was prepared in vacuo in a breakseal equipped
ampule. The red solution was filtered through a frit and divided into
ampules. The THF solutions of TPM and aMSK were reacted with each other
in vacuo at room temperature for 2 hrs. After the reaction the TPMK
solution was sealed from the line and divided into various ampules. The
concentration of the TPMK solution was measured as described later.
1-Lithio-1-(Phenvlsulfinvh Ethane (EPSU
EPSL [1, 2] was synthesized by a reaction of a 1.1 excess of
ethylphenylsulfoxide with methyllithium in THF at -78°C. The apparatus
used for the synthesis is illustrated in Figure 2-4. The apparatus was
attached to the line and evacuated. Argon was then charged into it through
the line and methyllithium was injected through the serum cap. The

21
Figure 2-4. Apparatus used for the synthesis of EPSL.

22
solvent was carefully removed by distillation into the trap as the solution
tended to bump in the apparatus. The serum cap was sealed off and THF
was distilled to make a solution of methyllithium. The solution was then
cooled to -78°C and ethylphenylsulfoxide was added from the ampule
through the breakseal. The solution started becoming yellowish as the
methyllithium reacted with ethylphenylsulfoxide to form the carbanion.
The solution was degassed several times to remove the methane gas and
was stirred at -78°C until no more methane gas evolved (as evidenced by
the bubbling of the solution upon degassing and the characteristic pump
noise). The yellowish-green solution was sealed from the line and poured
into a side ampule which was sealed off. The initiator was stored at -20°C
and divided as needed. The concentration of the initiator was determined
as described below.
Determination of Concentration of Carbanions
For polymerization reactions concentration determination of metal
alkyls and the delocalized carbanion salts was necessary. Thus, for anionic
polymerizations in the absence of terminating impurities the number
average molecular weight can in principle be predicted if the accurate
concentration of the initiator is known. Also for two-ended carbanions the
accurate determination of the concentration was imperative in order to
prove the "two-endedness" of the system. Two methods were used for
determination of concentration of initiators. The agreement between the
two methods was found to be excellent (±5%).
Titration with Fluorene
The fluorene (Aldrich) used in titrations of the carbanion solutions
was purified by crystallization from ethyl alcohol and pumped on the

23
vacuum line for several days to get rid of the traces of alcohol. Purity was
better than 99% by GC.
The carbanion solutions in THF are reacted with a known excess of
fluorene in THF at -78°C. In most cases the reaction of the carbanions
with fluorene was instantaneous as seen by an immediate color change of
the solution to yellowish-orange, the characteristic color of
fluorenyllithium. The fluorenyllithium was then reacted with an excess of
methyl iodide to form 9-methylfluorene and the ratio of fluorene to
9-methylfluorene was determined by capillary GC.
Determination of Concentration bv UV/Visible Spectroscopy
UV/Vis was found to be an excellent method for concentration
determination since most delocalized carbanions have distinct and strong
absorptions in the visible region.
All of the absorbance measurements were carried out under high
vacuum using an apparatus equipped with a UV cell. The absorbance of the
unknown carbanion was measured followed by a reaction with an excess of
fluorene. The absorbance of the fluorenyl carbanion thus formed was
measured. Comparison of the two absorbances and the molar absorptivity
of the fluorenyl carbanion from the literature [35, 36, 37] provided the
molar absorptivity and hence the concentration of the unknown carbanion
solution. This technique was found to be most convenient for solutions of
living polystyryllithium capped with 1,1-diphenylethylene. The capped
solutions are quite stable at room temperature during the time of
spectroscopic determination and it also avoids the problem associated
with the entrapment of fluorene and 9-methylfluorene in the polymer
matrix during precipitation of the polystyrene in methanol (Method I).

24
The ampule containing the carbanion solution was attached to an
apparatus which was provided with a quartz cell having a 2 mm path
length, in conjunction with a 1.9 mm spacer. The whole system was
attached to the line, evacuated, flamed and sealed off the line. The
carbanion solution was introduced in the cell from the ampule through the
breakseal and scanned in the visible and near UV regions. The fluorene was
then introduced. A change in color was noted as the carbanion reacted with
the fluorene to form fluorenyllithium. After all the carbanion reacted the
fluorenyllithium was scanned in the UV region.
Assuming Beer's law to be applicable to both the carbanion solutions
[25] one can write the following equations:
Ax = ex Cx 1 2 -1
Ay = £y Cy 1 2-2
Cy =Ay £X CX / AX £y 2-3
where x refers to the unknown carbanion solution and y to the
fluorenyllithium, A = absorbance, e = molar absorptivity, C = concentration
of the absorbing species, I = path length, determined using a known
standard solution of Potassium Chromate (e372nm = 4815) [37],
Since Cx = Cy (assuming no inadvertent protonation of the carbanion during
the reaction) we get ex = Ax/Ay ey. Knowing ex one can calculate the molar
concentration of the unknown carbanion solution using the equation 2-3.
Polymerization of Phenvlvinvlsulfoxide
The homopolymerization of phenylvinylsulfoxide (PVS) was carried
out using the apparatus illustrated in Figure 2-5. The system consists of
two round bottom flasks "a" and "b” (100 ccs and 50 ccs respectively)
joined together. The ampules containing the initiator (TPML, methyl
lithium, DPHL etc) and the terminating agent (usually methanol) were

25
Initiator
Figure 2-5 Apparatus used for the homo- and copolymerization of
PVS.

26
attached to "a" along with a ground glass joint to hook it to the vacuum
line. The monomer ampule is attached to the smaller flask ("b").
The apparatus was hooked to the vacuum line, evacuated and flamed
thoroughly. The initiator solution was introduced into flask "a" through the
break seal. The ampule was "washed" with the solvent using a cold cotton
dauber in order to remove all of the initiator solution. Dried THF was then
distilled in "a" to dilute the carbanion solution and the carbanion solution
was thoroughly cooled to -78°C. The apparatus was then carefully sealed
from the line at S1. The monomer breakseal was then broken and the
monomer was introduced in the flask ”b." THF was distilled into “b" from
the carbanion solution. Care was taken to see that the initiator solution
did not bump during the distillation. After sufficient dilution of the
monomer both the initiator and the monomer solutions were cooled to
-78°C as was the tube connecting the two flasks. The solutions were then
rapidly mixed by pouring "b" into "a." An immediate change in color is
usually seen, in the case of TPML from dark red to yellowish-green. This
indicated that the initiation of PVS is quite rapid. After a few minutes
more monomer is added. This procedure is repeated several times until all
the monomer is consumed. The time of polymerization varied from 15
minutes to 12 hours. The yellowish-green color of the living
a-phenylsulfinyl carbanion persists throughout the polymerization. The
chain terminating electrophile (usually methanol) was then added to the
polymerizing solution resulting in an immediate discharge of the
yellowish-green color.
The solvent from the polymerization reaction was rotovaped down
and the polymer was precipitated by pouring into a ten times excess
diethylether solvent. The yield of poly(phenylvinylsulfoxide) (PPVS) was
i

27
determined by weighing and the polymer was characterized further by NMR,
SEC etc. The PPVS was found to be thermally unstable and starts becoming
yellow within a matter of days. It was thus found necessary to store the
polymer in the freezer under argon.
±Poly(phenylvinylsulfoxide): 1H NMR (CDCI3, 200 MHz, 3 in PPM):
1.1-2.1 (2H), 2.5-3.5 (1H), 7.2-8 (5H)
±Poly(phenylvinylsulfoxide): 13C NMR (CDCI3, 50 MHz, 3 in PPM): 26-
32 (methylene in the chain), 56-60 (methine), 123-126, 128-130, 131,
140-142 (aromatic carbons)
(+) Poly(phenylvinylsulfoxide) [alpha]o20= 408: 1H NMR (CDCI3, 200
MHz, 3 in PPM): 1.3-2.3 (2H), 2.7-3.6 (1H), 6.7-7.7 (5H)
(+) Poly(phenylvinylsulfoxide): 13C NMR (CDCI3, 50 MHz, 3 in PPM):
55-57 (methylene), 23-26 (methine), 123-126 (aromatic meta carbons),
128-130 (aromatic ortho carbon), 130-132 (aromatic para carbon), 140
(substituted aromatic quarternary carbon).
PPVS upon oxidation to poly(phenylvinylsulfone) (PPVO) becomes
stable to air (or thermal) degradation. PPVS was oxidized to PPVO by
hydrogen peroxide [1, 2, 38]. The polymer was dissolved in glacial acetic
acid. An excess of 30% hydrogen peroxide was added. The polymer solution
was allowed to stir at room temperature for 12 hrs. A bright white ppt
was formed upon completion of the oxidation. The resulting PPVO was
found to be insoluble in most solvents and partially soluble in chloroform
and THF. Oxidation of the sulfoxide to the sulfone was seen to be
quantitative by IR measurements and also by XPS (see Chapter 4).

28
CoDolvmerization of Stvrene and Phenvlvinvlsulfoxide
A-B Copolymers
A-B copolymerization of styrene and PVS was carried out in two
steps: (a) Polymerization of styrene was first carried out at -78°C in THF
initiated by t-butyllithium [25] followed by capping with
1,1-diphenylethylene (1,1-DPE) followed by division of the capped living
polystyryllithium into various ampules, (b) Polymerization of various
amounts of phenyl vinyl sulfoxide was then carried out bousing the capped
living polystyryllithium as the initiator.
Polymerization of styrene was carried out in an apparatus
illustrated in Figure 2-6. Once again the basic apparatus consists of 2
round bottom flasks "a" and "b" (500 ml and 50 ml respectively). The
ampules containing the initiator (t-butyllithium) and the capping agent
(1,1-DPE) are attached to flask "a." The monomer (styrene) ampule is
attached to flask "b.” The flask "b" is connected to "a" with a tube which
extends into "a" at the top forming a lip. Additionally there are 2 ampules
A1 and A2 equipped with breakseals having volumes 10 ml and 100 ml
respectively.
Once the apparatus was assembled it was attached to the vacuum
line through the ground glass joint, evacuated, checked for pinholes and
flamed. The initiator was added from the ampule through the breakseal
into flask "a" and washed down using a cold dauber. THF was then distilled
into the initiator solution by cooling flask "a." The color of t-butyllithium
turned yellow upon distillation of THF. This was probably due to
deaggregation of the t-butyllithium in going from hexane to THF. It is also
known that t- butyllithium reacts with THF at 25°C to form various
alkoxides [25]. However the yellow color observed was probably not due to

29
Figure 2-6. Apparatus used for the polymerization of styrene.

30
this reaction since the solution was kept at -78°C at all times. Several
precautions were taken before styrene was distilled in; the level of the
isopropanol/dry ice bath was kept below the level of the initiator and the
path between the flasks "a" and "b" was kept warm using an air dryer.
These precautions were warranted to make sure of a uniform vapor phase
distillation of styrene into the rapidly stirring initiator solution and to
avoid any local concentration of the monomer which is undesirable. The
excellent molecular weight distributions bear testimony to the correctness
of this technique (see Chapter 3). The breakseal of the styrene ampule was
broken and styrene was slowly distilled from the flask "b" which was
cooled to -20°C. The color of the t-butyllithium solution turned cherry red
instantaneously. After all the styrene was distilled into "a" the solution
was further stirred for 10 to 15 minutes. 1,1 -DPE was then added to the
living polystyryllithium solution. The cherry red solution turned dark red
upon reaction. The apparatus was sealed off the line at S1. The solution
was allowed to warm up and was then carefully poured into the side
ampules. The constrictions S2 and S3 were washed using a cold dauber and
the ampules were sealed off the main body.
Ampule A1 was used for the detection of the concentration of the
living carbanions by UVA/isible spectroscopy and terminated by an
electrophile like fluorene or methanol. The polystyrene was precipitated in
an excess of methanol nonsolvent and characterized using SEC and NMR.
1 H NMR (CDCI3, 200 MHz, d in PPM): 0.6 (d, t-butyl), 1.2-1.8 (2H),
1.6-2.3 (1H), 6.3-6.9 (2H), 6.8-7.3 (3H).
13C NMR (CDCI3, 50 MHz, d in PPM): 40-41 (methylene), 42-48
(methine), 125.8 (para aromatic), 127 (ortho aromatic), 128 (meta
aromatic), 145 (substituted quarternary).

31
Ampule A2 was further attached to a divider (Figure 2-7), thoroughly
evacuated, flame degassed and sealed from the line. The carbanion solution
was introduced into the apparatus and was carefully divided into the
various ampules. After washing the constriction of each ampule the
divider was cooled in a large dewar to -78°C and each arm was carefully
sealed off.
The polymerization of phenylvinylsulfoxide initiated by the living
DPE capped polystyryllithium was carried out as described before for
homopolymerization. The length of the styrene block was kept constant
whereas the length of the poly(phenylvinylsulfoxide) was varied. The
composition of the block copolymer was calculated from the moles of
styrene and PVS used for each polymerization. The mole ratio of phenyl
vinyl sulfoxide / styrene was varied between 0.26 to 8.0. The apparatus
was the same as that for the homopolymerization of PVS (Figure 2-5).
Once again a color change from dark red to yellowish-green was noticed
upon addition of the monomer to the initiator and the living copolymer
turned colorless upon termination with methanol. The copolymer was
purified by precipitation in a solvent system comprised of ethyl ether and
methanol (75/25 v/v).
1 H NMR (CDCI3, 200 MHz, d in PPM): 0.6 (t-butyl), 1.2-1.8 (methylene
of both polystyrene and poly(phenylvinylsulfoxide) blocks), 1.5-2.4
(methine of polystyrene block), 2.5-3.5 (methine of
poly(phenylvinylsulfoxide) block), 6.3-6.9 (2H, ortho aromatic of
polystyrene block), 6.7-7.5 (3H, meta and para aromatic of polystyrene
block), 7-8 (5H, poly(phenylvinylsulfoxide) block)
The copolymer was stored in the freezer and characterized by SEC
and by NMR. Conditions for oxidation of the copolymer were the same as

32
Figure 2-7.
into several
Apparatus employed for division of a carbamon solution
smaller ampules.

that for the homopolymer using an excess of 30% hydrogen peroxide for 24
hrs, yielding the thermally stable poly(styrene-b-phenylvinylsulfone).
A-B-A Triblock Copolymers
The A-B-A copolymers of styrene and phenylvinylsulfoxide like the
AB copolymers were prepared in two steps: (a) formation of living two-
ended polystyryllithium using lithium naphthalide initiator [39] followed
by capping with 1,1-DPE and division of the capped living polystyryllithium
into various ampules and (b) polymerization of various amounts of PVS
using DPE capped two-ended polystyryllithium.
Living two-ended polystyryllithium was prepared in a manner similar
to the polymerization of styrene using t-butyllithium described before.
Lithium naphthalide was employed as the initiator. After assembling the
apparatus (Figure 2-6) it was attached to the vacuum line, evacuated,
checked for pinholes and flame degassed. The initiator solution was
introduced into ub" and cooled to -20°C. The usual precautions were taken
during distillation of styrene in the polymerization solution as described
before. An immediate color change from dark green to cherry red was seen
upon addition of styrene. After all of the styrene was distilled the
solution was further stirred at -78°C for 15 minutes. 1,1-DPE was then
added to the living polystyryllithium. The cherry red color changed to dark
red upon reaction with 1,1-DPE. The apparatus was sealed from the line
and the solution was divided into two ampules as described earlier. The
determination of concentration and workup were similar to that of the
one-ended system.
The second step in the triblock copolymerization was identical to the
diblock. Once again the styrene block length was kept constant whereas
the phenylvinylsulfoxide block length was varied depending on the moles of

34
styrene used and the ratio of phenylvinylsulfoxide to styrene desired.
Workup of the triblock copolymer was same as that of the diblock.
Monomer Conversion Study
It was found necessary to roughly determine the conversion of
monomer with time, so as to have a rough idea of the kinetics of the
polymerization reaction. Since aliquots of the polymerization mixture
were withdrawn at various times during the polymerization, the
polymerization had to be carried out under rigorously dried argon.
Naphthalene was employed as an internal standard in order to
monitor the consumption of monomer with time. Several factors were
considered for using naphthalene as an internal standard. Naphthalene and
PVS have retention times in GC which are quite different and measurable.
A calibration curve of ratio of moles of phenylvinylsulfoxide to
naphthalene versus the GC ratio of the areas of PVS to naphthalene (Table
2-1) gave a straight line with an excellent correlation coefficient (Figure
2-8). Also naphthalene is inert in presence of living the PPVS carbanions.
The apparatus used during the above polymerization was similar to
Figure 2-5 and consisted of 2 bulbs ”au and "bH joined together. The
initiator ampule was attached to "a" along with a high vacuum stop-cock.
To the flask Mb" was attached a monomer ampule and a short outlet with a
rubber septum for aliquot withdrawals. The apparatus was attached to the
vacuum line and the absence of pinholes was checked. Purified argon was
charged to the apparatus and a known amount of naphthalene was added to
flask "b" which was then evacuated again. Care was taken to see that none
of the naphthalene sublimed to the trap under the high vacuum. The
initiator was introduced in flask "a“ and the contents of the ampule were
washed down. Additional THF was distilled into the initiator solution

Table 2-1. Calibration for the determination of phenylvinylsulfoxide in the
presence of naphthalene as an internal standard.
mol PVS
x 104
mol NPH
x 104
mol PVS/mol NPH
A PVS/A NPH
6.1
1.7
3.6
2.56
5.7
4.3
1.3
0.96
7.7
7.7
1.0
0.68
5.9
9.7
0.61
0.39
5.7
12.2
0.47
0.33
6.5
15.3
0.42
0.31
Figure 2-8. Graph of ratio of moles of PVS to Naphthalene versus ratio of
areas (in GC) of PVS to Naphthalene.

36
through the vacuum line. The monomer was then introduced into "b", and
diluted with THF by distillation from the initiator. Both "a" and "b" were
cooled to -78°C. Argon was charged into the apparatus, through the line.
The argon had to be rigorously dried, which was accomplished by using a
solid KOH and drierite traps followed by a cold (-78°C) trap. The stopcock
S between the line and the apparatus was closed off and the apparatus
detached from the line Both the flasks were then cooled to -78°C. The
initiator solution was introduced into flask "b" by tilting the apparatus.
Aliquots of the polymerization solution were withdrawn at various times
during the polymerization through the rubber septum using a syringe and
were quenched in methanol. The quenched solution was added to an excess
of diethyl ether to precipitate the polymer, which was filtered and the
filtrate was rotovaped and analyzed by GC so that the change in
concentration of monomer with time could be determined. The polymer was
dissolved in THF and analyzed by SEC for the change in polymer molecular
weight with time.
Thermal Elimination
Thermal elimination of the homo- and copolymers in the solid state
was carried out using a Thermolyne tube furnace with a suitably equipped
pyrolysis tube (Figure 2-9). The polymer was dissolved in a minimum
amount of THF or chloroform. The solution of the polymer was introduced
into the section "a" using a pipette. The tube was attached to a rotovap in a
horizontal position and was evaporated with a gradual application of
vacuum. The application of vacuum and slow rotation ensured a thin
uniform film surface in the section "a." The tube was then inserted into
the Thermolyne furnace and hooked to the vacuum line. A cold (-78°C) trap
was used between the line and the tube to trap any condensables.

3 7
a
Figure 2-9. Pyrolysis tube used for the thermal eliminations of the
homo- and copolymers in the Thermolyne tube furnace.

Elimination was carried out by gradually increasing the temperature to
180-200°C and under high vacuum (10*® torr) for 1.5 hrs. The polymer
after heating became dark black and shiny and was handled under argon
(glove bag) at all times. The eliminated products obtained from the side of
the tube outside the furnace were analyzed by MS, GC, and NMR.
Instrumental Methods
Size Exclusion Chromatography (SEC1
SEC was carried out on a Waters 6000-A liquid chromatograph
Phenomenex (Rancho Palos Verdes, CA) TSK Gel G-3000H and G-5000H
columns were employed in series (column dimensions: 75mm x 30cm). The
columns were packed with spherical, crosslinked poly(styrene divinyl
benzene) particles having pore sizes 10^ Á and 10$ Á for G3000H and
G5000H respectively. The molecular weight limits for G3000H were 600
to 60,000 and that for G5000H were 10,000 to 106. Polystyrene standards
were supplied by Scientific Polymer Products, Polysciences INC., Pressure
Chemical Co. and Waters Associates. The standards ranged from a
molecular weight of 2000 to 2,00,000. All polymer solutions injected in
the columns were filtered through a 0.5 p PTFE filter ("Alltech", II.).
The eluting solvent was HPLC grade THF filtered through a 0.5 p
filter. The flow rate was usually 1 ml/minute. The model 6000A solvent
delivery system by "Waters Associate" was utilized. Injection into the
column was achieved by a Waters Associate Model U6K universal liquid
chromatograph injector which allowed loading and injecting samples at a
pressure of up to 600 psi without interruption of the solvent flow. A
Perkin-Elmer LC-75 spectrophotometric UV detector set at 254 nm was
used for detection of the eluting polymer. The detector was interfaced
with a Zenith PC-100 personal computer equipped with a MS-DOS Dascon-1

data collecting program operating at a rate of 1 Hz. The Basic programs
used for data acquisition, molecular weight calibration, computation of
molecular weight averages and distributions were written by W. Toreki in
our group [40]. The Basic program for the conversion of the data into a high
resolution graphics display was written by the author with help from Dr.
Gardiner Myers. Explanations of these Basic programs and the relevant
analytical chemistry involved with it are described elsewhere [40].
A calibration curve was created by injecting various polystyrene
standards and using a correction factor to account for band broadening. The
retention volume of PPVS was then compared to the calibration curve and
an apparent molecular weight for our system was determined. In the
absence of suitable PPVS standards this method was found to be quite
accurate for determination of apparent molecular weight and molecular
weight distribution of PPVS homopolymers and its copolymers with
styrene.
Capillary Gas Chromatography,.(QC)
Routine analyses of monomers and reagents were done by GC. A
Hewlett-Packard 5880A gas chromatograph was used for this purpose. The
system consisted of a 50 meter (G. E. Co. SE-54) fused silica capillary
column (0.2mm ID) coated with a 0.11 pM film of silicone gum, a
microprocessor capable of automation, a temperature programmable oven
and a flame ionization detector. Helium was used as the carrier gas. A
stepwise gradient temperature program was used so that the oven
temperature increased at a controlled rate for higher resolution.
Nuclear Magnetic Resonance Spectroscopy (NMR)
Proton and Carbon-13 NMR spectroscopy was used as an extensive
tool for structure determination, determination of purity of reagents, for

40
characterizing the microstructure in the copolymers and also for
monitoring the change in the structures of the homo- and copolymers upon
heating. Most of the NMR spectra were recorded on a Varían FT-NMR XL 200
spectrometer featuring distributed microcomputer control and a flexible,
high-storage-capacity memory capable of high resolution Fourier
transform. Deuterated chloroform was used as a solvent in most monomer
and polymer studies. The chemical shifts were reported in PPM using TMS
as a reference.
High temperature NMR was done on a Varían XL-300 NMR
spectrometer featuring the same software as the XL-200. Acetic acid-D4
was used as a solvent. A heavy-walled 5 mm tube was employed and the
polymer solution was sealed under a partial pressure under argon. The
spectra were recorded at room temperature and the temperature was
increased in steps of 20°C. A nitrogen atmosphere was used in the probe.
Spectra were recorded at 60, 80, 100, 120, 140, and 150°C.
Infrared Spectroscopy (IR)
Infrared spectroscopy was used for additional structure
determination of the polymers, determination of oxidation of sulfoxide to
sulfone and monitoring of the thermal degradation of PPVS. Routine
measurements were carried out using a Perkin-Elmer 281 IR
spectrophotometer using a pressed KCI pellet or a NaCI window coated with
the polymer. Spectra were also recorded on a Nicolet 5DXB FT-IR
spectrophotometer using NaCI windows under a nitrogen atmosphere. High
temperature IR runs were carried out by Ms. Jennifer Lin in the materials
science department. Spectra were recorded on a Nicolet 60SX FT-IR
spectrophotometer equipped with an "Omega" temperature controller. The
polymer was mixed in diamond powder, mounted and heated under nitrogen

41
atmosphere. The temperature was increased to 200°C over a period of time
at a heating rate of 5°C/min and the spectra were recorded continuously.
UV/Visible Spectroscopy
UV/VIS spectroscopy was used for determination of concentration of
carbanions. A Perkin-Elmer Lambda-9 UV/VIS/NIR spectrophotometer was
employed. Quartz cells having a 2 mm path length were used in conjunction
with a quartz spacer. The path length was calibrated using a known
standard solution of potassium chromate. The cells were usually attached
to the reaction vessel and the spectra recorded under high vacuum. A
special spectrometer cover was made by the chemistry department
machine shop designed to prevent extraneous light to interfere with the
measurement. The spectra were usually scanned from 700 nm to 300nm.
THF was the solvent in most cases. The response time was 1 second, scan
speed 120 nm/min, peak threshold 0.02 Á, cycles/time 1/0.05 min, using an
automatic lamp.
Polarimetrv
The optical activity of the optically active monomer and polymer
was measured using a Rudolph Research Autopol III automatic polarimeter.
Py.rQlysJs-Mass 5pectrQmetry
Pyrolysis-MS was used as a technique for characterizing the thermal
elimination on the homo- and copolymers. It was carried out by Dr. King in
the mass spectrometry laboratory. The mass spectrometer used for this
purpose was the AEI MS-30.
The polymer was inserted using a direct insertion probe. A gradient
temperature from 100 to 500°C was employed. Spectra were recorded
continuously at various temperatures and processed by a "Kratos" data
system.

42
Thermogravimetric Analysis (TGA)
TGA was carried out on a Perkin-Elmer TGA7 thermogravimetric
system. The system consists of the TGA7 thermogravimetric analyzer
controlled by the TAC7 thermal analysis instrument controller. The
analyzer permits the measurement of weight changes in a sample material
resulting from chemical reactions, decomposition, eliminations etc as a
function of either temperature or time.
The heart of the thermal analysis system is the 32 bit PE-7500
professional microcomputer which allows for totally computerized control
of the TGA7 analyzer. Thus the TGA7 can be programmed to scan a
temperature range by changing at a linear rate over several temperature
ramps or it can analyze data at isothermal temperatures to measure weight
loss/gain with time.
The TGA7 analyzer is made up of 2 major components: a sensitive
ultramicrobalance and a furnace element. Other components of the system
include the GSA-7 gas selector accessory and the graphics plotter.
Before each session the analyzer balance and the furnace were
calibrated over the temperature range used. A curie point temperature
calibration was also carried out using 2 standards: Alumel (163°C) and
Perkalloy (596°C). The polymers were usually scanned under a nitrogen
sample purge (50 ml/min) from 50°C to 900°C at a heating rate 10°C/min.
X-Rav Photoelectron Spectroscopy (XPS)
XPS (also known as Electron Spectroscopy for Chemical Analysis or
ESCA) was used for the determination of the surface composition of the
homo- and copolymers, the determination of oxidation of sulfoxide to
sulfone, and the observation of changes on the surface of the polymers upon
thermal treatment. A Kratos XSM-800 x-ray photoelectron

spectrophotometer was employed for the measurements. All the
measurements were done by Mr. Richard Crockett in the material science
department. The instrument consisted of 2 chambers: (i) sample
treatment chamber and (ii) sample analysis chamber.
The sample was mounted as a film on a 10-sample carousel.
Automation allowed analysis of 10 consecutive samples during a run. Once
the sample is mounted the sample treatment chamber is evacuated. A
rotary oil pump in conjunction with a turbomechanical pump and a cold trap
makes it possible to attain vacuum in the order of 10*8 Torr routinely. The
sample is transferred into the sample analysis chamber only after a
vacuum of 10*8 Torr is attained in both of the chambers.
The sample is irradiated with a low energy Mg K-alpha (1253.6 eV)
X-ray photoelectrons. The kinetic energy of the electron emitted due to the
interaction of the X-rays with the atomic orbital electron is measured and
the binding energy of the electron is calculated. The binding energies of
the various elements are standardized using the C-|S peak (285 eV) as the
reference. The instrument is occasionally calibrated using a thin silver
foil (Ag3S 368 eV).
High temperature XPS was carried out using a fast insertion
stainless steel probe mounted on a copper block. The polymer was mounted
on the copper block, introduced in the sample treatment chamber and
evacuated. The sample was scanned at room temperature and heated in the
sample treatment chamber to 100°C for 0.5 hrs. The thermocouple was
standardized to the sample temperature (50°C differential). After all the
condensables were removed as registered by the vacuum in the chamber
(10*7 to 10*8 Torr) the sample was introduced in the analysis chamber and
scanned. A similar procedure was followed at 200°C and 300°C.

44
Contact Angle of PPVS Homo- and Copolymers
Contact angle is a measure of the surface free energy of PPVS homo-
and copolymers. Measurement of the contact angle was carried out by the
captive air bubble method. The polymer was dissolved in chloroform,
coated on a glass slide and was thoroughly pumped in the vacuum oven to
get rid of residual solvent. The coated slide was immersed in water and
constant volume air bubbles were delivered between the polymer film and
the water surface using a 5 ^1 syringe. The contact angle of the air bubble
between the polymer film and the water surface was measured after 30 s.
A number of observations were made and the mean of the values was taken.
The contact angle is inversely proportional to the surface free energy.
Thus the higher the contact angle the lower is the surface free energy.

CHAPTER 3
HOMOPOLYMERIZATION AND COPOLYMERIZATION OF PVS
Homopolvmerization
The polymerization of phenylvinylsulfoxide (PVS) was investigated.
Most of the polymerization studies were carried out on the racemic
monomer. However the optically active monomer was also investigated
albeit not as thoroughly.
Attempts were made by Mulvaney and Ottaviani to polymerize R-(+)-
isopropenyl p-tolyl sulfoxide using various anionic and radical initiators
which were unsuccessful [41]. Homopolymerization of R-(+)-p-
tolylvinylsulfoxide was also attempted using initiators such as benzoyl
peroxide, azobisisobutyronitrile, n-butyllithium and boron trifluoride
etherate. Once again their attempts failed. n-Butyllithium most likely
attacked the sulfur displacing the aryl group [42] and thus failed to
polymerize the monomer. Kunieda et al. [43,44] tried polymerization of
optically active p-tolylvinylsulfoxide using n-butylmagnesium bromide as
initiator. This gave an optically active polymer of a molecular weight of
2400. However they obtained very poor yields (10%). The successful
polymerization of PVS has recently been carried out using methyllithium as
initiator in THF at -78°C [2].
In the present work the polymerization of PVS was carried out by
mixing a solution of the initiator and monomer in THF in vacuo at -78°C.
Various initiators were tried initially for the polymerization and are
summarized in Table 3-1.

46
Table 3-1. Homopolymerization of PVS Using Various Anionic Initiators in
THF at -78°C.
Initiator
Apparent
Weights (
Mw
Molecular
Exptl)a
Mn
Mn
Calcdb
Mw / Mn
Yield
(%)
TPML
2679
2066
1979
1.33
95
2747
2469
3200
1.11
60
5945
4219
5328
1.41
92
33100
24600
—
1.34
90
TPMLC
4502
3310
3970
1.36
90
TPMK
8060
6063
12500
1.33
95
DPHL
1240
1171
6089
1.1
>70
Methyl-
3025
2605
6241
1.16
94
lithium
10309
7423
7537
1.39
95
11261
7698
6729
1.46
90
17811
12349
12177
1.44
84
18384
15515
19976
1.18
75
EPSL
9751
7497
11873
1.3
70
14418
11982
11720
1.2
86
LiNph
18982
14594
15222d
1.3
90
a. From GPC using polystyrene standards
b. Mn Caled. = [monomer] converted/[initiator] x Mmonomer
c. solvent system 1:1 ::THF:toluene
d. Mn Caled. = [monomer]/[initiator] x 2 x Mm0nomer

It is seen from the Table 3-1 that the delocalized carbanions viz
triphenylmethyllithium (TPML), triphenylmethylpotassium (TPMK) and
diphenylhexyllithium (DPHL) are excellent initiators. TPML was, in fact,
the initiator of choice and most of the studies of the polymerization of
PVS (kinetics, temperature effects, etc.) were carried out using this
initiator. There were several reasons for the choice. TPML is very easy to
synthesize (Chapter 2) from a quantitative reaction of triphenylmethane
(which itself is a solid and easy to purify and handle) with n-butyllithium.
The carbanion salt is extremely stable even at R.T. in vacuo (although we
always stored it in the freezer). The solutions of TPML have an intense
absorption in the visible region (e at 500 nm = 31,000) so that their
concentrations can be accurately measured by UV/VIS spectrometry. The
intense color also helps in monitoring visually the initiation process since
a dramatic change in color is seen in going from the TPML carbanion to the
a-lithiosulfinyl carbanion (dark red to yellowish green). Also TPML is not
nucleophilic enough to attack the sulfur atom in the monomer causing side
reactions (at least at -78°C).
Methyllithium was the only alkyllithium successfully employed as
the initiator [1, 2]. n-Butyl and t-butyllithium, interestingly, attack the
sulfur atom causing an SN2 displacement of the aryl group [42, 45-48].
This has also been documented [44, 47] in alkyl aryl sulfoxides where the
alkyllithiums other than methyllithium prefer nucleophilic attack on the
sulfur of the sulfinyl rather than proton abstraction.
Electron transfer initiators like lithium naphthalide were also
employed for initiation. A two-ended polymerization of PVS was thus

48
achieved similar to conventional monomers like styrene [25]. Thus the
initiation of polymerization of PVS appears to be similar to the
conventional anionic polymerization for instance of styrene.
The dipole stabilized initiator 1-lithio-1-(phenylsulfinyl) ethane
(EPSL) which is a carbanion analogous to that of the growing chain was
also found to be an effective initiator giving polymers of controlled
molecular weight and narrow molecular weight distribution. As will be
discussed later polymeric initiators, both one-ended and two-ended can
also be used as initiators to give block copolymers.
The initiation of PVS is instantaneous as seen from an immediate
change in color from dark red (for the delocalized carbanion) to yellowish-
green color of the growing a-lithiosulfoxide carbanion (Figure 3-1).
Nature of the Propagating Carbanion
The living a-sufinyl carbanion has been shown to be a dipole
stabilized ion pair in THF [2], For instance the U.V. spectrum of
ethylphenylsulfoxide (EPS) and the carbanion derived from it show almost
no difference in the absorption maxima [2]. Also the 13C NMR signals for
the carbanion are almost the same as those of the parent hydrocarbon.
Since delocalization of the negative charge into the aromatic ring would
generally result in an upfield shift of the para carbon due to shielding [49-
SI], there appears to be little or no delocalization of the negative charge
into the aromatic ring. Also the IR spectra of the carbanion of EPS and the
parent hydrocarbon exhibit the same absorption wavelength for the S=0
stretch [2], All of these observations indicate the absence of
delocalization of the negative charge into the S=0 bond.
The bond moment of the S-0 bond has been determined to be 4.76 D
[51]. From the x-ray structure the S-0 bond length in EPS was found to be

C(Ph)3Li + Ch2 = CH — S — Ph
II
(Red)
-78°C,
O
THF
C(Ph)3—CH2—CH Li +
S=0
I
Ph
Initiation
(Yellowish-Green)
n CH2= CH — S — Ph
II
O
C(Ph)3— (CH^-CHt^ CH2—CH Li+
S=0
1
s=o
1
Propagation
1
Ph
1
Ph
1
r MeOH
C(Ph)3-
-(CH2-CH^-CH2—
-ch2
i
1
s=o
1
1
s=o
1
Termination
1
Ph
(colorless)
1
Ph
Figure 3-1. Homopolymerization of PVS.

50
1.47 Á [2], Using the equation: jx = e d, where |i is the dipole moment in
debye, e is the magnitude of charge in ESU and d is the bond length. The
magnitude of the apparent charges on oxygen and sulfur was thus found to
be 0.67 electrons. Thus the S-0 bond can be best described as a bond with
substantial ionic character.
Elegant 13C NMR studies by Marquet et al. [49-51] reveal that the
A1Jc-H in the a-lithio sulfoxide shows a large increase (+16.5 Hz) in 13C
NMR upon metalation of the a-carbon of methyl phenyl sulfoxide. Thus the
carbon bearing the negative charge was shown to have a high sp2 character
similar to that found in Ph2CHLi. In methyl phenyl sulfoxide it was found
that the 13C-1H coupling constant decreases in the cryptated potassium
salt as compared to the uncryptated complex. Thus the carbanion becomes
more pyramidal (or the sp3 character increases) upon cryptation. This
suggests that the planar sp2 configuration is stabilized by interaction with
the cation. It is therefore reasonable to assume a chelated structure
(Figure 3-2) possible because of the high charge density present on the
oxygen in the S-0 bond. This internal chelate interaction is strong even for
very polar solvents and is disrupted only upon using a very powerful
chelating agent such as a cryptand [51].
The chelated structure is possible even for potassium which is
expected to have a looser interaction with the anion. The a-potassio
sulfoxide would be expected to have similar properties as the a-lithio
sulfoxide. This is in fact what we find by using TPMK as initiator (Table
3-1). The molecular weight distribution which is a good indication of the
efficiency of the initiation is similar to that for TPML. The effect of
decreasing the solvent polarity from 100% THF to 1:1 THF: toluene would be
expected to increase the anion-cation interaction. However we see little

51
Figure 3-2. Chelated ion pair structure of a-sulfinyl carbanions with
lithium as counter ion.

52
change in the SEC of the polymerization product in going to a less polar
medium (Table 3-1).
Effect of Temperature
The effect of temperature in both the initiation and in the
propagation reaction was found to be dramatic. A series of experiments
were performed to explore the effect of temperature on the initiation and
polymerization. The results of these experiments are summarized in Table
3-2.
In runs 1 and 2 two parallel polymerizations were carried out having
similar concentrations of initiator and monomer. One of the
polymerizations was initiated at -85°C and was allowed to propagate at
-85°C using a mixture of dry ice and ethylether. The other was initiated at
-25°C and kept at -25°C using a mixture of dry ice and carbon
tetrachloride. Runs 3 and 4 were carried out by initiation and propagation
at -78°C and 25°C (room temperature) respectively.
Run 5 was carried out in an apparatus which was provided with a
side bulb connected through a high vacuum teflon stopcock. The reaction
was initiated at 25°C and the solution was then immediately divided into
two portions by pouring half of the reaction mixture in the side bulb
through the high vacuum teflon stopcock. The stopcock was then closed off
and the solution in the side bulb was quickly cooled to -78°C. The solution
in the main body, however, was kept at 25°C. In this way one can see the
effect of initiation at 25°C and propagation at -78°C and 25°C
respectively.
Run #6 was similarly initiated at -78°C and divided into two
portions; one was allowed to proceed at -78°C while the other was warmed
up to 25°C. Run #7 was simply a repeat of run #6.

Table 3-2. Effect of Temperature on Polymerization of PVS. Initiated by
TPMLinTHF.
Run #
Tj a
°C
Tpb
°C
Mw
Mn
Mn
Calcdc
Mw/Mn
Distribution
1
-85
-85
10810
7595
19025
1.42
unimodal
2
-25
-25
11012
7127
19025
1.55
unimodal
3
-78
-78
5945
4219
5328
1.41
unimodal
4
25
25
8495
3751
4892
2.26
bimodal
5
25
-78
9178
3671
4033
2.5
bimodal
25
25
8805
3108
4033
2.83
bimodal
6
-78
-78
6947
4533
4652
1.53
unimodal
-78
25
6829
3949
4652
1.73
unimodal
7
-78
-78
4795
3138
4567
1.53
unimodal
.zZS
AML
2ML
4567
unimodal
a. Temperature of initiation.
b. Temperature of polymerization.
c. Mn Caled. =[monomer]/[initiator] x Mmonomer

54
Effect of Temperature of Initiation of PVS
It was seen that during initiation of PVS at 25°C the color changed
from dark red (TPML) to yellowish-green, characteristic of the a-sulfinyl
carbanion, and then once again to red within minutes. The color
progressively became darker with time and did not discharge when the
carbanion solution was reacted with methanol. An attempt made to
monitor the formation of the colored side products using UV/VIS
spectroscopy failed. Only a tail was seen in the visible region which gave
no useful information as to the identity of the colored products.
The effect of temperature during initiation by TPML was of interest.
It was seen that initiation at low temperatures (<-25°C) led to a unimodal
distribution in the SEC chromatogram. However, initiation at 25°C gave
rise to a bimodal distribution (Figure 3-3) even when the solution is cooled
down to -78°C immediately after initiation (Figure 3-4).
This leads us to believe that at low temperatures the initiation
process forms only one propagating species. However, at higher
temperatures two distinct propagating or initiating species may be
present: a major giving rise to the high molecular weight peak in SEC with
a minor giving rise to the low molecular weight peak (Figures 3-3 and 3-4).
Obviously the high molecular weight (major) initiating species propagates
or initiates faster than the low molecular weight (minor) one.
It is seen from Table 3-1 that there is excellent agreement between
the calculated and experimental Mn in most runs. This indicates that the
"living" nature of the polymerization is similar to that of a conventional
anionic polymerization for instance of styrene.

5 5
Figure 3-3. SEC chromatogram of PPVS initiated by TPML at 25°C and
polymerized at 25°C in THF. Eluting solvent: THF. Flow rate: 1 ml/min.
h
pol

56
Figure 3-4. SEC chromatogram of PPVS initiated by TPML at 25°C and
polymerized at -78°C in THF. Eluting solvent: THF. Flow rate: 1 ml/min.

5 7
Reactions of alkyllithium with sulfoxides having an a-proton have
been well-studied [44-47], Methyllithium and LDA mainly abstract the
a-proton. n-Butyllithium and t-butyllithium, on the other hand, attack the
sulfur causing a ligand exchange on the sulfoxide. Jacobus and Mislow [44]
report the racemization and cleavage of optically active aryl methyl
sulfoxides with methyl and phenyllithium. According to their mechanism
racemization of the sulfoxide and exchange of the alkyl group takes place
via a sulfine intermediate (Figure 3-5). They also proposed a sulfurane
adduct to account for the exchange of the aryl group (Figure 3-6).
Durst et al. [47] have disagreed with the above mechanisms. They
found two competing reactions when various sulfoxides were reacted with
alkyllithiums: a) abstraction of an a-hydrogen to give a-lithio sulfoxide
and b) carbon-sulfur bond cleavage according to the equation
O O
>> II
S R2 + R3-Li â–º R1 S R3 + R 2" L i
They propose a simple SN2 displacement at sulfur and considered the
sulfurane as a transition state not an intermediate. In our system
displacement of the phenyl group by TPML at -78°C is unlikely because
TPML is less basic and more sterically hindered compared with
alkyllithium. The nature of the side reaction is possibly associated with
the presence of chelated stereoisomers some of which propagates faster
than others. A true side reaction, therefore may not be present.
We found the polymerization of PVS to be extremely rapid even at
-78°C. Thus at 25°C the polymerization is expected to be even more rapid.
The two initiating or propagating species (slow and rapid) that are seen

58
Ph
O
ti
,?>
R ¡ CH,
ch3u
Jo
R CH2L i
RLi + [CH2=S=0]
racemization ligand exchange
Figure 3-5. Sulfine intermediate formed during racemization of
sulfoxides.
O
CH,
Ph
O
II
Figure 3-6. Sulfurane intermediate formed during ligand
exchange in phenylmethylsulfoxide.

5 9
would be expected to form and propagate in the first few seconds of the
polymerization. Thus cooling the reaction mixture after initiation at 25°C
does not have much effect on the distribution and we still see the bimodal
nature of the chromatogram (Figure 3-4) (Run 5 in Table 3-2).
The total absence of bimodal distributions for the samples initiated
at -78°C suggests that at -78°C we form only one initiating species which
propagates further. Warming the solution up to 25°C after initiating at
-78°C does not give rise to bimodal distribution (Runs 6 and 7 in Table
3-2). However, the molecular weight distribution of the sample was
considerably broadened when it was warmed up to 25°C. This indicates a
different effect of temperature on the polymerization as compared to the
initiation (see below).
Also from Table 3-2 it is seen that lower the polymerization
temperature narrower the MW distribution. The difference in molecular
weight distributions observed at the same temperature (-78°C) for
different runs (Tables 3-1 and 3-2) for the same initiator is probably due
to the difference in the purity of monomer from batch to batch. Also this
small variation may be due to changes in the SEC conditions. Although all
the SEC runs were carried out as much as possible under identical
conditions and although the calibration curves were recalibrated from
month to month there would still be the some experimental error involved
with the system (i.e. change in flow rate due to wear and tear of the pump,
leakage in the system, difference in the injection conditions, difference in
the concentration of the solution injected, etc.).
Effect of Temperature on Polymerization
It was noticed that warming the polymerization mixture to 25°C
resulted in a change in color from yellowish-green to red which

60
progressively became darker with time. The dark red color did not
discharge when terminated with methanol. Furthermore the molecular
weight distributions of the polymers were found to broaden considerably at
higher temperatures (Table 3-2). This was an indication that
polymerization side reactions played an important role at ambient
temperatures. As mentioned before efforts to determine the colored side
products by UV/VIS spectometry failed due to the strong absorption of the
sulfoxide group in UV (Xmax 253 nm).
The side reactions are seen to be present even at -78°C. Thus a
tailing effect in the SEC chromatograms were usually observed (Figure
3-7), which was always in the low molecular weight region. The tailing
and consequent worsening of the molecular weight distribution was more
prominent for longer reaction times. Even at -78°C, after termination,
there was usually a yellowish tinge in the solution which was not due to
the living carbanions.
During the initial stages of our investigation of this system we
attributed the tailing due to our inability to completely purify PVS to
anionic polymerization standards. As mentioned in Chapter 2 the
importance of rigorous purification of solvents and reagents during anionic
polymerization cannot be overemphasized. The presence of parts per
million of electrophilic impurities could be disastrous especially for the
preparation of high molecular weight polymers [25, 26]. Sulfoxides are
known to form strong hydrogen bonds so that hydrogen bonds may have
formed with electrophiles such as water. PVS is probably synthesized
from a Grignard reaction of vinyl magnesium bromide with
ethylbenzenesulfinate [2]. It is conceivable that some of the reactants may

61
Figure 3-7. SEC chromatogram of PPVS initiated by TPML in THF at -78°C
and polymerized at -78°C for 33 hours. Eluting solvent: THF. Flow rate: 1
ml/min.

62
have been left behind which may have very close boiling points and thus
cannot be completely removed through distillation.
Another possibility is the decomposition of the monomer during
distillation at high temperatures. Mislow did extensive studies on the
thermal racemization of alkyl aryl sulfoxides [52, 53]. They estimated the
bond dissociation energy of cleavage of C-S bonds in alkyls and aryls to be
about 56-69 kcals/mole whereas the activation energy of the pyramidal
inversion was estimated to be about 36 kcal/mole [52], Thus they
discounted the homolytic cleavage-recombination mechanism for
racemization except in case of benzyl p-tolylsulfoxide which gives rise to
benzyl and p-toluenesulfinyl radicals upon cleavage of the benzylic C-S
bond [53]. Another possibility is a five-center pyrolytic cis-elimination
mechanism for sulfoxides having a [5-hydrogen (Figure 3-8) [3, 54]. A
detailed discussion of this elimination will be given in Chapter 4.
The absence of detectable impurities in GC leads us to believe that
the tailing effect in the low molecular weight side in polymerizations
carried out at -78°C may be due to factors other than impurities in the
monomer. It was noticed that the side reactions were more prominent in
polymerizations with long reaction times so that the growing polymer
chain is somehow deactivated during the polymerization. Several
explanations are possible since we have a number of sites in the polymer
chain which could be attacked by a carbanion leading to various side
products. Apparently these side reactions are strongly temperature
dependent and lead to broad molecular weight distribution (Table 3-2).
Probable deactivation reactions could be
i. E2 elimination of phenyl sulfenic acid in the polymer chain by a growing
carbanion [55, 56] to form polyene linkages in the chain

63
¡i. Deprotonation of an a proton in the chain to form a dipole stabilized
carbanion [44-48]
iii. Attack on the sulfinyl of a polymer chain by the growing a-lithio
sulfoxide [47]
The pKa of LDA [57] is very similar to that of the a-lithio sulfinyl
carbanions [48]. Thus it was decided to investigate the effect of LDA on
PPVS. LDA was prepared in vacuo by a reaction of diisopropyl amine and

64
Figure 3-8. Possible elimination reaction in phenylvinylsulfoxide at high
temperatures.

65
methyllithium. The ratio of LDAisulfoxide was about 1:1. The THF solution
of PPVS was then added to the THF solution of LDA at -78°C. It was seen
that the polymer solution turned dark red (similar to that of the solution of
polymerization at 25°C ). After about 15 minutes methanol was added to
quench any LDA left behind and the polymer was purified by precipitation in
ether. The polymer was not completely soluble in THF. The SEC of the
soluble polymer showed a decrease in molecular weight as compared to the
starting polymer. Thus a cleavage of chains by LDA at -78°C may have
occurred. The change in color upon reaction of LDA with PPVS may be due
to the formation of low MW polyenes in the polymer due to a p elimination
of phenyl sulfenic acid as discussed above.
Conversion of (±) PVS With Time
A rough idea of the conversion of monomer with time and the
kinetics was highly desirable. This would give us the half life of the
polymerization reaction and would help us decide when to terminate the
polymerization so as to obtain reasonable yields without the side reactions
associated with long reaction times.
A polymerization reaction was carried out at -78°C under rigorously
dried argon and aliquots of the polymerizing solution were withdrawn by
syringe at various times. Naphthalene was employed as an internal
standard to monitor the concentration of the monomer at various times
during polymerization (Chapter 2). The polymer was also characterized by
SEC. The results of one of the runs are summarized in Table 3-3.
Surprisingly the variation in molecular weight was negligible from 5
minutes to 3 hours. Also no detectable monomer was found by GC even
after just a few minutes of reaction. This indicated that the
polymerization of PVS was extremely rapid even at -78°C.

66
Table 3-3. SEC Results of the Conversion of Monomer with Time. Initiated
by TPML in THF at -78°C under Argon.
TIME
minutes
Mpa
SEC
Mw
Mnb
Mw / Mp
5
5859
6559
3772
1.74
15
6215
7209
4096
1.76
60
6691
7852
4708
1.67
1 20
6790
7515
4001
1.88
1 80
6891
7907
4053
1.95
a. With reference to polystyrene standards.
b. Mn Calculated = 2854.
Since stop-flow techniques were not available, an experiment was
devised wherein the polymerization reaction was terminated at incomplete
conversion. The time of reaction was 21 seconds after which the
polymerizing solution was quenched with methanol. The polymer was
precipitated as usual in excess of ether and the concentration of monomer
in the filtrate was determined by GC.
The rate constant for the pseudo-1st order polymerization reaction
(at a concentration of living polymer chains of approximately 10'3 M)
determined in this way was found to be 0.17 sec'1 with a half life of 4.1
seconds. Thus the polymerization reaction is seen to be extremely rapid.
Several factors must be considered before accepting the above value
of the rate constant. There could be errors involved in the determination of
the time of polymerization. Also the rate of polymerization may not
necessarily be pseudo-1st order (i.e., the assumption that the
concentration of the living ends is constant may not be true).

6 7
Polymerization and Studies of (+FPVS
Optically active (+)-PVS {[a^o = 358.5°} was polymerized using a
procedure similar to that used for the racemic monomer using TPML in THF
at -78°C. The polymer shows some unique properties.
It was found that the optically active monomer does not lose its
optical activity upon polymerization. This is expected since sulfoxide
sulfur does not epimerize under the polymerization conditions (1, 2], As
seen from the 13c NMR (Figure 3-9) all of the signals from the optically
active polymer are considerably sharper than the corresponding ones of the
racemic PPVS (Figure 3-10). This suggests a highly stereoregular
structure of (+)-PPVS as compared to the racemic polymer. The (+)-PPVS
would be expected to be isotactic as suggested by the broad methylene
absorption in NMR and by the stereochemistry of the dimers and trimers
studied extensively by Buese and Hogen-Esch [1, 2]. The polymer was found
to be only partially soluble in THF and chloroform both of which are
excellent solvents for racemic PPVS. The polymer is soluble in glacial
acetic acid. The decrease in solubility of (+)-PPVS also points to a more
regular structure. The polymer was found to be monodisperse (Mn = 1359,
Mn Calculated = 2920, Mw/Mn = 1.19).
Cooolvmerization of Stvrene and PVS
Both A-B and A-B-A type of copolymers were synthesized as
described in the experimental section.
A-B Copolymers
Figure 3-11 illustrates the various steps in A-B block
copolymerization and Table 3-4 summarizes the SEC data of various A-B
f'9
copolymerizations.

68
Figure 3-9. 50 MHz 13C NMR of (+)-PPVS in CDCI3 at room temperature.

6 9
Figure 3-10. 50 MHz 13C NMR of racemic PPVS in CDCI3 at room
temperature.

Table 3-4. A-B Diblock Copolymerization of Styrene and PVS in THF at -78°C
Sample
Moles
Polyst
yrene Block
Moles
Moles
A
B Diblock
Yield
PPVS
Styrene
Mn
Mp
Myy/Mn
DPPÜ3
PVS
Mn
Mp
Mw/Mn
%e
%f
x10-3
Calc'd3
SEC
x10-3
Added
Calc'dC
SECd
x10i2
AB21
8.76
3,432
2,713
1.10
0.360
2.25
3,664
3,979
1.16
98.6
21.32
AB53
6.13
3,432
2,713
1.10
0.250
6.75
6,790
7,954
1.22
97.0
47.08
AB66
7.00
3,432
2,713
1.10
0.288
14.30
10,271
11,245
1.27
96.9
66.82
AB85
6.13
3,432
2,713
1.10
0.252
35.00
16,920
17,101
1.24
68.1
74.85
AB90
1.93
3,432
2,713
1.10
0.079
15.80
19,055
19,252
1.41
54.3
78.37
PSPVS
28.40
8,687
9118
1.04
0.250
23.00
16,647
13,120
1.09
56.2
47.42
ABd89
10.00
2,359
3,341
1.09
0.440
2.25
4,121
3,733
1.18
95.6
—
a. Mn Calculated = moles styrene / moles t-butyllithium x 104.
b. DDPL = Polystyryllithium capped with DPE. Measured by UV/Vis.
c. Mn Calculated = moles PVS converted / moles DPPL x 152.22 + Mn polystyrene block.
d. Mp SEC with reference to polystyrene standards.
e. % Yield = gs of polymer / gs of monomer x 100.
f. % PPVS calculated from the ratio of aromatic absorptions of sulfoxide phenyl (3=7.4 PPM) and polystyrene
phenyl (3=7.0 PPM {meta and para protons} and 3=6.5 PPM{ortho protons}).
g. Diblock using styrene-d8.

71
(GHgJgC Li -P nCH2 —CH-Ph
-78°C/THF
(CH3)3C-CH2 — CH—(CH2 — CH)n Li+
Ph Ph
living polystyryllithium (cherry- red)
Ph
CH2-C^
Ph
(CH3)3C- (CH2- CH)n— CH2— C(Ph)2Li+
Ph
capped living polystyryllithium (dark red)
mCH2= CH — S—Ph
II
O
(CH3)3C- (CH2- CH)n— CH2— C(Ph)2- (CH2— CH)
_r^mLi+
Ph
(yellowish green)
MeOH
S— O
i
Ph
(CH3)3 C- (CH2 - CH)n— CH2— C(Ph)2- (CH2— CH) — H
I I
Ph
(colorless)
S = 0
Ph
Figure 3-11. A-B copolymerization of styrene and PVS.

72
Styrene was polymerized by a slow vapor phase addition of the
monomer onto a rapidly stirred initiator solution at -78°C in vacuo [25,
26]. Several initiators like methyllithium, s-butyllithium, etc. were tried.
However we found purified t-butyllithium to be the most efficient. This
initiator gave polymers with reproducible molecular weights and narrow
molecular weight distributions.
As can be seen from Table 3-4 the Mn calculated from the
concentrations of monomer and initiator (determined by UV) was quite
close to the one determined by SEC. Also the molecular weight distribution
for the styrene block was narrow (<1.1) which indicates negligible killing
of the growing polystyryllithium chains. Thus the DPE capped
polystyryllithium was seen to be an excellent initiator for PVS. The
molecular weight distributions were also better than for homopolymers of
PVS which is expected since we start out with polymeric initiators of
narrow molecular weight distribution. However at high PVS concentrations
considerable termination during polymerization was observed as seen from
the worsening molecular weight distribution and lower yields (entries 4
and 5 in Table 3-4).
Figure 3-12 shows a typical SEC chromatogram of the polystyrene
homopolymer (i) and styrene-PVS copolymer (ii). The PPVS content in the
copolymer was calculated from the 1 H aromatic absorptions of the
polystyrene phenyls (3 = 7.0 PPM {meta and para} and 3 = 6.5 PPM {ortho})
and the sulfoxide phenyls (3 = 7.5 PPM). Figure 3-13 is a 200 MHz 1H NMR
of a styrene-PVS A-B diblock copolymer and Figure 3-14 is the
corresponding 200 MHz 1H NMR of poly(phenylvinylsulfoxide) initiated by
TPML in THF at -78°C. The ortho protons in polystyrene are seen to be

73
Figure 3-12. SEC chromatograms of i) Polystyrene homopolymer (Mp =
8200, Mw/Mn = 1.09) and ¡i) A-B copolymer of styrene and PVS (Mp =
13,120, Mw/Mn = 1.09). Eluting solvent: THF at 1 ml/min.

Figure 3-13. 200 MHz 1H NMR of poly(styrene-b-PVS) copolymer in CDCI3
at room temperature.

7 5
Figure 3-14. 200 MHz 1H NMR of PPVS (initiated by TPML in THF at -78°C)
in CDCI3 at room temperature.

shifted upfield relative to the meta and para. This is due to the shielding
of the ortho protons being in the anisotropic field of the ^-electron current
of the neighboring ring [58],
In the runs 1-5 the polystyrene block was kept constant (Mp SEC =
2,713) whereas the sulfoxide content was varied. There was a good
correlation between the sulfoxide content calculated (from the ratio of
moles of styrene to moles of PVS) (21%, 53% and 66%) and that observed
from 1H NMR (21%, 47% and 67% respectively) for the first three runs.
However, a large variation was seen for runs 4 and 5 (85% and 90%
calculated and 75% and 78% observed). This also indicates substantial
killing during runs 4 and 5, where the concentration of PVS was high.
Run 7 was carried out using styrene-d8 and the corresponding
copolymer was used for the structure determination of the thermal
elimination product.
A-B-A Cooolvmers
Figure 3-15 illustrates the various steps in the A-B-A block
copolymerization and Table 3-5 summarizes the SEC data of the A-B-A
runs.
Lithium naphthalide was employed as the initiator for the two-ended
polymerization of styrene [39]. As is well known [25, 26] lithium
naphthalide initiates polymerization of styrene by electron transfer to
form the radical anion of the monomer which then immediately couples and
forms the dimer with two anions on either end. This dimer can further
propagate in both directions to give a two-ended polystyryllithium.
Excellent results were obtained when lithium naphthalide was
prepared using excess of naphthalene (Table 3-5) (Figure 3-16). However,
when lithium naphthalide was prepared by using an excess of lithium metal

77
(dark green)
7
CH2=CH — Ph
-78°C/THF
Li+ CH CH2CH2—CM Li+
Ph
(cherry red)
Ph
2mCH2=CH —Ph
Li^CH — CH2) CH CH2 CH2—CH (CH2—CH)mLi+
Ph
Ph
(dark red)
Ph
Ph
Li^CH —CH2)
AAA^A/VW»
+ 2n CH2= CH—S-Ph
O
(CH2— CH)nLi+
s=o s=o
phx ph/
(yellowish-green)
MeOH
PPVS-PS-PPVS triblock copolymer
(colorless)
j
Figure 3-15
A-B-A copolymerization of styrene and PVS.

Table 3-5. A-B-A triblock copolymerization of Styrene and PVS in THF at -78°C
Sample
Moles
Styrene
x10'3
Polyst
Mn
Calc'd3
yrene Bk
Mp
SEC
)ck
Mw/Mn
Moles
DDPPL*3
x10'3
Moles
PVS
Added
x10^
A-B-
Mn
Calc'dc
A Tribloc
Mp
SECd
k
Mw/Mn
Yield
%e
PPVS
%f
ABA30
6.35
11,960
11,393
1.07
0.132
2.7
14,506
18,152
1.14
97.9
41.80
ABA50
6.10
11,960
11,393
1.07
0.127
6.1
18,668
21,201
1.23
96.6
49.86
ABA78
5.55
11,960
11,393
1.07
0.116
19.7
29,967
30,601
1.33
74.3
65.50
ABA90
2.96
11,960
11,393
1.07
0.062
26.0
33,357
28,117
1.51
35.4
69.79
ABASO
19.0
55,000
59,520
1.08
0.079
15.0
79,233
79,060
1.12
90.5
29.46
ABAS1
25.0
26,666
29,750
1.04
0.169
15.0
43,672
48,078
1.10
98.2
35.53
ABAd89
9.60
9,793
10,553
1.08
0.188
3.8
13,597
14,921
1.10
95.0
—
a. Mn Calculated = moles styrene / moles lithium naphthalide x 2 x 104.
b. DDPPL = Dianion of DPE capped polystyryllithium. Concentration measured by UV/Vis.
c. Mn Calculated = moles PVS converted / moles DDPPL x 152.22 + Mn polystyrene block.
d. Mp SEC with reference to polystyrene standards.
e. % Yield = gs of polymer / gs of monomer x 100.
f. % PPVS calculated from the ratio of aromatic absorptions of sulfoxide phenyl (3=7.4 PPM) and polystyrene
phenyl (3=7.0 PPM {meta and para protons} and 3=6.5 PPM{ortho protons}).
g. Triblock using styrene-d8.

79
we ended up with a bimodal distribution in the SEC chromatogram (Figure
3-17). When lithium naphthalide is prepared using excess of lithium metal
one also gets the formation of naphthalene dianion alongwith the radical
anion [31]. The dianion itself may initiate styrene and a naphthalene group
may thus be incorporated in the middle of the chain [59]. In absence of
more extensive experimental evidence we will not attempt to interpret in
detail these anomalous results.
Table 3-5 once again shows that the dianion of polystyryllithium is
an excellent initiator for PVS. Again the molecular weight distribution of
the copolymer increases with increasing content of sulfoxide. This
indicates some termination when larger amounts of PVS are used.
Proof of Pianion Formation in the Lithium Naphthalide Initiated
Polvstvrvllithium
The "two-endedness" of the DPE capped living polystyryllithium
initiated by lithium naphthalide was proved in the following manner.
Styrene was independently initiated by lithium naphthalide in THF at -78°C
and capped with 1,1-DPE. The concentration of the carbanions was
measured using UV/VIS spectrometry (Table 3-6). The carbanion solution
was attached to an apparatus equipped with a quartz cell and a quartz
spacer. An excess of fluorene in a break-seal was also attached to the
apparatus. This was then evacuated and the carbanion solution was poured
in the cell through the break-seal and the absorbance of the red carbanion
solution was measured at its ¿.max (500 nm, Table 3-6). The living
carbanion was then reacted with fluorene. An immediate change in the
color of the solution was noticed on formation of the fluorenyllithium from
dark red to yellow. The absorbance of the solution of fluorenyllithium was
measured at its Xmax (373 nm) (Table 3-6). The extinction coefficient of

80
¡¡ i
Figure 3-16. SEC chromatograms of i) Polystyrene homopolymer (Mp =
10,553, Mw/Mn = 1.08) and ii) A-B-A copolymer of styrene and PVS (Mp =
14,921, Mw/Mn = 1.1). Polystyrene block initiated by lithium naphthalide
prepared by using an excess of naphthalene. Eluting solvent: THF at 1
ml/min.

81
Figure 3-17. SEC chromatograms of i) Polystyrene homopolymer and ¡I)
A-B-A copolymer of styrene and PVS. Polystyrene block initiated by
lithium naphthalide prepared by using an excess of lithium metal. Eluting
solvent: THF at 1 ml/min.

82
Table 3-6. UV/Visible data for various carbanion initiators in THF at 25°C.
CARBANIONS
*max
nm
MOL4R
EXTINCTION
COEFFICIENT (z)
TPML
500
30,980
TPMK
486
26,420
Lithium Naphthalide
367
10,263
326
22,350
292
32,550
aMS-22Li+
342
19,700
Polystyryllithium capped with
1,1-DPE, dianion
501
56,000
Fluorenyllithium3
373
9,600
Fluorenylpotassiumb
362
11,500
Potassium Chromate3
372
4815
a. From references 35-37.
b. Estimated from e of fluorenylsodium (Xmax 356 nm) =10,800 and
fluorenylcesium (Xmax 364 nm) = 12,000 [37],

83
the carbanion was thus calculated (e at Xmax = 28,000) from that of
fluorenyllithium which is well-known (e at X max = 9,600) [35-37], Hence
the concentration of the dianion of diphenyl polystyryllithium was
determined (moles of the carbanion solution = 3.03 x 10*6).
The terminated polystyrene was purified by precipitation in excess
of methanol and injected in SEC (Mw = 9199, Mn = 8633, Mw/Mn = 1.07, Mn
calculated = 9591). The polymer was weighed and hence the number of
moles of polymer was calculated from Mn (Moles of polymer = 1.48 x 10*4
moles.). Thus the ratio of moles of carbanion / moles of polymer was found
to be 2.05. This confirms that there are two moles of carbanion for every
mole of the polymer (i.e., two carbanions per growing polymer chain).
In conclusion, it is seen that homo- and copolymerization of PVS can
be carried out using conventional anionic polymerization techniques. A
variety of initiators could be employed but it was seen that delocalized
carbanions like TPML are excellent initiators. Electron transfer initiators
could also be employed to achieve two ended polymerization of PVS. There
was an excellent correlation between the calculated Mn and the
experimental Mn determined by SEC and 1H NMR. The molecular weight
distribution in most homopolymers was found to be narrow (<1.4). The
effect of temperature on initiation and propagation was seen to be
dramatic. In general lower temperatures resulted in well-defined and
narrow molecular weight distribution polymers. Initiation at -78°C led to
unimodal distribution indicating one initiating species whereas initiation
at 25°C led to a bimodal distribution due to the possible presence of two
initiating species. The polymerization of (±)-PVS was seen to be
extremely rapid with a pseudo-first order rate constant of 0.17 sec*1 and

84
a half-life of 4.1 seconds. Optically active (+)-PVS was also polymerized
and the resulting polymer was found to be stereoregular in structure.
Both A-B and A-B-A block copolymers of styrene and PVS were
synthesized. The A-B diblock copolymerization was carried out by vapor-
phase polymerization of styrene in THF at -78°C using t-butyllithium as
initiator followed by capping with 1,1-DPE. The capped polystyryllithium
was used for initiation of the PVS block. The A-B-A triblock
copolymerization was carried out by reacting two-ended polystyrene
prepared by using lithium naphthalide as initiator with 1,1-DPE to give a
capped stable living dianion of polystyryllithium which initiated PVS at
both ends to give an A-B-A triblock copolymer, polystyrene being the inner
block. The molecular weight distributions of the block copolymers were, in
general, narrower than the homopolymers.

CHAPTER 4
THERMAL ELIMINATION STUDIES
The thermal instability of sulfoxides has been recognized for more
than a century [60]. However, the synthetic utility of sulfoxides in organic
chemistry and the detailed mechanism of elimination of sulfoxides was
pioneered by Kingsbury and Cram [3]. They demonstrated the facile
elimination of phenyl sulfenic acid from 1,2-diphenyl-1-
phenylsulfinylpropane to give the isomeric 1,2-diphenylpropene. The
mechanism they proposed involved a stereospecific cis elimination similar
to the E¡ Cope elimination in amine oxides [61] and elimination in
selenoxides [62].
Mechanism of Sulfoxide Elimination
The mechanism of sulfoxide elimination proposed by Kingsbury and
Cram [3] is accepted even today. The mechanism they proposed is similar
to the classical mechanism for the internal elimination reaction. The
leaving group (Ph-S-O) abstracts a hydrogen from the [3-carbon (Figure 4-
1). The elimination is stereospecific; the erythro (1R, 2R or 1S, 2S)
sulfoxide gives trans-1,2-diphenylpropene whereas the threo (1S, 2R or 1R,
2S) gives cis-1,2-diphenylpropene at least at low temperatures.
At higher temperatures the reaction is less stereospecific. Thus at
higher temperatures a C-S homolytic bond cleavage was proposed to form a
sulfinyl and a benzyl radical pair without the radicals ever leaving the
solvent cage [3] (Figure 4-2). Other workers in this field [7, 65, 66, 67]
have accepted the above mechanism with some changes. Block [77]
85

86
l
(1 R, 2S)-1,2-diphenyl
propane
1 -phenylsulfinyl
CH3
Ph
C
C
H
Ph
Cis 1,2-diphenylpropene
Figure 4-1. Thermal eliminations in (1R, 2S)-1,2 -diphenyl
1-phenylsulfinyl propane at low temperatures.

87
H
Ph
ch3
n1' C"
/
H
Ph
S—O'
Ph^ \
O
CPU''
Ph
H
I
, C-
/
(1 R, 2S)-1,2-dipheny 1-1 phenylsulfinyl
propane
Ph
+
C 'ii /
Ph
H
CH3
Ph
C=C
*>
Transí ,2-diphenylpropene
Figure 4-2. Thermal eliminations in (1R, 2S)-1,2-diphenyl
1-phenylsulfinylpropane at high temperatures.

88
considered the sulfoxide elimination analogous to that of the amine oxides,
involving a five-membered six-electron transition state (4 electrons from
the C-S and C-H a bonds and 2 electrons as a lone pair on oxygen) and
termed it as a a2s + o2s +co2s sigmatropic elimination.
Kwart et al. [54] carried out a detailed comparison of the sulfoxide
and amine oxide thermolysis. A temperature dependence of the kinetic
deuterium isotope effect was found for the deuterated sulfoxides. This
result was apparently in keeping with what has been established for a
planar, concerted, pericyclic transition state. In contrast the amine oxide
elimination was indicative of a bent, cyclic transition state.
Use of Sulfoxides as Acetylene Svnthons
Vinyl sulfoxides have been extensively used in synthetic organic
chemistry as acetylene equivalents. It would serve us well to know a little
about the synthetic value of sulfoxides to introduce a vinyl group in a
molecule.
Michael Addition-Elimination.
Vinyl sulfoxides react with certain nucleophiles to give Michael-type
addition [4-9]. This Michael-adduct could then be subjected to thermolysis
to introduce a vinyl group. Thus vinyl sulfoxides were shown to be
acetylene synthons in Michael addition. This is illustrated in Figure 4-3 [4,
5] and Figure 4-4 [6]. The Michael adduct could also be subjected to
reductive desulfurization [9].
Alkylation-Elimination.
Trost [63, 69] carried out a series of synthetic reactions involving
the alkylation of a-sulfinyl carbanions and eliminations of the resulting
sulfoxides to give a-p unsaturated olefins (Figure 4-5).

8 9
X H + CHo =
Base/THF
CH —S —Ar ►
II
O
X—CH2— CH — S — Ar
II
O
H+
X CH=CH2 +
Ar-S-O-H
X— CHp— CHp- S — A r
II
O
Figure 4-3. Michael addition-elimination of vinyl sulfoxides.
1)NaH/THF
2) H+
O
II
C-0-CH2-CH3
CH2-CH2-S-Ph
O
(50%)
Figure 4-4. PVS as a vinyl synthon.

90
-CH2-Ph
O
1) LiNR^DME
2) Ph-CH2-Br
Ph
Ph-^-CH-CH2-Ph
O
A
Ph-CH=CH-Ph
Trans-stilbene (79%)
Figure 4-5. Alkylative eliminations.
R-i — CH2 — CH2 — C — R 1) Base
O
2) R2-S-S-R2 r
/CH2\
CH
O
II
/c\
R
S-R;
O
R1-CH=CH-C-R
A
-r2soh
[O]
o
ch2x cs
R1 CH r
I
o=s-r2
Figure 4-6. Sulfenylation-dehydrosulfenylation route to unsaturated
ketones and esters.

91
Sulfenvlation-Dehvdrosulfenvlation.
Trost [64-65] utilized the facile elimination of R-S-OH from
sulfoxides to introduce unsaturation a,p to a carbonyl group. A general
scheme for their approach of sulfenylation of ester and ketone enolates and
the oxidation and thermal elimination of the resulting sulfides is shown in
Figure 4-6.
Diels-Alder Cvcloadditions and Elimination
Paquette et al. [10] used PVS as an acetylene equivalent in Diels-
Alder cycloadditions. They utilized the dienophilicity of PVS and the in
situ thermal extrusion of phenyl sulfenic acid to give a one-pot reaction
giving the product of an acetylene-like Diels-Alder cycloaddition (Figure
4-7).
1.3 Dipolar Cvcloaddition and Elimination
Matsumoto et al. [68] used the above Diels-Alder reaction in 1,3
dipolar cycloadditions of PVS to dicyanomethylids. Thermal elimination of
the adducts gave 3-cyanoindolizines in moderate to good yields (Figure
4-8) indicating the use of PVS as an acetylene synthon in 1,3-dipolar
cycloadditions.
Elimination of PPVS and PS-PPVS Copolymers
Thermal elimination of the homo- and copolymers was carried out in
the solid state as described in Chapter 2. The polymer was dissolved in
chloroform or THF and a thin film of the polymer was cast in the pyrolysis
tube by a combination of vacuum and slow rotation on the rotovap. The tube
was then inserted in the furnace and the elimination carried out at 190-
200°C under high vacuum (10'6 Torr) for 1.5 to 2.0 hours. The yellowish-
white polymer became shiny black upon elimination and was handled under
argon at all times.

92
O
II
dibenzobarrelene (83%).
Figure 4-7. Use of PVS as an acetylene equivalent in Diels-Alder
cycloadditions.

93
Toluene/reflux
Figure 4-8. Use of PVS as an acetylene equivalent in 1,3
dipolar cycloaddition.

94
The polymer film after elimination became heterogenous as a result
of the "spitting out" of the benzene sulfenic acid (Figure 1-1). Thus the
polymer film had to be scraped out. The polymer after elimination was
found to be brittle. It was insoluble in all solvents. It was characterized
by IR, TGA, XPS and elemental analysis. Results of the characterization by
IR, TGA, and XPS will be discussed in the appropriate sections in this
chapter. Elemental analysis on the themolyzed homopolymer showed 3.0%
sulfur content (90% loss of sulfur). Elemental analysis on the thermolyzed
copolymer did not show any traces of sulfur.
Some of the products of elimination condensed on the side of the
tube outside the furnace in the form of crystalline needles. Much of it also
condensed in the cold trap. The eliminated products obtained from the
condensation in the cold trap showed a slew of products in GC and gave no
useful information. However the products of elimination obtained as
crystalline needles from the side of the tube showed two major peaks in
the GC consisting of a lower boiling fraction (86.8%) and the higher boiling
one (11.9%). From mass spectrometry, 1H NMR and 13C NMR (Figure 4-9),
the lower boiling elimination product was identified as diphenyl disulfide
(Ph-S-S-Ph) whereas higher boiling product was identified as
benzenesulfonothioic acid, S-phenyl ester (Ph-SC>2-S-Ph) (phenyl
benzenethiolsulfonate).
Fate of Phenvl Sulfenic Acid.
Sulfenic acids are notorious for their instability [3, 69-76]. Only in
very few cases have they proved capable of actual isolation [74, 75,.76].
Shelton and Davis [74] report isolation of t-butylsulfenic acid. Penicillin
i

Figure 4-9. 50 MHz 13C NMR of the products of elimination of phenyl sulfenic acid from PPVS

96
sulfenic acid, anthraquinone sulfenic acids have been the only other
sulfenic acids known [72],
Sulfenic acids under ambient conditions dehydrate immediately to
form the anhydride. In our case phenyl sulfenic acid is expected to
dehydrate to give the anhydride benzenesulfinothioic acid, S-phenyl ester
(Ph-S(O)-S-Ph) (phenyl benzenethiolsufinate). This dehydration reaction is
shown in Figure 4-10.
The sulfenic acids associated by hydrogen bonding may be functioning
as both S nucleophiles and S electrophiles [72]. The sulfenic acid
dehydration reaction is essentially irreversible. Kice and Cleveland [75]
suggest that the dehydration reaction in phenyl sulfenic acid is favored
over its hydration (hydrolysis of the phenyl benzenethiolsulfinate) by a
factor of at least 106.
The thiolsulfinate itself is not thermally stable [73] and
disproportionates rather readily. Fava did extensive kinetic and
mechanistic studies on the disproportionation of aryl arenethiolsulfinates
[73]. They found that the rate equation of disproportionation of
thiosulfinates contain one first-order and one three-halves-order term.
This form of rate equation suggested a unimolecular decomposition along
with an induced decomposition. The first order path was due to the
homolytic fission of the labile S(0)-S bond to give a sulfinyl and a thiyl
radical (Figure 4-11, equation i). Dimerization of the thiyl radical gives
diphenyl disulfide (Figure 4-11, equation ii). Dimerization of the sulfinyl
radical give phenyl benzenesulfonothioic acid through an anhydride
intermediate (Figure 4-11, equation iii). However, in this case as well as
our's the ratio of disulfide to thiolsulfonate is found to be greater than one
(from GC shown above) which indicates formation of other products besides
I

97
Ph-S-O-H
O
II
Ph S S—Ph +
benzenesulfinothioic acid, S-phenyl ester
Figure 4-10. Dehydration of phenyl sulfenic acid.
H20
Ph-
O
II
S-
S—Ph
2 Ph-S
O
II
2 Ph-S â– 
O
Ph-S • +
Ph-S-S-Ph
diphenyl disulfide
S—Ph (i)
(Ü)
r ft) n
Ph —S S—Ph
(iii)
I n
Ph-S-O-S-Ph
ii
O
o
Ph-S-S-Ph
II
O
— benzenesulfonothioic acid,
S-phenyl ester
Figure 4-11. Disproportionation of benzenesulfinothioic acid,
S-phenyl ester.

98
the two detected. Fava [73] suggested the formation of sulfonic anhydride
(Ph-S02-0-S02-Ph) which undergoes further fragmentation and
recombination. The reactions in Figure 4-11 were also consistent with the
pyrolysis-MS of homo PPVS. The mass spectra of the elimination products
will be discussed below.
Thermal Methods for Study of Elimination
Thermoaravimetric Analysis (TGA1
TGA involves the continous monitoring of loss in weight of a sample
as it is heated at a constant rate of change of temperature or a change in
weight with time at a constant temperature. The heating is usually carried
out in an inert gas flow (nitrogen, 50 ml/min) (Chapter 2).
The polymer was ground into a fine powder. Usually a sample size of
two mgms was used for most runs. A heating rate of 10°C/min was
employed from 50°C to 900°C.
PPVS Homopolymer
PPVS homopolymers show two distinct stages of decomposition
(Table 4-1). Most thermograms also show loss of moisture/solvent etc.,
which may have been entrapped in the polymer matrix, at around 100°C.
The first stage of decomposition shows an onset at around 120°C and
reached a maximum rate (seen from its first derivative) at around 200°C.
There is usually an 80% loss in the first stage which corresponds to the
elimination of phenyl sulfenic acid (Figure 4-12a). The theoretical loss of
phenyl sulfenic acid would correspond to 83% loss assuming complete
elimination of phenyl sulfenic acid. The temperature of elimination of
phenyl sulfenic acid from PPVS homo- and copolymers is lower than most
vinyl polymers containing pendant electronegative groups X which can on

99
Table 4-1. TGA data for (a) PPVS homopolymers, (b) After thermal
elimination of phenyl sulfenic acid in vacuo at 200°C for 2 hrs. (c) After
oxidation of PPVS to poly(phenylvinylsulfone). (d) Genuine polyacetylene
sample.
Sample
First Stage
Second Stage
tonset°c¡
tmax °c"
tmax °c»¡
a. PPVS
120.2
205.2
480
125.2
208.0
450
134.2
210
460
(+)-PPVS
117.0
1 77
480
b. Thermolysed PPVS
—
—
453
c. PPVO
209
310
—
d. polyacetylene
—
—
476
i. Temperature of onset of decomposition determined from the first
derivative of the TGA curve (First Stage).
ii. Temperature at maximum rate of decomposition determined from the
first derivative of the TGA curve (First Stage).
iii. Temperature at maximum rate of decomposition determined from the
first derivative of the TGA curve (Second Stage).

Waight 100
1
Figure 4-12. Weight % vs Temperature (TGA) curves for PPVS
homopolymer: (a) Before thermolysis and (b) After thermal elimination of
phenyl sulfenic acid in vacuo at 200°C for 2 hrs.

101
elimination of HX give polyacetylene-like polymers. This was extensively
studied by Montaudo et al. [78].
The TGA thermogram of (+)-PPVS shows some unique features. There
is a considerable decrease in the thermal stability of the optically active
polymer as evident from a decrease in the temperature of maximum rate of
elimination (175°C). Apparently stereoregularity of (+)-PPVS translates
into decreased thermal stability.
The elimination of phenyl sulfenic acid would be expected to be a
cyclic, sigmatropic, six-electron elimination as shown before. A "zipper"
mechanism is most likely; the formation of one double bond would create a
"seed" for the propagation of the next and so on down the chain. It has been
well-documented in sulfoxide eliminations [63, 69] that the ease of
hydrogen abstaction decreases in the order allylio benzylio secondary>
tertiary. Thus, formation of one double bond would create an allylic site
for the next and elimination would proceed more easily.
The phenyl sulfenic acid once eliminated would immediately
dehydrate (see above) forming the thiolsulfinate ester which itself
undergoes disproportionation to the thiolsulfonate ester and the disulfide.
Thus ultimately the products of disproportionation of the thiolsulfinate
ester are obtained. None of the phenyl sulfenic acid would be expected and
none was seen by GC, MS, etc.
The second stage of decomposition in the TGA of the homopolymer
shows a maximum rate of decomposition around 450°C. This is typically
the temperature at which the polyene sequences in polyacetylene start to
degrade yielding various alkyl aromatics [78, 80, 81]. A discussion of
polyacetylene decomposition will follow in the section of pyrolysis-MS.

102
Table 4-1 also summarizes the data from the TGA curves of the
thermolysed PPVS. The thermogram (Figure 4-12b, Figure 4-13a) is
conspicuous by the total absence of the first step of decomposition seen in
the precursor (±) PPVS at around 200°C. The TGA curve of the thermolysed
PPVS is comparable to the thermogram of polyacetylene (Figure 4-13b,
Table 4-1 entry d). The sample of polyacetylene was made in our group by
Dr. K. Al-Jumah using the Shirakawa catalyst [12]. The thermogram of
thermolysed PPVS is also comparable to the second step of degradation in
the vinyl polymers studied by Montaudo [78] and TGA of polyacetylene from
the literature [80, 81].
The thermal elimination of phenyl sulfenic acid is seen only in
sulfoxides. On oxidation of PPVS to poly(phenylvinylsulfone) (PPVO) the
polymer becomes thermally stable. This is corroborated by the TGA curve
of PPVO (Entry c, Table 4-1). Only one degradation step is seen at a high
temperature (300°C). Thus we see a distinct difference in the thermal
behavior of sulfoxides and sulfones.
Stvrene-PVS Copolymers
Table 4-2 summarizes the TGA data of the copolymers of styrene and
PVS and Figure 4-14 shows a typical thermogram of styrene-PVS
copolymer. Once again two distinct stages of decomposition are seen in
the TGA thermogram of the copolymer (both A-B and A-B-A). The first
stage of decomposition shows an onset which varies from 120-140°C.
However the maximum rate of elimination is around 210°C for most
polymers. This corresponds to the first stage in the decomposition of homo
PPVS wherein phenyl sulfenic acid would be expected to eliminate through
a sigmatropic elimination step to form what would be styrene-acetylene
block copolymers. It is significant to note that polystyrene degrades at a

Weight CWt. Z>
103
Figure 4-13. Weight % vs Temperature (TGA) curves for (a) Thermolysed
PPVS homopolymer and (b) Polyacetylene.

104
Table 4-2. TGA data of styrene-PVS A-B diblock and A-B-A triblock
copolymer.
Sample
First Stage
Second Stage
tonset°c£
tmax °cb
tmax °cc
1
polystyrene
—
—
445
2
AB21d
120
205
422
3
AB53
1 38
208
446
4
AB66
1 39
222
447
5a
AB85
127
216
437
b
HAB85e
—
—
460
c
OAB85f
200
310
—
6
AB90
137
217
432
7a
ABd8
120
196.5
417
b
HABd89
—
—
448
8
ABA30h
130
205
445
9
ABA50
1 48
215
424
10
ABA78
150
211
454
1 1
ABA90
140
207
436
12a ABAd8
1 44
212
457
b
HABAd8'
—
—
450
13
ABASO
142
210
450
14a ABAS1
1 36
207
441
b
HABAS1Í
--
--
425
a Temperature of onset of decomposition determined from the first
derivative of the TGA curve (First Stage).
b. Temperature at maximum rate of decomposition determined from the
first derivative of the TGA curve (First Stage).
c. Temperature at maximum rate of decomposition determined from the
first derivative of the TGA curve (Second Stage).
d. For information on the A-B copolymers see Table 3-4.
e. Thermolysed AB85.
f. Oxidised AB85.
g. Thermolysed ABd8.
h. For information on the A-B-A copolymers see Table 3-5.
i. Thermolysed ABAd8.
j. Thermolysed ABAS1.

105
Figure 4-14. Weight % vs Temperature (TGA) curves for Styrene-PVS
copolymer (sample AB-85, Table 4-2) (a) Before thermolysis and (b) After
thermolysis in vacuo at 190°C for 1.5 hrs.

106
much higher temperature (Entry 1, Table 4-2). Thus at the lower
temperatures used for the elimination of phenyl sulfenic acid the
polystyrene block would be mostly unaffected. This is also shown by
pyrolysis-MS which will be discussed later.
The second stage of decomposition in the block copolymers occurs
around 440-450°C which is the temperature at which styrene
depolymerizes by an unzipping mechanism (Entry 1, Table 4-2) [82, 83] and
at which the polyene sequences of the polyacetylene block rearrange and
decompose to yield various aromatic hydrocarbons [80, 81].
The sample AB85 containing 74.9% of sulfoxide in the A-B copolymer
was oxidized as before using 30% H2O2. The oxidized copolymer,
interestingly enough, shows only one high temperature degradation stage
(Entry 5C, Table 4-2), although one would expect to see two stages
corresponding to the sulfone decomposition at 300°C and polystyrene
depolymerization at 450°C.
Several copolymers were subjected to thermolysis in vacuo at
190°C. The products are brittle cellophane like transparent yellow films.
The TGA of the heated copolymers is also summarized in Table 4-2 (Entries
5c, 7b, 12b, and 14b). Once again only one high temperature degradation
step was noted around 450°C. This also confirms the almost quantitative
elimination of phenyl sulfenic acid from the copolymer.
Pvrolvsis-Mass Spectrometry
Mass spectrometry (MS) is much less used for structure
determination in polymers than in low MW organic compounds. Since MS
techniques require transfer of the sample in the gas phase, the low
volatility of polymers has constituted a serious drawback for the
application of mass spectrometric analysis to polymer systems.

107
Remarkable progress was achieved when polymers were introduced directly
into the mass spectrometer and pyrolysis performed close to the ion source
[84], Recent advances [84-86] in laser technology, however, have spawned
a lot of interest in MS of polymer systems especially laser desorption/FT-
MS [85].
Montaudo [78, 79] carried out studies of thermal degradative
mechanisms in vinyl polymers with a pendant electronegative group which
on elimination would lead to the formation of polyene structures. Ours
being a similar system, it was decided to carry out pyroiysis-MS on PPVS
homo and copolymers.
PPVS Homopolvmers
Distinct differences were found in the MS of PPVS at low and high
pyrolysis temperatures. The MS at low pyrolysis temperature (<190°C) is
consistent with the elimination of phenyl sulfenic acid and its further
reactions. The positive ion fragments (m/z) in the pyrolysis-MS of homo
PPVS at 190°C along with the assignments of the peaks are summarized in
Table 4-3. The m/z 218 (Ph-S-S-Ph) absorption was observed as the base
peak. The MS was compared with the actual MS reported in the EPA/NIH
Mass Spectral Data Base. From the comparison we conclude that the MS
observed at low temperatures is mainly due to Ph-SO-S-Ph, Ph-SC>2-S-Ph
and Ph-S-S-Ph that were also previously identified.
There was no indication of presence of phenyl sulfenic acid which
corroborates our conclusion that it dehydrates to the sulfinothioic ester
immediately upon formation (Figure 4-10). Although the presence of Ph-
SO-S-Ph is detectable it is mainly its disproportionation products (Ph-
SC>2-S-Ph and Ph-S-S-Ph) (Figure 4-11) that constitute the MS at low
temperatures.

108
Table 4-3. Data from the pyrolysis-M.S. of homo PPVS at 190°C
Positive Ion Fragments
M/Z
Ph-S-S-Ph
Ph-S02-S-Ph
Ph-S-Ph
Ph-Ph
Ph-S02
Ph-SO
Ph-SH
Ph-H
H2O
218 Base peak
250
1 85
1 54
141
125
1 1 0
78
18
Table 4-4. Data from the pyrolysis-M.S. of homo PPVS at 450°C
Positive Ion Fragments
M/Z
Ph-SH
110 Base peak
propyl anthracene
220
ethyl anthracene
206
methyl anthracene
192
anthracene
178
propyl naphthalene
1 70
ethyl naphthalene
156
methyl naphthalene
142
naphthalene
128
propyl benzene
120
xylene
1 06
toluene
91
benzene
78
H2O
18

109
At high pyrolysis temperatures (>400°C) a totally different picture
emerges (Table 4-4). The base peak is m/z 110 (PhSH) which indicates
presence of the decomposition products in the polymer matrix (mainly
PhSSPh and PhSC>2SPh). However the most intense peaks are due to alkyl-
aromatic hydrocarbons, seen as periodic clumps of high mass peaks [78,
79], Polyacetylene exhibits a similar pyrolysis-MS at 490°C [78] showing
toluene as the base peak and other substituted aromatics of higher masses.
According to Chien et al. [81] in the pyrolysis of polyacetylene the
initiation process of degradation is probably the thermal excitation of
bonding k electrons to the antibonding state resulting in bond dissociation
to form vinyl radicals (Figure 4-15) followed by intramolecular electron
migration and ring closure leading directly to benzene. Other alkyl-
aromatics can be accounted for by a series of proton-electron migrations
which may be quantum-mechanical tunneling in nature. The formation of
alkyl-aromatics probably involve cleavage of cross-linked polyacetylene
chains at high temperatures (>450°C) (Figure 4-15) [78].
Stvrene PVS Copolymers
Like the homopolymer, the copolymer also shows distinct differences
in the decomposition at low and high pyrolysis temperatures.
At low temperatures (<190°C) (Table 4-5) once again we see the MS
due to the elimination of phenyl sulfenic acid and its further reactions.
From the total ion current it is seen that the polystyrene block is mostly
unaffected even at 225°C. Formation of styrene, which is indicative of
depolymerization of the polystyrene block, is only beginning around 225°C.
This result was significant for our purpose since we can safely carry out

cross-linked
polyacetylene
Substituted
Aromatics
Figure 4-15. Scheme for the formation of alkyl-aromatics in the pyrolysis
of polyacetylene at high temperatures (>450°C).

Ill
Table 4-5. Data from the pyrolysis-M.S. of styrene-PVS copolymer at
150°C.
Positive Ion Fragments
M/Z
Ph-S
109 Base peak
Ph-S02-S-Ph
250
Ph-S-S-Ph
218
Ph-S-Ph
1 85
Ph-Ph
154
Ph-S02
141
Ph-SO
125
Ph-SH
110
Ph-H
78
Ph
77
H2O
18
Table 4-6 Data from the pyrolysis-M.S. of styrene-PVS copolymer at
435°C.
Positive Ion Fragments
M/Z
Ph-CH=CH2
propyl anthracene
ethyl anthracene
methyl anthracene
anthracene
naphthalene
propyl benzene
toluene
benzene
104 Base peak
220
206
192
178
128
120
91
78

112
the elimination of the copolymers at lower temperatures without
significantly degrading the polystyrene block in the copolymer.
Formation of styrene is greatly accelerated at temperatures above
250°C and in fact above 300°C styrene becomes the base peak in the MS
(Table 4-6). Once again at higher temperatures we see (although to a
lesser extent because of polystyrene degradation) alkyl-aromatics typical
of polyacetylene decomposition.
Studies of the Elimination of PPVS bv Spectroscopic Methods
X-Rav Photoelectron Spectroscopy (XPS)
XPS or electron spectroscopy for chemical analysis (ESCA) is
generally regarded as a key technique for surface characterization and
analysis of polymers. This technique provides a total elemental anaysis of
the top 10-100 Á of any solid surface or film [87, 88].
The basic principle of XPS is the photoelectric effect. Low energy
X-rays (magnesium K-a) impinge the surface of a thin film. Absorption of
these X-rays results in interaction with one of the core atomic orbital
electrons such that there is a total and complete transfer of the energy of
the photon to the electron. Since the photon energy is greater than the
binding energy of the electron in the atomic orbital, the electron is ejected
from the atom. The total energy of the X-ray photon must be accounted for
and to a first approximation it is partitioned in two ways. One of the
components is the binding energy of the electron Eb and can also be thought
of as the energy required to remove the electron from the atom or the
ionization energy of the electron. The energy in excess of Eb appears as the
kinetic energy of the electron after it is emitted (Ek). It is this kinetic
energy that the spectrometer measures and hence calculates the binding
energy of the electron. Thus the basic equation for XPS is

113
Eb = hu - Ek
where hv> is the energy of the X-ray photon.
The X-ray photons statistically interact with the atomic and
molecular orbital electrons in the sample. Some fraction of the
photoelectrons produced are directed up and out of the sample and analyzed
by the analyzer which basically measures the number of electrons and their
different kinetic energies and produces a spectrum of photoelectron
intensity as a function of binding energy. The binding energy (B.E.) position
of each of the key peaks allows identification of the atoms involved and
measuring the area under each peak allows quantitation of each of the
elements present on the surface of the polymer film. There are many
variables involved and there may be charging effects of the sample which
would tend to shift the B.E. from sample to sample. Thus an internal
reference has to be used for calibration. Commonly this is the carbon 1s
peak at 285.0 eV.
We used XPS for a) surface elemental composition of PPVS homo- and
copolymers, b) surface elemental composition for the homo- and
copolymers after thermolysis, c) determination of the oxidation of
sulfoxides to sulfones, and d) to monitor changes on the surface of the
polymers upon heating in the XPS spectrometer.
Table 4-7 summarizes the data obtained on various samples. The
B.E.s are reported with respect to the C1s peak (285 eV). In the homo-
PPVS (entry 1, Table 4-7) the sulfoxide sulfur shows a S2p B.E. of 166 eV.
This is comparable to the sulfoxide S2p B.E. of 165.9 eV in Ph2SO reported
in the literature [89]. Oxidation of PPVS to PPVO results in a shift of +3
eV (B.E. = 168.9 eV for PPVO, Entry 2, Table 4-7). Oxidation of sulfoxide to

114
Table 4-7. Data from the ESCA spectra of PPVS homopolymers, styrene-PVS
copolymers and their thermolysed and oxidized products.
Sample
Element
Binding Energy
(eV)
Atomic Cone.
(%), Exp’tal
Atomic Cone.
(%), Calc'd
1. PPVS
C1s
285.0
78.9
80.0
homopolymer
01s
531.3
12.2
10.0
S2p
166.2
8.9
10.0
2. Oxidised
C1s
285.0
83.4
72.7
PPVS
01s
532.4
11.6
18.2
S2p
168.9
5.0
9.1
3. Thermolysed
C1s
285.0
PPVS
01s
532.9
4. AB85a
C1s
285.0
82.4
91.4
01s
531.6
14.9
4.3
S2p
166.2
2.6
4.3
5. Oxidised
C1s
285.0
82.2
87.4
AB85
01s
532.2
15.4
8.4
S2p
169.0
2.42
4.2
6. Thermolysed
C1s
285.0
91.3
1 00
AB85
01s
532.5
8.5
0.0
7. ABASlb
C1s
285.0
90.0
95.7
01s
532.4
8.5
2.1
S2p
166.8
1.47
2.1
8. Oxidised
C1s
285.0
77.0
95.0
ABAS1
01s
531.8
19.2
3.3
S2p
168.5
3.8
1.7
9. Thermolysed
C1s
285.0
92.0
100
01s
534.1
7.88
0.0
a. For information on AB85 see Table 3-4.
b. For information on ABAS1 see Table 3-5.

sulfone results in a more electropositive sulfur and hence greater B.E. of
the core electrons (chemical shift effect) [87].
The thermolysed PPVS does not show any presence of sulfur in the
XPS spectrum. However surface oxidation, presumably during handling,
resulted in an 01s peak at 533 eV (Entry 3, Table 4-7). It was seen that
most of the spectra in XPS showed a decided sensitivity to surface
oxidation as revealed from the inflated atomic concentration of 01s.
Oxygen was also detected from the residual silicon grease in the polymer
(or in the sample holder) which has a low surface free energy and tends to
"creep up" during scanning. However oxygen from grease could be easily
detected by a consequent absorption of the Si2s peak at 153 eV and Si2p
peak at 102 eV.
There was a good correlation between the experimental and
calculated atomic concentrations for PPVS. However the correlation
between the experimental and calculated atomic concentration in the
copolymers (both A-B and A-B-A) was seen to be quite poor. The surface
free energy of a polymer is inversely proportional to the contact angle of
an air bubble in water in contact with the polymer film. The contact angle
of PPVS, AB and ABA copolymers and polystyrene was measured by the
captive air bubble method [90] (described in the Experimental section). The
contact angle varied from 50° for PPVS to 86° for polystyrene. The
copolymers show an intermediate contact angle depending on the
composition. From this rough experiment it was seen that PPVS has a
higher surface free energy compared to the copolymers. It is thus possible
that the polystyrene block in the copolymer would occupy much of the top
50-100 Á which is the range of the XPS experiment. This might be a reason

116
for the poor correlation between the experimental and calculated atomic
concentrations in copolymers.
The oxidized copolymer AB85 (Entry 5, Table 4-7) also reveals the
chemical shift effect of oxidation of sulfoxide to sulfone. The thermolysed
copolymers once again do not show any presence of S2p but do show
presence of 01s.
XPS was also employed to monitor the change in the polymer
composition with temperature. The experimental details of high
temperature XPS studies have been discussed in the Experimental section.
Figure 4-16 shows the dramatic change in XPS in going from room
temperature to 300°C. The S2p peak starts disappearing around 100°C.
Interestingly enough although at higher temperatures (>200°C) the 166 eV
S2p peak of sulfoxide completely disappears three other S2p peaks show up
albeit of less intensity (Figure 4-17) at (i) 164.0 eV which could be
assigned to Ph-S-S-Ph [89] and (ii) 169.0 eV and (iii) 169.5 eV which could
be assigned to Ph-S(0)2-S-Ph [89]. These are the final products of
elimination. Thus we see that some of the eliminated products
contaminates the polyacetylene formed. This was also seen in IR
spectroscopy which will be discussed later.
Figure 4-16 also reveals the persistence of the 01s peak even at
300°C. As seen before this might be due to presence of residual silicon
grease in the polymer.
Nuclear Magnetic Resonance (NMR1
One of the drawbacks of polyacetylene is its intractable nature. It is
insoluble in all solvents. Spectroscopic methods involving the study of
polyacetylene of necessity are thus solid-state based [1.1-1.4]. It was
therefore highly desirable to see if solution properties of polyacetylene

Figure 4-16. Change in the XPS spectra of PPVS homopolymer with temperature going from room temperature to
300°C.

íoefti
PPVS: R.T.
600
01S
CIS
S2P
1000 800 600 <00 200
Binding Energy (*U)
600
ol s
CIS
s2p
1000 800 600 <00
Binding Energy (*U>
800
118

119
180
170 160
Binding Energy (eU)
150
Figure 4-17. XPS spectrum of the S2p region of PPVS at 200°C.

120
could be measured as a block copolymer containing a soluble block. Thus
our system of A-B and A-B-A copolymers of polystyrene-b-acetylene was a
potentially attractive way to study soluble polyacetylenes. However we
found that the presence of more than 10 polyene units or more than 5
mole% of polyacetylene in the copolymer renders the precursor insoluble
upon thermal elimination. The copolymer AB21 (Table 3-4) containing
21-32% of sulfoxide was found to be soluble in chloroform upon
elimination. It is seen that the polyene sequences in the thermolysed
copolymer are overlapped by the ortho aromatic absorptions of the
polystyrene phenyl (3 = 6.2-6.8 PPM). This is also confirmed by the
decrease in the integration of the sulfoxide methine absorption at 3.0 PPM
and sulfoxide methylene absorption at 1.8 PPM (which overlaps in the
precursor sample with the methine absorption of polystyrene). It was thus
decided to see if the acetylenic =CH absorption could be observed in a
copolymer which is not complicated by the ortho aromatic absorptions of
the polystyrene block. Thus copolymers (both A-B and A-B-A) were
synthesized with styrene-d8. However we were unsuccessful in
solubilizing the thermolysed copolymer with a high enough polyene content
for NMR analysis.
The thermal elimination of phenyl sulfenic acid from PPVS was
monitored by 1H NMR from 30°C to 150°C. The polymer was dissolved in
glacial acetic acid-d4 and sealed inder a partial pressure of argon. The
partial pressure of argon was necessary to improve resolution at high
temperatures (private communication from Dr. Roy King). Figure 4-18 a-d
dramatizes the effect of temperature on the 1H NMR of PPVS. Several
interesting features are worth noting. It is seen that up to about 100°C
there was little change in the 1H NMR. At 100°C , however, we see several

121
(b). 100°C
Figure 4-18. Change in the 300 MHz 1H NMR spectra of PPVS
homopolymer with temperature: (a) room temperature (b) 100°C in
CD3COOD.

122
(d). 150°C
Figure 4-18 (continued). Change in the 300 MHz 1H NMR spectra of
PPVS homopolymer with temperature: (c) 120°C (d)150°C in
CD3COOD.

123
changes. The CH and CH2 absorptions at 53.2 PPM and 51.8 PPM respectively
show a decrease in intensity. Simultaneously we see two peaks showing up
in the vinyl region at 55.7 and 56.3 PPM. The aromatic absorptions become
sharper. At 120°C the above events become more enhanced. The CH and
CH2 absorptions have decreased further whereas the vinylic absorptions
have intensified. At 150°C all of the peaks disappear except for the
aromatic absorptions probably as a result of polymer precipitation.
We give the following interpretation of the above events. As the
temperature is increased from room temperature to 100°C we see the
formation of polyene linkages due to the sigmatropic 6-tc elimination of
phenyl sulfenic acid from PPVS as illustrated in Figure 4-19. A decrease
in the -CH2- and -CH- absorptions of the sulfoxides was noticed concurrent
with the development of broad absorptions in the vinyl region. Table 4-8
summarizes the normalized area of the vinyl protons as compared to the
normalized area of the sulfoxide methine from which the percentage of the
polyene groups (both cis and trans) could be calculated. We see a dramatic
increase in the % polyene from 80°C to 100°C (10% to 40%). Obviously the
polyenes form at the expense of the methylene and methine of PPVS. The
polymer is still soluble because of the presence of a substantial
percentage of sulfoxide groups in the polymer (Table 4-8). Thus random
and/or block copolymers may be formed. The two peaks in the vinyl region
indicate two different types of olefins; cis/trans or internal/terminal.
The fact that we do not see a change in the chemical shift of the polyene
peaks with temperature indicate that they are most likely due to geometric
isomers. Also the chemical shifts observed (5 5.8 PPM and 5 6.3 PPM) are
close to those observed in low MW conjugated cis and trans polyenes from
the literature [91-93] {Cis 1,3,5 hexatriene (5 in PPM): 5 5.1 (4H), 5 5.9

124
+
Ph-S-O-H
Ph-S-O-H â–º Ph-S-S-Ph + Ph-S02-S-Ph + H20
CD3-COOD + H20 â–º CDg-COOH + HOD
Figure 4-19. Sequence of events in the high temperature 1H NMR
studies of PPVS in CD3COOD.
Table 4-8. Data from the high temperature 300 MHz 1H NMR of PPVS in
CD3COOD.
Temperature
°C
Area of
polyenes3
Area of
PPVS methine^
% Polyenes
80
0.1745
0.8255
9.56
1 00
0.5561
0.8255
38.5
120
0.7021
0.2979
54.1
140
0.7311
0.2689
57.6
a. Normalized area of integration of the polyene absorptions at 3 5.7
and 3 6.3 PPM.
PPM
b. Normalized area of integration of the PPVS methine absorption at 3 3.2
PPM.

125
96.7 (2H). Trans 1,3,5 hexatriene (9 in PPM): 9 5.1 (4H), 9 6.2 (4H). (E,E)-
Octa-1,3,5,7-tetraene (9 in PPM): 9 4.9-5.5 (4H), 9 6.3 (6H). (E,E,E)-Nona-
1,3,5,7-tetraene (9 in PPM): 9 1.8 (3H), 9 4.9-6.0 (2H), 9 6.0-6.5 (7H).
(E,E,E)-Deca-1,3,5,7,9-pentaene (9 in PPM): 9 5.0-5.3 (4H), 9 6.3 (8H)}.
Thus absorptions at 9 5.8 PPM and 9 6.3 PPM are reasonably attributable to
cis and trans polyenes. Sharpening of peaks in the aromatic region is seen
because of the formation low molecular weight elimination products as
shown before. At 150°C all the peaks (except the aromatic absorptions of
the eliminated products) disappear. At this stage (55% polyene, Table 4-8)
the polyene linkages renders the polymer insoluble and it precipitates out.
Infrared (IR)
IR was used both for routine identification of homo- and copolymers
as well as for the interpretation of the thermolysis process in PPVS.
Unfortunately we could not derive much information of the polyacetylene
absorptions from IR because of the high absorptivity of the residual
sulfoxide groups in IR which overlaps with the =C-H bend absorption of
polyacetylene.
A case in point is seen from Figure 4-20 which shows the change in
IR of PPVS with temperature. The polymer was mixed with diamond
powder and heated insitu under a flow of nitrogen. The spectra were
scanned at various temperature intervals. At 30°C we see the
characteristic IR of PPVS showing a strong absorption at 1041 cm*1 due to
the S=0 stretch of the sulfoxide group. Upon heating the polymer to 240°C
we see the disappearance of the 1041 cm-1 absorption concurrent with the
appearance of a strong absorption at 1143 cm'1, medium absorptions at
1323 cm*1, 1436 cm-1, 1474 cm'1 and a weak absorption at 1575 cm'1.
The IR of PPVS at 240°C was identical to that of Ph-S-S-Ph and

transmittance
126
NICOLET FT-IR
m
jt*
to -
to
cn
o
(O2000
1Ó00 iioo i"ioo íéoo íóoo
WAVENUMBER
Figure 4-20. Change in the IR spectra of PPVS homopolymer with
temperature: (a) 30°C and (b) 240°C, under nitrogen.

127
Ph-S02-S-Ph (Sadtler). Thus the strong absorption at 1143 cm*1 and 1323
cm'1 are probably due to the 0=S=0 stretch and S-S stretch respectively of
Ph-S02-S-Ph whereas the ones at 1436 cm'1, 1474 cm'1 and 1575 cm-1
are due to Ph-S-S-Ph. Thus the eliminated products cloud the IR window
and/or are left behind on the eliminated polymer giving no useful
information on the cis or trans =CH absorptions.
In conclusion, the thermal elimination of phenyl sulfenic acid from
PPVS homo- and copolymers was studied by TGA and pyrolysis-MS. The
TGA of homopolymers typically show two degradation stages: one at lower
temperature corresponding to elimination of phenyl sulfenic acid and one at
higher temperatures corresponding to polyacetylene degradation.
Pyrolysis-MS was used for elucidating the fate of phenyl sulfenic acid
formed upon elimination. It was seen that the phenyl sulfenic acid, once
formed, irreversibly dehydrates to form the anhydride benzenesulfinothioic
acid, S-phenyl ester. This compound itself is not thermally stable and
disproportionates rather readily to give diphenyl disulfide and
benzenesulfonothioic acid, S-phenyl ester. There was a decided difference
in the pyrolysis-MS at low and high temperatures. At low temperatures MS
corresponding to the elimination of phenyl sulfenic acid and its further
reaction was seen. At higher temperatures, however, formation of various
aromatic hydrocarbons was seen typical of PA decomposition. XPS was
used to monitor the elimination reaction with temperature. At high
temperatures (>200°C) the characteristic S2p peak at 166 eV disappears
indicating complete elimination of phenyl sulfenic acid. Proton NMR was
also used to characterize the elimination process and shows formation of
cis and trans polyenes at high temperatures (>100°C). A change in IR

128
spectra with temperature was observed but gave no useful information
about the polyenes formed.

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BIOGRAPHICAL SKETCH
Rustom Sam Kanga was born in Bombay, India, with twelve fingers.
At the time of securing his doctorate he was left with eleven.
135

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
Dr. Thieo E. Hogen-Esch, Chairman
Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
Dr. George B. Butler
Professor Emeritus of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
Dr. Kenneth B. Wagener ^
Associate Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
V
Dr. Merle A. Battiste
Professor of Chemistry

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
Dr. Russell S. Drago
Graduate Research Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
Dr. Christopher D. Batich
Associate Professor of Materials Science
and Engineering
This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Liberal Arts and Sciences and to
the Graduate School and was accepted as partial fulfillment of the
requirements for the degree of Doctor of Philosophy.
December 1988
Dean, Graduate School

UNIVERSITY OF FLORIDA
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