Polymer Degradation and Stability 39 (1993) 279-284

Degradation of sulfur-containing aromatic

polymers (II): Change in fluorescence spectra
of polyphenylenesuifide (PPS) during
annealing
Takashi Yamashita," Takafumi Kudo, b Kazuyuki Horie, b Shingo Maeda, ~
& Kimitoshi Nagat#
a Research Center for Advanced Science and Technology, The University of Tokyo, Komaba 4-6-1, Meguro-ku,
Tokyo 153, Japan
b Department of Reaction Chemistry, Faculty of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku,
Tokyo 113, Japan
c Polymer Research Center, Toso Co., Kasumi 1-8, Yokkaichi-shi, Mie 510, Japan

(Received 7 February 1992; accepted 24 February 1992)

The fluorescence of PPS film and model compounds were measured, and
changes were observed during thermal curing. Fluorescences from both
intramolecular conjugated sites and from ground state intermolecular aggreg-
ates were observed. The intensities of these fluorescences increase during
annealing due to conformational rearrangement and increase in molecular
packing. The formation of intermolecular aggregates could be one reason for
coloration of PPS film during thermal treatment. The rates of increase of the
fluorescence intensity are different between samples annealed in air and in
nitrogen. The effect of the atmosphere is believed to result from the change in
the extent of chemical degradation of the PPS during thermal treatment as
well as physical change of the polymer solid state.

INTRODUCTION degradation is not clear at present because of the

Polyphenylene sulfide (PPS) is one of the
engineering plastics widely used in the microel-
ectronics field as shielding materials. PPS has
good thermal stability, owing to the high bonding
energy between its phenyl groups and sulfur
atoms, and high crystallinity due to the strong
intermolecular interactions. 1 PPS has also good
stability against water, acid, and many other
chemicals as well as excellent mechanical
properties due to the sulfur atoms which also
endow the polymer with flexibility. These sulfur
atoms, however, cause problems such as
so-called cross-linking and coloration when the
polymer is heated in the presence of oxygen. This
limits the use of the polymer. 2 The mechanism of
Polymer Degradation and Stability 0141-3910/93/$06.00
1993 Elsevier Science Publishers Ltd.
279
insolubility of the PPS. The changes in PPS
during thermal curing may be caused both by
chemical reactions such as main chain scission or
cross-linking of the polymer, and by physical
changes in the polymer structure such as
crystallization or aggregation. We have investi-
gated the thermal and photo-degradation of
many aromatic polymers, 3-T and discussed their
degradation behavior from point of view of the
solid state reactions and solid state structure of
polymers. 8 Recently, we have been developing
an extensive study of fluorescence measurements
for monitoring the miscibility of polyimide-
polyimide blends, 9 phase transitions in poly(acryl
amide) gels, 1 orientation of liquid crystalline
polymers, 11 and the reactivity of a photosensitive
polyimide system, 12 and we have found that the
fluorescence technique is an effective tool for
observing changes in polymer solid states because
280 Takashi Yamashita et al.
it is quite sensitive to the intermolecular
interaction of the chromophores. In the present
paper, we examine the characteristics of the
intermolecular and intramolecular fluorescence
of PPS, and describe the changes in the solid
state in the early stages of degradation.
EXPERIMENTAL
Preparation of sample films
The chemical structures of PPS and the
corresponding model compounds used in these
experiments are shown in Fig. 1. The PPS
powder, PPS cyclic oligomer with 10 monomer
units, phenylenebisphenylsulfide trimer, and
diphenylsulfide dimer were supplied by TOSO
Co. Ltd. They were used without further
purification.
Films of PPS for curing in nitrogen were
prepared as follows. Small amounts of PPS
powder were melted between quartz plates on a
hot-plate and were then cooled rapidly in water
to erase their thermal history. Samples for curing
in air were prepared similarly, but only one
quartz plate was used in order to expose the film
to the air.
Films of the model compounds for fluorescence
anisotropy measurements were prepared as
G-s-O
Dimer Model
Z>s- s-O
Trimer Model
PPS
Cyclic Oligomer (M=IO00)
Fig. 1. Chemical structures of PPS and its model
compounds.
follows. Poly(methylmethacrylate) (PMMA) and
about 10-4M of the model compounds were
dissolved in CH2C12, cast on quartz plates and
dried under vacuum.
Annealing of the films
The apparatus for annealing was the same as that
reported previously. 6 Samples were placed on the
bottom of the tube which was sealed. In the case
of the reaction under nitrogen, the reaction tube
was evacuated and filled with nitrogen three
times. The tube was then warmed to the curing
temperature which was maintained with a PID
type thermo-controller. In the case of the
reaction in air, the same apparatus was used but
the reaction tube was heated without substitution
of the atmosphere.
Measurement of fluorescence spectra
Fluorescence spectra of the films were recorded
with a Hitachi 850 type fluorescence spectro-
photometer. The fluorescence anisotropy ratio, r,
was determined from the following equation,
r = (lvv - GlvH)/(Ivv + 2GIvH)
where, I is the fluorescence intensity, whose first
and second subscripts are the direction of the
polarizers for incident and emitting lights,
respectively, with V and H standing for the
vertical and horizontal directions, respectively. G
is a constant for the instrument.
RESULTS AND DISCUSSION
Characteristics of absorption and fluorescence
spectra for the model compounds and their
intramolecular conjugated sites
Figure 2 shows the absorption and fluorescence
spectra of benzene, the dimer model, the trimer
model, and the cyclic oligomer model in CH2C12
solution. The absorption band around 260 nm for
benzene is of the forbidden :t-:r* transition. ~3
Two absorption maxima are observed for the
dimer model at 250nm and 275nm, and they
shift to a longer wavelength with an increase in
molecular chain length; to 250 nm and 285 nm for
the trimer model, and to 270 nm and 290 nm for
the oligomer model. This shift in the absorption
spectrum shows that the absorption is due to
 Degradation of sulphur-containing aromatic polymers (H) 281

400 &

A
; ,,i i
, ! \,
iJ ~ %. P. 300
ii I 1% i ~,.
,I .O__~_ O
e- I
o -'I- -I'-
e-
e- g
' I" \
I I t I" x"x
JO
lu. i I I I I
@ 0 200
, ~ ! .~ - . u} 3 5 7 9 11
o
c
t
,, ~ a
I
~
/
l"
'
\
"~
'" J~
m <~ N u m b e r of P h e n y l e n e Ring
o
m Fig. 3. Wavelength of the absorption ( I ) , excitation (O),
P
0 and emission (/x) maxima of the model compounds in
i
CH2C12 solution.
it
ii ~ i.I "%
I t 1" ~'.
the transition momentum between the absorption
I \ I" S "%
t I" "% and the emission because the molecular motion
in the excited state of the models is forbidden in
I
such a solid matrix, and because no energy
'200 300 400 500
migration is thought to occur due to the dilution
Wavelength (nm) of the models. These results are summarized in
Table 1. The maximum in the emission intensity
Fig. 2. The absorption ( ), excitation ( . . . . . . ), and
emission ( . . . . . . . . ) spectra for benzene, the dimer model,
for the PPS oligomer model in CH2C12 solution is
the trimer model, and the cyclic oligomer model in CH2CI2 observed to be 400 nm and is larger than the
solution. emission maximum for the sample in solid
PMMA (370 nm), showing that there are longer
transitions between energy levels which involve intramolecular resonance absorption and emis-
several phenylene rings and are stabilized by the sion sites in the solution system possibly due to
resonance effect. This is quite similar to the case easier conformation changes than in the solid
of polysilanes, TM which also form intramolecular state. For bulk PPS film r is thought to be
absorption sites by o-conjugation of Si--Si bonds affected not only by the formation of the longer
along the main chain. 15 The wavelength maxima conjugated sites but also by the effect of
of the excitation spectra of PPS correspond to intermolecular interaction of the absorption and
those of the absorption spectra, showing that the emission sites, as described below.
emissions occur from the same excited states for
absorption sites. The wavelengths of the
absorption, excitation and emission maxima for 0.2
these models are shown in Fig. 3. Shifts in the A,
emission spectra are much larger than those for 370
absorption of excitation spectra, showing that the 0.1
energy surfaces in the excited states are much
affected by the elongation of the resonance. "~ 320
In order to estimate the change in the 0.0
transition momentum during photo-excitation of
the models, solid state samples containing less
than 10-4M of the models in PMMA matrices 270 -0.1
3 5 7 9 11 PPS
were prepared and the fluorescence anisotropy Number of Phenylene Ring
ratios, r, for these samples were measured (Fig.
4). A decrease in r is observed with increase in Fig. 4. Fluorescence anisotropy ratio, r, of PPS and the
model compounds (O), and the related absorption ( I ) ,
the molecular chain length for the models, and r excitation (O), and emission (/x) maxima for these samples
is thought to be affected only by the change in in PMMA matrices.
 282 Takashi Yamashita et al.

Table 1. Absorption and emission peaks of the model compounds and PPS films as we]] as their fluorescence
anisotropy ratios, r

Sample CH2C12 solution PMMA solid

Absorption Excitation Emission Absorption Excitation Emission

(nm) (nm) (nm) (nm) (nm) (nm)

Dimer 250 260 315 . . . .

275 285 330 285 290 355 0.143

"Filmer 250 265 . . . . .
285 295 360 290 295 360 0-132
Oligomer 270 270a . . . . .

290a 300 400 300a 300 370 0"056

PPS Filmb . . . . c (300)b 380 b _0.015 b
. . . . 400 b 480 b __d

a shoulder
b measured for bulk solid film
c shorter than 360 nm
d see Fig. 9

Fluorescence of PPS film and the corresponding excitation maximum is observed at

intramolecular and intermolecular emission sites
Figure 5 shows the absorption, excitation, and
emission spectra for PPS thin film cast between
quartz plates. The thickness of this film is
estimated to be less than 1/~m, but an absorption
peak was not observed. An emission is observed
with a peak at 380 nm when the film is excited by
wavelengths below 380nm. This emission is
thought to correspond to the emission from
intramolecular emission sites which is observed
for the model systems. Another emission at a
longer wavelength is observed when the excita-
tion wavelength is around 400 nm. This emission
maximum is observed at 480nm, and the
400nm, which is not consistent with the
absorption spectra. So, this emission band
originates in another absorption species. This
ground state absorption and emission site is
thought to be due to an intermolecular
aggregation of the PPS, because it is not
observed for the other model systems whose
concentration is so small that they have no
intermolecular interaction. The intramolecular
conjugated site and the ground state inter-
molecular aggregate in PPS film are illustrated in
Fig. 6.

A " ~ ,hv3
. ~ :, ~ 1 "
5
Excitation Emission Excitation Emission
\ , SS /
(Em=3e0) (Ex=300) (Era=480) (Ex=400)
s m

1/I \r "1 / ....... ......

C t lf x. /
t-
in
,,,,,/
C
O
ii

im

E Absorption -~; .............

Iii I .... r ....
30O 4OO 50O h v 1'
Wavelength (nm) Fig. 6. Illustration of emissions from a monomer unit (hvl),
Fig. 5. Absorption (. . . . . . ) and fluorescence ( - - - for an intramolecular conjugated site (hvz), and a ground state
excitation, a n d - for emission) spectra for PPS film. intermolecular aggregate (hv3) of PPS.
 Degradation of sulphur-containing aromatic polymers (H) 283

Fluorescence of PPS film and the intermolecular
emission site
The PPS sample films were annealed in both air
and nitrogen, and the changes in the intensity of
the intramolecular and intermolecular fluores-
cences at 380 nm and 480 nm were measured with
the excitation wavelength at 300 nm and 400 nm,
respectively. Figure 7(a) shows the relative
intensities of the fluorescence of PPS film at
380nm during annealing, normalized by the
initial fluorescence intensities. The open points
represent the samples annealed in nitrogen. The
intensities for the samples under nitrogen
increase rapidly in the early stage of annealing at
ll0C and 150C, and become saturated after
20 min. The intensities of the samples annealed
in air, the solid plots, increase gradually at
~' 3t 380nm
=.
"~ 1' o affected by the increase in the ground state
n-
O I I I
0 20 40
AnnealingTime (min)
>,3 480nmu
. .-
.. ~.a...
,F...r
m
ll0C, 150C, and 200C, and they become not
less than those for the corresponding open plots
after 60 rain. These increases in the fluorescence
intensities at 380 nm show that the number of
intramolecular emission sites of longer conjuga-
tion increases during annealing due to the
relaxation of the conformation of the molecular
chain in PPS. The effect of air is not clear at
present, but quenching of the fluorescence is not
considered to be included because the final
fluorescence intensities of the samples annealed
in air are not smaller than those in nitrogen. The
change in intramolecular fluorescence of PPS
annealed in air may be affected by the chemical
changes in the samples such as chain scission,
molecular rearrangement, or oxidation of PPS, as
well as the physical change observed for the
samples in nitrogen. Figure 7(b) shows the
change in the fluorescence intensities at 480 nm,
and the behaviour is similar to the changes in the
fluorescence at 380nm. This change in the
fluorescence at 480 nm shows that the number of
the ground state intermolecular aggregate sites
also increases during the thermal treatment due
to the increase in the molecular packing density
or crystallization. Coloration and turbidity of
PPS during thermal treatment is believed to be
intermolecular aggregate and the degree of
crystallization of the polymer.
I
The fluorescence intensities after saturation at
60 80 various temperatures are shown in Fig. 8. The
intensities of the fluorescence at both 380 nm and
480 nm do not change so much below 85C in
3
1
'-u- e-
2
,, e-

I ~'~.~
m I: 0 u 0 0 el)
tr
rr

I I I I 0 I I I

0 20 40 60 80 0 100 200 300 400

AnnealingTime (min) Annealing Temperature(C)

Fig. 7. Change in the relative fluorescence intensity of PPS
during annealing. Fluorescence at (a) 380nm and (b),
480 nm annealed at 85C (O), 110C (A), 150C (E]) under
nitrogen, and 110C (A), 150oc (11), 250C(.) under air.
Fig. 8. The relative intensities of the fluorescence of PPS
after saturation during annealing. Fluorescence at 380 nm
for the samples annealed in air (A) and in nitrogen (A).
Fluorescence at 480 nm for the samples annealed in air (O)
and in nitrogen (Q).
 284
0.20
o aggregates of PPS. This conclusion is consistent
L.. 0.10
0.0(
- - m w
-0.10 I
0 50
A n n e a l i n g T i m e (rain)
Fig. 9. Change in the fluorescence anisotropy ratio, r, of
PPS during annealing at 110C. Fluorescence at 380 nm (&)
and at 480 nm (0).
nitrogen. That is explained by the fact that the
glass transition temperature (Tg) of PPS is 85C,
and molecular motion of main chains is difficult
below this temperature. Above Tg, the fluores-
cence intensities increase rapidly, but they
decrease again above 150C. Finally the intensity
of the intramolecular fluorescence decreases to
unity for the sample annealed in air. The
decrease in the fluorescence intensities is due to
molecular relaxation, since the melting point of
PPS is 285C. The difference between the
intramolecular and intermolecular fluorescence
intensities at 300C may be affected by chemical
changes.
Figure 9 shows the changes in the fluorescence
anisotropy ratios for a PPS film annealed at
110C under nitrogen. For the fluorescence, r at
380 nm is just below zero at the beginning and
remains so until 90 min of thermal treatment.
This is caused by the change in transition
momentum between absorption and emission due
to the conjugation over several phenylene rings,
as already discussed above for Fig. 4. For the
fluorescence, r at 480nm is 0-22 before the
thermal treatment, but decreases to near zero in
the early stages of annealing. The rapid decrease
in r at 480 nm is believed to be due to the rapid
increase in energy migration from one to other
intermolecular aggregation sites which increase in
the early stage of annealing, as described in the
change in the fluorescence intensities.
CONCLUSION
Fluorescence measurements of PPS film and its
model compounds show that absorption and
emission of PPS consists of two kinds of
Takashi Yamashita et al.
electronic transitions. One is from the in-
tramolecular conjugated sites constructed by the
resonance of several phenylene rings, and the
other is from the ground state intermolecular
with the shifts of the wavelength maxima in the
absorption, excitation and emission spectra of the
model compounds to the longer wavelength with
increase in the molecular chain length. The
intensities of the intramolecular fluorescence and
the intermolecular fluorescence of PPS are found
100 to increase during annealing, reflecting the
conformational rearrangement and increase in
molecular aggregation. The increase in the
fluorescence intensity for the PPS sample
annealed under nitrogen is rapid in the early
stages, but it soon becomes saturated. On the
other hand, the intensity of the fluorescence for
the sample annealed in air gradually increases,
supposedly due to the gradual progress of
chemical change in PPS as well as physical
changes in the solid state polymer. The
fluorescence technique can be a powerful tool for
measuring these phenomena, which are supposed
to be the origin of the coloration and turbidity of
PPS.
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