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

insolubility of the PPS. The changes in PPS
Polyphenylene sulfide (PPS) is one of the during thermal curing may be caused both by
engineering plastics widely used in the microel- chemical reactions such as main chain scission or
ectronics field as shielding materials. PPS has cross-linking of the polymer, and by physical
good thermal stability, owing to the high bonding changes in the polymer structure such as
energy between its phenyl groups and sulfur crystallization or aggregation. We have investi-
atoms, and high crystallinity due to the strong gated the thermal and photo-degradation of
intermolecular interactions. 1 PPS has also good many aromatic polymers, 3-T and discussed their
stability against water, acid, and many other degradation behavior from point of view of the
chemicals as well as excellent mechanical solid state reactions and solid state structure of
properties due to the sulfur atoms which also polymers. 8 Recently, we have been developing
endow the polymer with flexibility. These sulfur an extensive study of fluorescence measurements
atoms, however, cause problems such as for monitoring the miscibility of polyimide-
so-called cross-linking and coloration when the polyimide blends, 9 phase transitions in poly(acryl
polymer is heated in the presence of oxygen. This amide) gels, 1 orientation of liquid crystalline
limits the use of the polymer. 2 The mechanism of polymers, 11 and the reactivity of a photosensitive
polyimide system, 12 and we have found that the
Polymer Degradation and Stability 0141-3910/93/$06.00 fluorescence technique is an effective tool for
1993 Elsevier Science Publishers Ltd. observing changes in polymer solid states because
279
280 Takashi Yamashita et al.

it is quite sensitive to the intermolecular follows. Poly(methylmethacrylate) (PMMA) and

interaction of the chromophores. In the present about 10-4M of the model compounds were
paper, we examine the characteristics of the dissolved in CH2C12, cast on quartz plates and
intermolecular and intramolecular fluorescence dried under vacuum.
of PPS, and describe the changes in the solid
state in the early stages of degradation. Annealing of the films

The apparatus for annealing was the same as that

EXPERIMENTAL reported previously. 6 Samples were placed on the
bottom of the tube which was sealed. In the case
Preparation of sample films of the reaction under nitrogen, the reaction tube
was evacuated and filled with nitrogen three
The chemical structures of PPS and the times. The tube was then warmed to the curing
corresponding model compounds used in these temperature which was maintained with a PID
experiments are shown in Fig. 1. The PPS type thermo-controller. In the case of the
powder, PPS cyclic oligomer with 10 monomer reaction in air, the same apparatus was used but
units, phenylenebisphenylsulfide trimer, and the reaction tube was heated without substitution
diphenylsulfide dimer were supplied by TOSO of the atmosphere.
Co. Ltd. They were used without further
purification. Measurement of fluorescence spectra
Films of PPS for curing in nitrogen were
prepared as follows. Small amounts of PPS Fluorescence spectra of the films were recorded
powder were melted between quartz plates on a with a Hitachi 850 type fluorescence spectro-
hot-plate and were then cooled rapidly in water photometer. The fluorescence anisotropy ratio, r,
to erase their thermal history. Samples for curing was determined from the following equation,
in air were prepared similarly, but only one
r = (lvv - GlvH)/(Ivv + 2GIvH)
quartz plate was used in order to expose the film
to the air. where, I is the fluorescence intensity, whose first
Films of the model compounds for fluorescence and second subscripts are the direction of the
anisotropy measurements were prepared as 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.

G-s-O RESULTS AND DISCUSSION

Dimer Model
Characteristics of absorption and fluorescence
spectra for the model compounds and their

Z>s- s-O intramolecular conjugated sites

Figure 2 shows the absorption and fluorescence

Trimer Model 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
PPS
molecular chain length; to 250 nm and 285 nm for
Cyclic Oligomer (M=IO00) the trimer model, and to 270 nm and 290 nm for
Fig. 1. Chemical structures of PPS and its model the oligomer model. This shift in the absorption
compounds. 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 400nm, which is not consistent with the
absorption spectra. So, this emission band
Figure 5 shows the absorption, excitation, and originates in another absorption species. This
emission spectra for PPS thin film cast between ground state absorption and emission site is
quartz plates. The thickness of this film is thought to be due to an intermolecular
estimated to be less than 1/~m, but an absorption aggregation of the PPS, because it is not
peak was not observed. An emission is observed observed for the other model systems whose
with a peak at 380 nm when the film is excited by concentration is so small that they have no
wavelengths below 380nm. This emission is intermolecular interaction. The intramolecular
thought to correspond to the emission from conjugated site and the ground state inter-
intramolecular emission sites which is observed molecular aggregate in PPS film are illustrated in
for the model systems. Another emission at a Fig. 6.
longer wavelength is observed when the excita-
tion wavelength is around 400 nm. This emission
maximum is observed at 480nm, and the

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

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. 8. The relative intensities of the fluorescence of PPS
Fig. 7. Change in the relative fluorescence intensity of PPS after saturation during annealing. Fluorescence at 380 nm
during annealing. Fluorescence at (a) 380nm and (b), for the samples annealed in air (A) and in nitrogen (A).
480 nm annealed at 85C (O), 110C (A), 150C (E]) under Fluorescence at 480 nm for the samples annealed in air (O)
nitrogen, and 110C (A), 150oc (11), 250C(.) under air. and in nitrogen (Q).
 284 Takashi Yamashita et al.

electronic transitions. One is from the in-

0.20 tramolecular conjugated sites constructed by the
resonance of several phenylene rings, and the
other is from the ground state intermolecular
o aggregates of PPS. This conclusion is consistent
L.. 0.10
with the shifts of the wavelength maxima in the
absorption, excitation and emission spectra of the
model compounds to the longer wavelength with
0.0(
- - m w increase in the molecular chain length. The
intensities of the intramolecular fluorescence and
the intermolecular fluorescence of PPS are found
-0.10 I
0 50 100 to increase during annealing, reflecting the
conformational rearrangement and increase in
A n n e a l i n g T i m e (rain)
molecular aggregation. The increase in the
Fig. 9. Change in the fluorescence anisotropy ratio, r, of fluorescence intensity for the PPS sample
PPS during annealing at 110C. Fluorescence at 380 nm (&) annealed under nitrogen is rapid in the early
and at 480 nm (0).
stages, but it soon becomes saturated. On the
nitrogen. That is explained by the fact that the other hand, the intensity of the fluorescence for
glass transition temperature (Tg) of PPS is 85C, the sample annealed in air gradually increases,
and molecular motion of main chains is difficult supposedly due to the gradual progress of
below this temperature. Above Tg, the fluores- chemical change in PPS as well as physical
cence intensities increase rapidly, but they changes in the solid state polymer. The
decrease again above 150C. Finally the intensity fluorescence technique can be a powerful tool for
of the intramolecular fluorescence decreases to measuring these phenomena, which are supposed
unity for the sample annealed in air. The to be the origin of the coloration and turbidity of
decrease in the fluorescence intensities is due to PPS.
molecular relaxation, since the melting point of
PPS is 285C. The difference between the
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