Polymer Degradation and Stability 39 (1993) 355-366

FT-IR analysis of the photooxidation of

styrene-acrylonitrile copolymers
M. Sargent, J. L. Koenig
Case Western Reserve University, Department of Macromolecular Science, Cleveland, Ohio 44106, USA

&

N. L. Maecker
The Dow Chemical Company, Designed Thermoplastics Research, Midland, Michigan 48667, USA

(Received 17 June 1991; accepted 1 March 1992)

Infrared spectroscopy was used to study the photooxidation of the styrene-

acrylonitrile (SAN) copolymer samples that were exposed to ultraviolet
radiation having a minimum wavelength of 290 nm. It was determined that the
photooxidation of SAN occurs exclusively at the styrene repeat units within
the copolymer structure. The major infrared spectral changes resulting from
the degradation process involve the appearance of new peaks within the
hydroxyl and carbonyl regions. Using factor analysis results, it was concluded
that there are a minimum of four different types of hydroxyl groups and three
different types of carbonyl groups formed during the photooxidation of SAN.
Furthermore, it was found that after 200 h exposure the rate of increase in the
concentration of the carbonyl groups within the degraded material is greater
than the rate of increase in the concentration of the hydroxyl groups.

INTRODUCTION within the material during photooxidation.

Styrene-acrylonitrile copolymers (SAN) are
recognized for their high optical clarity, rigidity
and resistance to heat and chemicals. 1 SAN is
commonly used by the automotive industry in
applications such as tail light lenses, dash
components and interior trim. Other products
made from SAN include blenders, mixers and
other household appliances, as well as packaging
materials such as bottles and vials.
When SAN is exposed to solar radiation in the
presence of oxygen, the copolymer turns yellow
in color and experiences a decrease in its surface
quality due to crazing. Furthermore, the
mechanical properties deteriorate as measured by
a decrease in the toughness, ultimate tensile
strength and impact strength. 2-5 However, desp-
ite the commercial importance of SAN very little
is known about the chemical reactions occurring
355
It is the purpose of this experiment to study
the photooxidation of SAN and gain new insight
into the chemical reactions occurring within the
copolymer during the degradation process. This
will be accomplished by using infrared spectro-
scopy to follow the extent of the photooxidation
reactions as a function of exposure time.
Experimental
The styrene-acrylonitrile random copolymers
were obtained from the Dow Chemical Com-
pany. They had a copolymer composition of
74wt% styrene and 26wt% acrylonitrile, as
determined by precipitation fractionation imple-
mented on liquid chromatography equipment6
and a weight average molecular weight (Mw) of
160 950. The SAN copolymer was obtained in the
pellet form and then pressed into thin films on a
heated Carver press.
356 M. Sargent, J. L. Koenig, N. L. Maecker
The thin (0.08 + 0.01 mm) film samples were
exposed in an Atlas Ci65 Weather-Ometer for
periods of 200 h, 400 h, 600 h, 800 h, 1000 h and
1500 h. The Weather-Ometer was equipped with
a xenon arc source and was designed for
controlled irradiance. To simulate the emission
profile of natural daylight in the full ultraviolet
region as well as its short wavelength limit,
borosilicate inner and outer filters were used to
achieve a short wavelength limit of 290 nm. The
xenon arc source operated at 0 . 3 5 W / m 2 at
340 nm and the black panel temperature of the
Weather-Ometer was 63C. A repetitive 2 h
humidity cycle was used which consisted of
108 min of light followed by 12 min of light plus a
water spray of deionized water. While the water
spray was not in operation the wet bulb
depression was 10C.
A second series of samples was also analyzed
that had been exposed at a Florida outdoor
testing facility. Thin film samples were exposed
at an angle of 45 facing south for periods of 3
weeks, 5 weeks and 6 weeks, beginning in
November 1988.
Transmission spectra were collected at room
temperature on a Digilab F r s - 6 0 F T - I R
Spectrometer. The spectrometer was purged with
dry air and used an MCT detector cooled with
liquid nitrogen. One thousand scans of each
sample were collected at a resolution of 4 cm -1.
All spectra were transferred to a Microvax II for
subsequent data processing.
RESULTS A N D DISCUSSION
A series of thin film SAN copolymer samples
with a copolymer composition of 74 wt% styrene
and 26wt% acrylonitrile was exposed in the
Weather-Ometer for periods of 200h, 400h,
600 h, 800 h, 1000 h and 1500 h. It was deter-
mined that reproducible transmission spectra
could be obtained from these thin film samples of
SAN. To correct for variations in thickness
between samples, the spectra were scaled
according to the area under the aromatic band at
1952cm -1. The signal-to-noise ratio of the
spectra is approximately 400:1, which provides
excellent conditions for detecting very small
changes in the spectra resulting from the
photooxidation process. Attempts were made to
increase the time of exposure beyond 1500 h.
However, it was found that the films exposed for
periods beyond this time limit were too brittle to
handle and reproducible spectra of such samples
were not able to be obtained.
Before the samples exposed to ultraviolet
radiation are analyzed to determine the chemical
reactions occurring within SAN during photo-
oxidation, it is necessary to establish that no
thermal oxidation has occurred within the
copolymer prior to irradiation. Thermal oxida-
tion could have occurred within the material
either during polymerization or while the thin
film samples were being made with the heated
press.
It has been established by Gueskens & Bastin 3
that when thermal oxidation of SAN occurs,
acetophenone end groups and hydroperoxide
groups are formed. The presence of these groups
can be identified by the appearance of infrared
spectral peaks at 1685cm -1 and 3340cm -1,
respectively. The SAN will also turn yellow from
the formation of conjugated structures formed by
the cyclization of the acrylonitrile units. This
cyclization results in the disappearance of nitrile
groups and the formation of ~ N groups. The
presence of these ~ N groups can be identified
by the appearance of an infrared band in the
region of 1690-1480 c m - 1 . 7
Within the instrumental limits of detection,
infrared analysis of the SAN samples used in this
experiment reveals no presence of any acetophe-
none end groups, hydroperoxide groups or ~ N
groups before exposure to ultraviolet radiation.
It can therefore be concluded that any chemical
changes detected in the samples exposed in the
Weather-Ometer result from photooxidation
occurring within the SAN copolymer.
Shown in Fig. 1 are the spectra of both an
unexposed SAN sample and a sample of SAN
exposed for 1500 h. It can clearly be seen that the
major spectral changes resulting from the
photooxidation occur in the hydroxyl region
between 3700cm -1 and 3200cm -1 and the
carbonyl region between 1800 cm -1 and
1650 cm-L
Examining first the hydroxyl region, Fig. 2
shows this spectral region for all six samples
exposed from periods of 200-1500 h along with
the spectrum of the unexposed sample. From
these spectra the increase in peak intensity with
exposure time is evident. The spectral changes
occurring within this region were then isolated by
obtaining the difference spectrum at each
exposure time. This involved the subtraction of
 FT-IR analysis of photooxidation of styrene-acrylonitrile 357

changes result from a combination of several

EXPOSURE il~ . (~ ~
overlapping peaks appearing within this region.
This implies that rather than only one type of
hydroxyl group forming as a product of the
chemical reactions occurring during the degrada-
tion process, several different types of hydroxyl
groups are actually being formed.
Factor analysis was performed on the
difference spectra to determine the number of
components that could be spectroscopically
determined within the hydroxyl region. As seen
in Table 1, the indicator function attains its
0 HR. minimum value when the number of components
is equal to four. This means that there are a
4000 3290 2580 1870 1160 449
minimum number of four chemically different
Wavenumber (m-1)
types of hydroxyl groups being formed during the
Fig. 1. The infrared spectra of an unexposed SAN sample photooxidation of SAN. The term minimum is
and a sample of SAN exposed for 1500h in the stressed because factor analysis is a mathematical
Weather-Ometer (AA = 1-78).
procedure which can determine the number of
spectroscopically identifiable, linearly independ-
the spectrum of the unexposed SAN from the ent components in a series of spectra. Therefore,
spectrum of the degraded sample. if two or more different types of hydroxyl groups
The difference spectra of all exposed samples are being formed at the same rate, factor analysis
are shown in Fig. 3. It is evident from these will only be able to detect the presence of one
difference spectra that the changes occurring in type of hydroxyl group.
the hydroxyl region do not result from the In Fig. 4 is shown the carbonyl region for the
formation of one new peak. Rather, the spectral unexposed SAN sample along with all six

TRANSMISSION SPECTRA

iO0 h r .

370
~ ~ ~ 0 hr.
3100 cm - 1

Fig. 2. A three-dimensional plot of the hydroxyl region of the infrared spectra for the SAN samples exposed from 0 h to 1500 h
(AA = 0.47).
358 M. Sargent, J. L. Koenig, N. L. Maecker

DIFFERENCES P E C T R ~

EXPOSURETIME j
(HOURS~

,oo J / J
i000 _~
800 J ~
600
400
200

I I I I I I
3800 3700 3600 3500 3400 3300 3200 3100
Wavenumber(cm"1)

Fig. 3. The hydroxyl region of the difference spectra for the six SAN samples exposed from 200 h to 1500 h (AA = 0-47).

samples exposed from 200 h to 1500 h. Again it Factor analysis was performed on the
can be seen that the new peaks forming in this difference spectra in the carbonyl region. As
spectral region increase in intensity as the illustrated in Table 2, the indicator function
exposure time is increased. The difference attains its minimum value when the number of
spectra of these samples were obtained to isolate components is equal to three. Therefore, there
the degradation peaks forming within this area. are a minimum of three different types of
This subtraction procedure eliminates the com- carbonyl groups being formed during the
bination and overtone bands from the phenyl photooxidation of SAN.
ring on the styrene repeat unit. Two other new spectral peaks are formed
The difference spectra for the carbonyl region during the degradation process. These weakly
are shown in Fig. 5. As was found with the new absorbing peaks appear at 1515cm -1 and
spectral peaks formed in the hydroxyl region, the 1266cm -1 and the difference spectra revealing
difference spectra in Fig. 5 reveal that the their presence are shown in Figs 6 and 7,
changes occurring within the carbonyl region respectively. The maximum absorbance for the
result from a combination of several overlapping peak at 1515 cm -1 in the SAN sample exposed
peaks. There is therefore more than one type of for 1500h is only 0.05. Correspondingly, the
carbonyl group being formed during the de- maximum absorbance of the peak at 1266 cm -~ in
gradation process. the spectrum of the same sample is 0-03.
Although both of these peaks are very weak, it is
clearly evident that their intensities increase with
Table 1. Factor analysis results the time of exposure in the Weather-Ometer.
from the hydroxyl region of the This indicates that these peaks can most likely be
difference spectra of the SAN
copolymers assigned to products formed from chemical
reactions occurring during the photooxidation of
Number of Indicator SAN. However, other possible sources of origin
components function
(n) ( 10-5) of the substances responsible for these peaks are
minerals, salts, etc. dissolved in the water used
1 13-14 during the humidity cycle in the Weather-
2 4.91
3 3.85 Ometer. If chemical substances are being
4 3.35 deposited on the SAN films during the water
5 5.90 spray cycle, the concentrations of these deposits
6 17-46
will increase with exposure time.
 FT-IR analysis of photooxidation of styrene-acrylonitrile 359

TRANSMISSION SPECTRA

O0 h r .

..~.~_~~~,~/

2050 cm - 1

~ 0 hr.

Fig. 4. A three-dimensional plot of the carbonyl region of the infrared spectra for the SAN samples exposed from 0 h to 1500 h
(AA = 0.70).

To d e t e r m i n e w h e t h e r the peaks at 1515 cm -~ Table 2. Factor analysis results

from the carbonyl region of the
and 1266cm - ' are in fact due to chemical difference spectra of the SAN
reactions occurring during the degradation copulymers
process or instead are due to products deposited
Number of Indicator
on the S A N films, several different experiments components function
were performed. T h e first test involved placing (n) ( 10-5)
A T R crystals in the W e a t h e r - O m e t e r . A f t e r
1 44.93
being exposed to environmental conditions 2 9.44
3 4.99
4 6.08
5 11.83
DIFFERENCSE P ~ 6 46.63

identical to those experienced by the S A N

samples, these crystals were analyzed by infrared
-':::::'"' / /p,,\ ,,._ spectroscopy to d e t e r m i n e if any type of deposit
had collected on their surfaces. Because no
detectable deposits could be found on these
crystals, it seems probable that the peaks at
200 ~ 1515 c m - ' and 1266 cm -~ do not result from any
deposits left on the S A N film surface during the
water spray cycle. H o w e v e r , to confirm these
1900
I
18~0 1800 1750
I I I
1700
I
16S0 la0O
results S A N samples were exposed in the
(cm-1)
wavenumber W e a t h e r - O m e t e r without the use of a water
Fig. 5. The carbonyl region of the difference spectra for the spray cycle. Analysis of these films revealed the
six SAN samples exposed from 200 h to 1500 h (AA = 0.70). presence of both peaks in the resulting infrared
360 M. Sargent, J. L. Koenig, N. L. Maecker

new peak around 1510cm -1 in the spectra of

DIFFERENCE
SPECTRA/~ degraded samples of all three products. Sufficient
data is not available to make a definite
EXPOSURE
TIME / assignment of this band. However, because the
intensity of this peak in the spectrum of the
degraded SAN is much less than the intensities of
the new peaks appearing in the carbonyl and
hydroxyl regions, it can be concluded that this
peak most likely results from a side reaction
occurring within the SAN copolymer. This
6DO ~ reaction may involve the degradation of im-
purities present in very low concentrations within
,oo
the copolymer.
200 In any degradation experiment in which an
1530 1525
i

Wavenumber
1520
(cm-1)
i
1515
i
1510
I
1505 1500 artificial method of exposure is used to simulate
the conditions under which a sample is exposed
Fig. 6. The appearance of a new peak at 1515cm-' is in its natural environment, it is necessary to
revealed in the difference spectra of the SAN samples confirm that the changes occurring within the
exposed from 200 h to 1500 h ( A A = 0-05).
material under artificial weathering conditions
duplicate those occurring under natural weather-
ing conditions. Because of this need to verify the
spectra. To further confirm that the origins of experimental results of the SAN samples exposed
these peaks are products formed from chemical in the Weather-Ometer, a series of samples was
reactions occurring within the material during exposed in an outdoor testing facility.
photooxidation, these peaks were also isolated in The carbonyl region of the samples subjected
the spectra of samples exposed in an outdoor to outdoor weathering conditions is shown in Fig.
testing facility and discussed below. 8 for samples exposed for periods of 3 weeks, 5
Although no previous studies have reported weeks and 6 weeks. As compared to those
the observation of a peak near 1266cm -~ in samples which were exposed in the Weather-
infrared photooxidation studies of SAN or Ometer, the changes occurring in the carbonyl
similar materials, a peak has been reported near region of these spectra appear to be negligible.
1515cm-L In a study of the photooxidation of However, from the difference spectra shown in
ABS, ASA and SAN, Priebe e t al. 5 reported a Fig. 9 it can be seen that the spectral changes in
the carbonyl region are very similar to those
occurring in the spectra of the artificially exposed
samples shown in Fig. 5. Similarly, from the
DIFFERENCE
$PEC~ difference spectra shown in Fig. 10 it is evident
that the changes occurring in the hydroxyl region
of the spectra of the samples exposed outdoors
are very similar to those occurring in the samples
exposed in the Weather-Ometer. As previously
mentioned, weakly absorbing peaks at 1515 cm -1
and 1266cm -1 were also detected in these
samples exposed in the outdoor testing facility. It
can therefore be concluded that the degradation
1oo0 j ~ reactions occurring within the artificially weath-
ered SAN samples accurately reflect the de-
~00 _ ~ . . .
gradation occurring within SAN that has been
I I I i I I exposed to natural weathering conditions.
1290 12%5 1280 1275
1~averlumber
1270
(cm-1) 1265 1260 1255
The areas under the peaks appearing in the
Fig. 7. The appearance of a new peak at 1266cm -~ is
difference spectra shown in Figs 3 and 5 were
revealed in the difference spectra of the SAN samples determined and plotted in Fig. 11 as a function of
exposed from 200 h to 1500 h ( A A = 0-03). exposure time. Although it has been established
 FT-IR analysis of photooxidation of styrene-acrylonitrile 361

SAMPLES EXPOSEDTO OUTDOORWEATHERING CONDITIONS

EX,OSURE

5 WEEKS

3W E E K S ~

I I t I
2100 2000 1900 1800 1700 1600
Wavenumber (cm -1)
F i g . $ . T h e carbonylregion ofthein~ared spectra forthe SAN samples exposed to naturaisunlight(AA = 0.26).

that there are several different types of hydroxyl
and carbonyl groups formed during the photo-
oxidation of SAN, the peaks occurring in these
regions were integrated to give a combined value
for all hydroxyl groups being formed and another
value for all carbonyl groups being formed. In
other words, values for the total concentration of
all types of hydroxyl groups, as well as the total
concentration of all types of carbonyl groups,
were determined.
To correct for the fact that the extinction
coefficients are different for each of the four

SAMPLES EXPOSED TO OUTDOOR WEATHERING C0N01TIONS

DIFFERENCE SPECTRA/\

EXPOSURETIME

6 WKS

5 WK5

1800 17'77 1"/54 17'31 J,7'09 1686

Wavenumber (cm-I)
Fig. 9. The carbonyl region of the difference spectra for the SAN samples exposed to natural sunlight (AA = 0-06).
362 M. Sargent, J. L. Koenig, N. L. Maecker

SAMPLES EXPOSED TO OUTDOOR WEATHERING CONDITIONS

EXPOSURE /' ~

3599 3563 3527 34'92 34'56 3420

Wavenumber (c= - 1 )
Fig. 10. The hydroxyl region of the difference spectra for the SAN samples exposed to natural sunlight (AA = 0-04).

60.
[]
Spectral Reqton
7oo - 3200 c.-."
~0.
X 1800 - 1650 cm_l-~
A 1520 - 1505 c=_l
1"-1 1280 - 1255 cm
40. --

P
e
8
k
30.-
A
I"
e
8
20. 0 A

10. []
0

0.~ I I I I I I I
0 200 400 600 800 I000 1200 1400 1600
Exposure Ttme ( h o u r s )
Fig. ][1. A plot of the peak area versus exposure time for the four spectral regions in which new peaks formed during the
photooxidation of SAN.
 FT-IR analysis of photooxidation of styrene-acrylonitrile
spectral regions of interest, all peak areas were
normalized according to the values obtained for
the SAN sample exposed for 200 h. This meant
that in order to make comparisons between the
concentration changes of the various species
occurring as the photooxidation process ad-
vanced, the assumption has to be made that at
200 h exposure the concentrations of all degrada-
tion products are equal. Because this assumption
is made, comparisons in the changes occurring
over time can only be made relative to the
concentrations of these products that exist within
the SAN sample exposed for 200 h. Furthermore,
this data should not be used to compare the
absolute values of the concentrations of the
various species present in the photooxidized SAN
but rather should be used to compare the rates of
change in the concentrations of these degradation
products.
From the data shown in Fig. 11, it can be seen
that after 200 h exposure the rate of increase in
the concentration of the carbonyl group within
the degraded material is greater than the rate of
increase in the concentration of the hydroxyl
groups. Comparing the data from the peaks at
1515cm -~ and 1266cm-', their peak areas
remain essentially equal to one another through
1000h exposure and are below those values
determined for the hydroxyl and carbonyl peaks.
However at 1500 h exposure, while the area of
the peak at 1515 cm -' remains below those of the
hydroxyl and carbonyl peaks, the area of the
peak at 1266cm -' increases dramatically to a
value which is greater than all other peaks
analyzed.
The fact that the species responsible for the
appearance of the peak at 1266cm -~ suddenly
increases in concentration at long exposure times
may be attributed to the fact that this species
may actually be a product of secondary reactions
occurring within the degraded SAN. In other
words, the products formed during the photo-
oxidation process in the early stages of exposure
could then act as reactants in secondary reactions
which occur later in the degradation process. The
species to which the peak at 1266 cm-' could be
assigned may therefore be a product of one of
these secondary reactions occurring within SAN.
At this point it is desirable to compare the
results of the photooxidation study of SAN to
that which is known about the photooxidation of
the constituent homopolymers--namely, poly-
styrene (PS) and polyacrylonitrile (PAN).
363
A thorough literature search extending back
through the past thirty years resulted in the
identification of only one published report
concerning the photooxidation of PAN. The
reason for this shortage of information is most
likely due to the fact that PAN is known to be
very stable when exposed to sunlight. Instead,
because PAN is used as a precursor in the
formation of carbon fibers, nearly all of the
degradation studies of this material have involved
the analysis of its thermal stability. However, a
report published by Nakamura et al. 8 compared
the chemical reactions occurring within PAN
during photooxidation and the thermal oxidation
of the material.
From infrared analysis of the photooxidized
PAN, Nakamura et al. 8 found that after exposure
to ultraviolet radiation in air there appeared new
spectral peaks at 3375 cm -1 , 3212 cm -1,
1715 cm -~, 1668 cm -t, 1625 cm -1 and 1592 cm -I.
The first two peaks were assigned to the chemical
group N - - H , while the remaining peaks were
assigned to the groups ~ O (aliphatic), ~ O
(conjugated), ~ N , and a combination of ~ C
and ~ N (aromatic), respectively. There was
also a corresponding decrease in the intensities of
the nitrile peak at 2240 cm -1 and the methylene
peak at 1450cm -~. Furthermore, it was con-
cluded by a comparison of the infrared spectra
of photooxidized and thermally oxidized PAN
that the chemical reactions occurring within the
material during these two types of degradation
process are not equivalent.
The study of the photooxidation of polystyrene
using infrared spectroscopy has, however, been
the subject of many published reports. 9-'9 It is
generally accepted that the photooxidation
process results in the formation of several
different types of carbonyl groups, including
various types of ketones, aldehydes and acids, as
well as many different types of hydroxyl groups.
The major infrared spectral changes reported to
occur from the photooxidation of polystyrene
involve the appearance of new peaks in the
hydroxyl and carbonyl regions. The generally
accepted basic degradation mechanism that
results in the formation of these different types of
chemical species is given below:
----CHz--CH-- h~ ~ --CH2--C--- + H"
 364 M. Sargent, Z L. Koenig, N. L. Maecker
- ~ C H 2 - ~ - - + 02
OO.
I I
---CH~--C-- + - - C H 2 - - C H - -
OOH
I I
---C--CH2--CH--
As previously mentioned, the SAN copolymer
samples were exposed to ultraviolet radiation
that had a minimum wavelength of 295 nm.
However, it has been well-established that PS
cannot absorb ultraviolet radiation of wave-
lengths above 290 nm. It is generally accepted
that the absorption of radiation with wavelengths
above 290 nm is due to the presence of impurities
within the molecular structure of the PS. 2-25
These impurities may include hydroperoxide
groups, carbonyl groups, in-chain peroxides and
monomer residues. Therefore, when PS is
exposed to ultraviolet radiation above 290 nm the
polystyryl radical is not generated by the
abstraction of the tertiary hydrogen as shown in
the above reaction scheme. Rather, these
impurities act as initiators (IN) by absorbing the
ultraviolet radiation to produce a radical. This
initiator radical then reacts with the PS to
produce the polystyryl radical as shown below:
IN h, ) IN"
IN. + - - C H 2 ~ C H - - , ~CH2--C--
Once this polystyryl radical is formed, the
photooxidation process will then proceed as
shown in the first reaction scheme.
Turning back now to the photooxidation study
of SAN, it has already been established in this
report that there exist characteristic peaks in the
OO.
I
) ---CH2--C--
OOH
) - - C H 2 - - C - - + ---CH2--'C--
O. O
Jl
~C---CH2~CH-- ) ----C + CH2 C H - -
difference spectra of the degraded SAN that
correspond to the formation of carbonyl and
hydroxyl groups. Furthermore, none of the new
peaks which are reported by Nakamura et al.8 to
result from the photooxidation of PAN can be
found in the difference spectra of the photo-
oxidized SAN. More specifically, there is no new
peak formed near 1625cm -~ which would
indicate the formation of ~ N groups. There is
also no measurable decrease in the peak area of
the nitrile band. These results indicate that the
photooxidation of SAN occurs exclusively at the
styrene repeat units within the copolymer
structure.
It has just been established that there is no
measurable decrease in the peak area of the
nitrile band after SAN has been exposed to
ultraviolet radiation. However as shown in Fig.
12, changes do occur within this region during
the photooxidation process. The nitrile band in
the difference spectrum of the SAN sample
exposed for 1500h in the Weather-Ometer
resembles that of a derivative-type peak.
However, what is actually happening is that the
peak is shifting to higher frequencies during the
degradation process. Considering the fact that
this peak shifts in frequency yet the actual peak
area does not change, it is evident that rather
than there occurring a decrease in the number of
nitrile groups present in the photooxidized SAN
copolymer, the chemical environment around
these nitrile groups is actually changing. This
change in the chemical environment would, in
fact, be a result of the degradation reactions
 FT-IR analysis of photooxidation of styrene-acrylonitrile
0.10
OIFFERENCE SPECTRUM
0.08
1500 HR EXPOSURE TIME
0.06 (1500 MR - 0 MR)
0.04 -
0.02
0.00
-0.02
-0.04
I
-0.06 "
-0.08 I I
2320 2300 2280
Wavenumber (cm-I)
Fig. 12. The nitrile band in the difference spectrum of the SAN sample exposed for 1500 h.
occurring within the surrounding styrene repeat
units of the copolymer.
The shift of the nitrile peak to higher
frequencies during the photooxidation of SAN
can be better understood by referring to a study
conducted by Wolfram et al. 26 which included an
examination of the position of the nitrile band as
a function of the copolymer composition of SAN.
For samples containing 25wt%, 40wt% and
85 wt% acrylonitrile, the frequency of this peak
was reported to be 2236cm -1, 2237cm -1 and
2240cm -1, respectively. This shift in peak
position to a higher frequency as the amount of
acrylonitrile is increased in the SAN copolymer
was attributed to the fact that the peak position is
very sensitive to the strong intermolecular
dipolar bondings which occur between nitrile
groups on adjacent chains in the bulk copolymer.
It has been suggested in studies by Andrews &
Kimmet27-29 that because nitrile groups on
adjacent chains in PAN should have their dipoles
oppositely directed, dipolar bonding should occur
between these groups as they approach each
other. A similar analysis can therefore be made
to the nitrile groups in the SAN copolymer.
365
I I I I
2260 2240 2220 2200 2180
The nitrile stretching peak will attain its
highest frequency when the nitrile bond has the
greatest electron density. Correspondingly, the
electron density is highest when the number of
dipolar bonds between nitrile groups is maxi-
mized. A high acrylonitrile content in the
copolymer therefore increases the probability of
having two nitrile groups on adjacent chains in
close enough proximity to permit the formation
of dipolar bonds between them.
The findings of these studies can also be used
to explain the nitrile peak shift in the infrared
spectrum of photooxidized SAN. As previously
mentioned, it has been determined earlier in this
report that one of the results of the photooxida-
tion of SAN is the formation of carbonyl groups.
Therefore, if dipolar bonding can occur between
nitrile groups on adjacent chains in either PAN
or the SAN copolymer, dipolar bonding should
also occur between nitrile groups and carbonyl
groups on adjacent chains in photooxidized SAN.
This dipolar bonding between the nitrile and
carbonyl groups would increase the electron
density of the nitrile bond and cause its infrared
band to shift to higher frequencies.
366 M. Sargent, J. L. Koenig, N. L. Maecker
CONCLUSIONS
When SAN is exposed to solar radiation or
simulated solar radiation having a short wave-
length limit of 290nm, the photooxidation of
SAN occurs exclusively at the styrene repeat
units within the copolymer structure. The major
infrared spectral changes resulting from the
degradation process involve the appearance of
new peaks within the hydroxyl and carbonyl
regions. Factor analysis reveals that there are a
minimum of four different types of hydroxyl
groups and three different types of carbonyl
groups being formed during the photooxidation
of SAN. After 200 h exposure in the Weather-
Ometer, the rate of increase in the concentration
of the carbonyl groups within the degraded
material is greater than the rate of increase in the
concentration of the hydroxyl groups.
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