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.
It is the purpose of this experiment to study
the photooxidation of SAN and gain new insight
Styrene-acrylonitrile copolymers (SAN) are into the chemical reactions occurring within the
recognized for their high optical clarity, rigidity copolymer during the degradation process. This
and resistance to heat and chemicals. 1 SAN is will be accomplished by using infrared spectro-
commonly used by the automotive industry in scopy to follow the extent of the photooxidation
applications such as tail light lenses, dash reactions as a function of exposure time.
components and interior trim. Other products
made from SAN include blenders, mixers and Experimental
other household appliances, as well as packaging
materials such as bottles and vials. The styrene-acrylonitrile random copolymers
When SAN is exposed to solar radiation in the were obtained from the Dow Chemical Com-
presence of oxygen, the copolymer turns yellow pany. They had a copolymer composition of
in color and experiences a decrease in its surface 74wt% styrene and 26wt% acrylonitrile, as
quality due to crazing. Furthermore, the determined by precipitation fractionation imple-
mechanical properties deteriorate as measured by mented on liquid chromatography equipment6
a decrease in the toughness, ultimate tensile and a weight average molecular weight (Mw) of
strength and impact strength. 2-5 However, desp- 160 950. The SAN copolymer was obtained in the
ite the commercial importance of SAN very little pellet form and then pressed into thin films on a
is known about the chemical reactions occurring heated Carver press.
355

Thermal oxida- achieve a short wavelength limit of 290 nm. the spectra were scaled Examining first the hydroxyl region. The presence of these groups depression was 10°C. 1000 h and were not able to be obtained. L. 800 h. From excellent conditions for detecting very small these spectra the increase in peak intensity with changes in the spectra resulting from the exposure time is evident. It was deter. obtaining the difference spectrum at each However. The tion could have occurred within the material xenon arc source operated at 0 . To correct for variations in thickness 1650 cm-L between samples.01 mm) film samples were periods beyond this time limit were too brittle to exposed in an Atlas Ci65 Weather-Ometer for handle and reproducible spectra of such samples periods of 200 h. It can clearly be seen that the Weather-Ometer for periods of 200h. 7 dry air and used an MCT detector cooled with Within the instrumental limits of detection. experiment reveals no presence of any acetophe- All spectra were transferred to a Microvax II for none end groups. 1 are the spectra of both an with a copolymer composition of 74 wt% styrene unexposed SAN sample and a sample of SAN and 26wt% acrylonitrile was exposed in the exposed for 1500 h. 400h. Sargent. Koenig. The spectral changes photooxidation process. liquid nitrogen. 600 h. 400 h. To simulate the emission reactions occurring within SAN during photo- profile of natural daylight in the full ultraviolet oxidation. photooxidation occur in the hydroxyl region mined that reproducible transmission spectra between 3700cm -1 and 3200cm -1 and the could be obtained from these thin film samples of carbonyl region between 1800 cm -1 and SAN. While the water acetophenone end groups and hydroperoxide spray was not in operation the wet bulb groups are formed. This involved the subtraction of . beginning in cyclization results in the disappearance of nitrile November 1988. 800 h. It can therefore be concluded that any chemical changes detected in the samples exposed in the RESULTS A N D DISCUSSION Weather-Ometer result from photooxidation occurring within the SAN copolymer. hydroperoxide groups or ~ N subsequent data processing. One thousand scans of each infrared analysis of the SAN samples used in this sample were collected at a resolution of 4 cm -1.I R by the appearance of an infrared band in the Spectrometer. This weeks. The Weather-Ometer was equipped with Before the samples exposed to ultraviolet a xenon arc source and was designed for radiation are analyzed to determine the chemical controlled irradiance. A series of thin film SAN copolymer samples Shown in Fig. humidity cycle was used which consisted of It has been established by Gueskens & Bastin 3 108 min of light followed by 12 min of light plus a that when thermal oxidation of SAN occurs. The SAN will also turn yellow from testing facility. J. The signal-to-noise ratio of the exposed from periods of 200-1500 h along with spectra is approximately 400:1. water spray of deionized water. Attempts were made to occurring within this region were then isolated by increase the time of exposure beyond 1500 h. A repetitive 2 h press.1 . 3 5 W / m 2 at either during polymerization or while the thin 340 nm and the black panel temperature of the film samples were being made with the heated Weather-Ometer was 63°C. Thin film samples were exposed the formation of conjugated structures formed by at an angle of 45 ° facing south for periods of 3 the cyclization of the acrylonitrile units.6 0 F T . L. thermal oxidation has occurred within the borosilicate inner and outer filters were used to copolymer prior to irradiation. can be identified by the appearance of infrared A second series of samples was also analyzed spectral peaks at 1685cm -1 and 3340cm -1. groups and the formation of ~ N groups. groups before exposure to ultraviolet radiation. Fig. which provides the spectrum of the unexposed sample. The Transmission spectra were collected at room presence of these ~ N groups can be identified temperature on a Digilab F r s . major spectral changes resulting from the 600 h. it was found that the films exposed for exposure time. 5 weeks and 6 weeks. that had been exposed at a Florida outdoor respectively. The spectrometer was purged with region of 1690-1480 c m . 2 according to the area under the aromatic band at shows this spectral region for all six samples 1952cm -1. Maecker The thin (0.356 M. 1500 h.08 + 0. N. it is necessary to establish that no region as well as its short wavelength limit. 1000 h and 1500 h.

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. 3100 cm . . 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. linearly independ- the spectrum of the unexposed SAN from the ent components in a series of spectra. Factor analysis was performed on the difference spectra to determine the number of components that could be spectroscopically determined within the hydroxyl region. 370 ~ ~ ~ 0 hr.47). minimum value when the number of components is equal to four. if two or more different types of hydroxyl groups The difference spectra of all exposed samples are being formed at the same rate. As seen in Table 1.1 Fig. 1. Rather. 4 is shown the carbonyl region for the formation of one new peak. procedure which can determine the number of spectroscopically identifiable. Therefore. The infrared spectra of an unexposed SAN sample photooxidation of SAN. 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. factor analysis are shown in Fig. spectrum of the degraded sample. 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. the indicator function attains its 0 HR. (~ ~ overlapping peaks appearing within this region. 3. 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). 2. FT-IR analysis of photooxidation of styrene-acrylonitrile 357 changes result from a combination of several EXPOSURE il~ . the spectral unexposed SAN sample along with all six TRANSMISSION SPECTRA iO0 h r .

the spectrum of the same sample is 0-03. 5 reveal that the their presence are shown in Figs 6 and 7. Sargent.05. are a minimum of three different types of This subtraction procedure eliminates the com. Two other new spectral peaks are formed The difference spectra for the carbonyl region during the degradation process. L. changes occurring within the carbonyl region respectively. salts. The difference attains its minimum value when the number of spectra of these samples were obtained to isolate components is equal to three. carbonyl groups being formed during the bination and overtone bands from the phenyl photooxidation of SAN. N. maximum absorbance of the peak at 1266 cm -~ in gradation process.358 M. other possible sources of origin components function (n) (× 10-5) of the substances responsible for these peaks are minerals. there the degradation peaks forming within this area. L. Factor analysis results the time of exposure in the Weather-Ometer.85 Ometer. These weakly are shown in Fig. Therefore. the carbonyl group being formed during the de. If chemical substances are being 4 3. etc. As spectral region increase in intensity as the illustrated in Table 2. The hydroxyl region of the difference spectra for the six SAN samples exposed from 200 h to 1500 h (AA = 0-47). J. Again it Factor analysis was performed on the can be seen that the new peaks forming in this difference spectra in the carbonyl region. 3.35 deposited on the SAN films during the water 5 5. the indicator function exposure time is increased. Maecker DIFFERENCES P E C T R ~ EXPOSURETIME j (HOURS~ . 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.90 spray cycle.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.91 3 3. dissolved in the water used 1 13-14 during the humidity cycle in the Weather- 2 4. Correspondingly. However. it is clearly evident that their intensities increase with Table 1. The maximum absorbance for the result from a combination of several overlapping peak at 1515 cm -1 in the SAN sample exposed peaks. samples exposed from 200 h to 1500 h. the 1266cm -1 and the difference spectra revealing difference spectra in Fig. Koenig. the concentrations of these deposits 6 17-46 will increase with exposure time. Although both of these peaks are very weak. As was found with the new absorbing peaks appear at 1515cm -1 and spectral peaks formed in the hydroxyl region. There is therefore more than one type of for 1500h is only 0. 5. ring on the styrene repeat unit. .

O m e t e r without the use of a water Fig.' and 1266 cm -~ do not result from any deposits left on the S A N film surface during the water spray cycle. several different experiments components function were performed. Fig. T h e first test involved placing (n) (× 10-5) A T R crystals in the W e a t h e r .93 being exposed to environmental conditions 2 9. Factor analysis results from the carbonyl region of the and 1266cm .~.83 DIFFERENCSE P ~ 6 46. it seems probable that the peaks at 200 ~ 1515 c m . A f t e r 1 44.~_~~~. presence of both peaks in the resulting infrared .\ .44 3 4.' 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. 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)._ spectroscopy to d e t e r m i n e if any type of deposit had collected on their surfaces.1 ~ 0 hr..70).08 5 11. 4.O m e t e r . Analysis of these films revealed the six SAN samples exposed from 200 h to 1500 h (AA = 0.~/ 2050 cm .. Because no detectable deposits could be found on these crystals. To d e t e r m i n e w h e t h e r the peaks at 1515 cm -~ Table 2. . 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 . 5..99 4 6.63 identical to those experienced by the S A N samples. The carbonyl region of the difference spectra for the spray cycle.. FT-IR analysis of photooxidation of styrene-acrylonitrile 359 TRANSMISSION SPECTRA O0 h r . H o w e v e r . these crystals were analyzed by infrared -':::::'"' / /p.

1290 12%5 1280 1275 1~averlumber 1270 (cm-1) 1265 1260 1255 The areas under the peaks appearing in the Fig. 5 reported a Fig. 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. 1515cm-L In a study of the photooxidation of However. Although it has been established . testing facility and discussed below.oo the copolymer. from the difference spectra shown in ABS. 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. Sargent. . 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. The appearance of a new peak at 1515cm-' is in its natural environment. Maecker new peak around 1510cm -1 in the spectra of DIFFERENCE SPECTRA/~ degraded samples of all three products. However. 6. N. This 6DO ~ reaction may involve the degradation of im- purities present in very low concentrations within . 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. 5. the changes occurring in the carbonyl similar materials. 7.360 M. it can be concluded that this peak most likely results from a side reaction occurring within the SAN copolymer. Koenig. 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). Because of this need to verify the spectra. from the DIFFERENCE $PEC~ difference spectra shown in Fig. L. 11 as a function of exposed from 200 h to 1500 h ( A A = 0-03). 5 Although no previous studies have reported weeks and 6 weeks. 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. weakly absorbing peaks at 1515 cm -1 and 1266cm -1 were also detected in these samples exposed in the outdoor testing facility. As previously mentioned. exposure time. J. L. Priebe e t al. 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. 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. 8 for samples exposed for periods of 3 weeks. a series of samples was reactions occurring within the material during exposed in an outdoor testing facility. gradation occurring within SAN that has been I I I i I I exposed to natural weathering conditions. 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. ASA and SAN. Sufficient data is not available to make a definite EXPOSURE TIME / assignment of this band. material under artificial weathering conditions duplicate those occurring under natural weather- ing conditions. a peak has been reported near region of these spectra appear to be negligible. . Similarly. It can therefore be concluded that the degradation 1oo0 j ~ reactions occurring within the artificially weath- ered SAN samples accurately reflect the de- ~00 _ ~ . photooxidation.

for all hydroxyl groups being formed and another To correct for the fact that the extinction value for all carbonyl groups being formed.OSURE 5 WEEKS 3W E E K S ~ I I t I 2100 2000 1900 1800 1700 1600 Wavenumber (cm -1) F i g . the peaks occurring in these concentration of all types of carbonyl groups. regions were integrated to give a combined value were determined. all types of hydroxyl groups. that there are several different types of hydroxyl other words. $ . FT-IR analysis of photooxidation of styrene-acrylonitrile 361 SAMPLES EXPOSEDTO OUTDOORWEATHERING CONDITIONS EX. . as well as the total oxidation of SAN. values for the total concentration of and carbonyl groups formed during the photo. T h e carbonylregion ofthein~ared spectra forthe SAN samples exposed to naturaisunlight(AA = 0.26). The carbonyl region of the difference spectra for the SAN samples exposed to natural sunlight (AA = 0-06). In 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.

~ I I I I I I I 0 200 400 600 800 I000 1200 1400 1600 Exposure Ttme ( h o u r s ) Fig. 60. L. N." ~0.1650 cm_l-~ A 1520 . -- P e 8 © k 30.1255 cm × 40. 10. X 1800 . . [] 0 0. The hydroxyl region of the difference spectra for the SAN samples exposed to natural sunlight (AA = 0-04). Koenig. Maecker SAMPLES EXPOSED TO OUTDOOR WEATHERING CONDITIONS EXPOSURE /' ~ 3599 3563 3527 34'92 34'56 3420 Wavenumber (c= .1 ) Fig.3200 c. 0 A × 10.-. L.1505 c=_l 1"-1 1280 . [] Spectral Reqton © 7oo . ][1.- A × I" e 8 × 20.362 M. J. A plot of the peak area versus exposure time for the four spectral regions in which new peaks formed during the photooxidation of SAN. Sargent.

the assumption has to be made that at very stable when exposed to sunlight. There was 1515cm -~ and 1266cm-'. Nakamura et al. However. the products formed during the photo. cluded by a comparison of the infrared spectra However at 1500 h exposure. Comparing the data from the peaks at and ~ N (aromatic). it was con- determined for the hydroxyl and carbonyl peaks. From the data shown in Fig. ~ O increase in the concentration of the hydroxyl (conjugated). while the area of of photooxidized and thermally oxidized PAN the peak at 1515 cm -' remains below those of the that the chemical reactions occurring within the hydroxyl and carbonyl peaks. chemical species is given below: At this point it is desirable to compare the results of the photooxidation study of SAN to ----CHz--CH-. In other well as many different types of hydroxyl groups. FT-IR analysis of photooxidation of styrene-acrylonitrile 363 spectral regions of interest. likely due to the fact that PAN is known to be vanced. the chemical reactions occurring within PAN this data should not be used to compare the during photooxidation and the thermal oxidation absolute values of the concentrations of the of the material. respectively. 3212 cm -1. 8 found that after exposure change in the concentrations of these degradation to ultraviolet radiation in air there appeared new products. Furthermore. 11. that after 200 h exposure the rate of increase in The first two peaks were assigned to the chemical the concentration of the carbonyl group within group N . h~ ~ --CH2--C--. words. nearly all of the is made. The concentration changes of the various species reason for this shortage of information is most occurring as the photooxidation process ad. Instead. This meant identification of only one published report that in order to make comparisons between the concerning the photooxidation of PAN. the area of the material during these two types of degradation peak at 1266cm -' increases dramatically to a process are not equivalent. ~ N . 8 compared the SAN sample exposed for 200 h.. using infrared spectroscopy has. poly- styrene (PS) and polyacrylonitrile (PAN). 200 h exposure the concentrations of all degrada. comparisons in the changes occurring degradation studies of this material have involved over time can only be made relative to the the analysis of its thermal stability. various species present in the photooxidized SAN From infrared analysis of the photooxidized but rather should be used to compare the rates of PAN. while the remaining peaks were the degraded material is greater than the rate of assigned to the groups ~ O (aliphatic). spectral peaks at 3375 cm -1 . Furthermore. 1625 cm -1 and 1592 cm -I. 1668 cm -t. as occurring within the degraded SAN. The hydroxyl and carbonyl regions. The major infrared spectral changes reported to oxidation process in the early stages of exposure occur from the photooxidation of polystyrene could then act as reactants in secondary reactions involve the appearance of new peaks in the which occur later in the degradation process.H .+ H" that which is known about the photooxidation of the constituent homopolymers--namely. a concentrations of these products that exist within report published by Nakamura et al. 9-'9 It is appearance of the peak at 1266cm -~ suddenly generally accepted that the photooxidation increases in concentration at long exposure times process results in the formation of several may be attributed to the fact that this species different types of carbonyl groups. however. their peak areas also a corresponding decrease in the intensities of remain essentially equal to one another through the nitrile peak at 2240 cm -1 and the methylene 1000h exposure and are below those values peak at 1450cm -~. been The fact that the species responsible for the the subject of many published reports. it can be seen 1715 cm -~. all peak areas were A thorough literature search extending back normalized according to the values obtained for through the past thirty years resulted in the the SAN sample exposed for 200 h. aldehydes and acids. including may actually be a product of secondary reactions various types of ketones. because PAN is used as a precursor in the tion products are equal. value which is greater than all other peaks The study of the photooxidation of polystyrene analyzed. The generally species to which the peak at 1266 cm-' could be accepted basic degradation mechanism that assigned may therefore be a product of one of results in the formation of these different types of these secondary reactions occurring within SAN. and a combination of ~ C groups. Because this assumption formation of carbon fibers. .

. O I I Jl ---C--CH2--CH-. + . the than there occurring a decrease in the number of photooxidation process will then proceed as nitrile groups present in the photooxidized SAN shown in the first reaction scheme. However.+ ---CH2--'C-- OOH O. it has been well-established that PS peaks which are reported by Nakamura et al. Maecker OO. ~CH2--C-. copolymer. It is generally accepted found in the difference spectra of the photo- that the absorption of radiation with wavelengths oxidized SAN.C . ) . result from the photooxidation of PAN can be lengths above 290 nm. This of SAN. ~C---CH2~CH-. These results indicate that the monomer residues. be a result of the degradation reactions . Furthermore. initiator radical then reacts with the PS to 12. Sargent. L. The nitrile band in the difference spectrum of the SAN sample IN h.8 to cannot absorb ultraviolet radiation of wave. it has already been established in this change in the chemical environment would.C H 2 .... Rather.~ . There is These impurities may include hydroperoxide also no measurable decrease in the peak area of groups. Considering the fact that this peak shifts in frequency yet the actual peak area does not change. in-chain peroxides and the nitrile band.C H .. I .C H 2 . 364 M. This ultraviolet radiation. OOH I I ---CH~--C-. when PS is photooxidation of SAN occurs exclusively at the exposed to ultraviolet radiation above 290 nm the styrene repeat units within the copolymer polystyryl radical is not generated by the structure.+ . ) IN" exposed for 1500h in the Weather-Ometer resembles that of a derivative-type peak. Therefore.. However as shown in Fig. More specifically.~ C H 2 .. 2°-25 indicate the formation of ~ N groups.. carbonyl groups. N. Koenig.- As previously mentioned. hydroxyl groups.C H 2 ~ C H .+ 02 ) ---CH2--C-- OO. there is no new above 290 nm is due to the presence of impurities peak formed near 1625cm -~ which would within the molecular structure of the PS. IN. the chemical environment around Turning back now to the photooxidation study these nitrile groups is actually changing. changes do occur within this region during produce the polystyryl radical as shown below: the photooxidation process. ) ----C + CH2 C H . abstraction of the tertiary hydrogen as shown in It has just been established that there is no the above reaction scheme. none of the new However. the SAN copolymer difference spectra of the degraded SAN that samples were exposed to ultraviolet radiation correspond to the formation of carbonyl and that had a minimum wavelength of 295 nm. it is evident that rather Once this polystyryl radical is formed. .. in report that there exist characteristic peaks in the fact. Z L. these measurable decrease in the peak area of the impurities act as initiators (IN) by absorbing the nitrile band after SAN has been exposed to ultraviolet radiation to produce a radical. what is actually happening is that the peak is shifting to higher frequencies during the degradation process.

the frequency of this peak of dipolar bonds between them. dipolar bonding should occur This dipolar bonding between the nitrile and between these groups as they approach each carbonyl groups would increase the electron other. dipolar bondings which occur between nitrile Therefore.08 1500 HR EXPOSURE TIME 0. 40wt% and close enough proximity to permit the formation 85 wt% acrylonitrile. As previously acrylonitrile is increased in the SAN copolymer mentioned. 26 which included an mized. occurring within the surrounding styrene repeat The nitrile stretching peak will attain its units of the copolymer. A high acrylonitrile content in the examination of the position of the nitrile band as copolymer therefore increases the probability of a function of the copolymer composition of SAN.04 I -0. . The nitrile band in the difference spectrum of the SAN sample exposed for 1500 h. FT-IR analysis of photooxidation of styrene-acrylonitrile 365 0. 0 MR) 0. 12. it has been determined earlier in this was attributed to the fact that the peak position is report that one of the results of the photooxida- very sensitive to the strong intermolecular tion of SAN is the formation of carbonyl groups.00 -0.04 - 0. dipolar bonding should Kimmet27-29 that because nitrile groups on also occur between nitrile groups and carbonyl adjacent chains in PAN should have their dipoles groups on adjacent chains in photooxidized SAN. was reported to be 2236cm -1. the frequencies during the photooxidation of SAN electron density is highest when the number of can be better understood by referring to a study dipolar bonds between nitrile groups is maxi- conducted by Wolfram et al. highest frequency when the nitrile bond has the The shift of the nitrile peak to higher greatest electron density. having two nitrile groups on adjacent chains in For samples containing 25wt%.02 -0. if dipolar bonding can occur between groups on adjacent chains in the bulk copolymer. respectively. A similar analysis can therefore be made density of the nitrile bond and cause its infrared to the nitrile groups in the SAN copolymer.06 " -0.06 (1500 MR .08 I I I I I I 2320 2300 2280 2260 2240 2220 2200 2180 Wavenumber (cm-I) Fig.02 0. oppositely directed. 2237cm -1 and The findings of these studies can also be used 2240cm -1. Correspondingly.10 OIFFERENCE SPECTRUM 0. nitrile groups on adjacent chains in either PAN It has been suggested in studies by Andrews & or the SAN copolymer. This shift in peak to explain the nitrile peak shift in the infrared position to a higher frequency as the amount of spectrum of photooxidized SAN. band to shift to higher frequencies.

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