Makromol. Chem., Macromol. Symp.

72,1-9(1993) 1

UNCOMMON METHODS FOR SPECTROSCOPIC ANALYSES OF POLYMERS

Edward G. Brame, Jr., the CECON GROUP, 2 4 2 N. James St.,
Suite 2 0 2 , Wilmington, DE 19804, USA
Abstract: The commonly used spectroscopic analyses of
polymers include infrared (IR), nuclear magnetic
resonance ( N M R ) , mass(MS), x-ray(XR), and the rapidly
growing near infrared(N1R). The uncommon methods that
are not frequently used include nuclear quadrupole
resonance(NQR), electron spin resonance, and combination
techniques such as gas chromatography-infrared, thermal-
infrared, gas chromatography-mass spectroscopy, and even
thermal-gas chromatography-infrared or mass spectroscopy.
The use of two of these methods (thermal-infrared(TGA-IR)
and NQR is described. Appropriate examples are shown to
point out how useful they can be.
INTRODUCTION
The various spectroscopic methods that are being used to
characterize polymers form a large battery of methods for
determining their structure, morphology, identification and
concentration of components so that any polymer from simple
polyolefins to complex polyurethanes or terpolymers can be
completely analyzed. Infrared, x-ray, and nuclear magnetic
resonance methods have been and continue to be leaders in
carrying out the analyses. Of course, these methods have
become even more sophisticated in recent years with infrared
instruments employing fourier transform techniques in its
instrumentation and surface reflectance in its sampling, and
with nuclear magnetic resonance techniques progressing from
solution to solids sampling. With these wonderful advances
all of which use a variety of computer technologies taking
place in their examinations, other and less common methods
are often overlooked. However, there have been advances
among these methods as well. Many of them are involved with
combination techniques. They include many kinds of
separation methods including thermal and combine them with
various kinds of spectroscopy methods such as FTIR. In
addition, pulse NQR methods have been found to be highly
useful for structure determination even if it is often in a
1imited manner (Refs. i -3).

0 1993 Huthig & Wepf Verlag, Basel CCC 0258-0322/93/$04.00

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RESULTS AND DISCUSSION

Today, I will describe an application of the thermal-
infrared (TGA-FTIR) method of analysis to illustrate how it
can be used to determine a minor component in a complex
material such as is the case with polyurethanes. By
heating a sample of polyurethane to high enough temperature
to degrade it and at the same time to detect all the
individual components that are separated by the thermal
treatment, any slight variation in the breakup of the
polymer can be seen from the FTIR spectra obtained. Figure
1 shows the temperature range over which the heating was
performed on a sample of polyurethane and the time that was
required to reach the maximum temperature of about 500 OC.
This figure shows a generally linear plot. Figure 2 shows
the percent weight remaining from the thermogravimetric
scale as the sample is heated over this temperature range to
about 500 "c. From the curve it is readily seen that the
maximum weight loss occurs around 400 'C.That is the
temperature where the sample degrades. Figure 3 shows the
evolved gas profile over the time of the analysis which
includes the upper limit of about 5 0 O 0 C -From this figure it
is apparent that the maximum amount of material evolved
occurs as the sample weight undergoes the maximum decline.
Then, in Figure 4 the FTIR spectrum taken at the temperature
of about 350'12 is seen.This infrared spectrum is seen to
cover the range from 4000 cm-l to 500 cm-l. Only a few
peaks of moderate intensity are seen. The expected peaks
for water and carbon dioxide are observed and at the same
time a few peaks from the polyurethane breakup are seen. It
is not until we get to higher temperatures that we begin to
see the decomposition products. Figure 5 shows the spectrum
obtained at 379 "C.Here, we see major absorption peaks in
the C-H stretch region as well as in the C=O stretch region.
The component which we are focusing on shows its carbonyl
peak at about 1750 cm-l. It is seen to be of moderate
intensity. In Figure 6 the spectrum obtained at 397 "C shows
the intensity of this peak to be relatively less than the
other peaks in the spectrum on comparison with its relation
to the other peaks in the previous figure. By the time the
 3

5oo-J

" 450-

c 400-

a
c,
m 300-

1%-
I I I I I I
0 5 10 15 20 25 30
Time in min

Figure 2

b
c 80-
.d
E
-4

g 40-
b
.d
m

200 250 300 350 400 450

Temperature in O C

0.000 I I I I I I I I I I ,
2 4 6 8 10 12 14 16 18 20 22
Time in min
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0.006 Figure 4

01 0.004
V
m
n
u 0.002
0
n
a:
0.000.
3
-0.002.

I I I I I I 1
41 I 3500 3000 2500 2000 1500 1000 500
Wavenumber in cm-l

o.ooeJ

0.006 1
0.004

a:
n 0.002 ,

I I I I
4000 3500 3000 2500 2000 1500 lob0 500
Wavenumber in cm-I

t I I I I I I 1
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber in cm-l
 5

temperature of 4 0 3 OC is reached (Fig. 7), this carbonyl

peak is seen to be much less intense than is seen in the
previously obtained spectra. Upon examining the sample
directly without performing the thermal separation, this
carbonyl peak is barely visible. Whereas upon using the
thermal separation procedure it can be seen very readily.

Another thermal procedure that has been widely touted lately

and is often used for identifying polymer materials that are
difficult to examine is to use the BRILL cell. This cell is
manufactured by CDS instruments in the US for use with FTIR
instruments. We can do the same kind of analysis with it
that is done through the TGA method except that it produces
a total degradation product which is a complete breakup of
the polymer. The results of this analysis on our
polyurethane is shown as one FTIR pattern in Figure 8 . This
Figure shows the result of heating the sample from room
temperature to 5 0 0 OC at a rate of 90 O C per second and
obtaining the FTIR spectrum shown. The total gas evolved
produced a spectrum that is seen here. The 1750 cm-I marker
band is also seen here but it is not as readily
descriminated as a distinguishable band as we found with the
thermal separation procedure. Thus, from the thermal
separation procedure that tears apart components in a
complex polymer such as a polyurethane allows for an easier
identification of them by FTIR than can be obtained directly
on the material or sometimes with the use of this BRILL
cell. However, it does have its place as a direct and
simple approach to the IR analysis of polymers.

Another uncommon spectroscopic method that has a place in

performing structure studies on polymers is NQR. Continuous
wave methods have been the most common procedure for this
system of analysis. However, along with other spectroscopic
techniques pulse methods have found their way here as well.
One of the major problems with NQR in its examination of
polymers is that line widths are generally broad and that
individual lines that can be assigned to separate structures
are rarely observed. With the pulse methods some of these
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Figure 7

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber in cm

0
P SfiMPLE = 03070
0

Ln
PI

0 3
2 6.
m
n
:g
n .
a:
-
m
0

Wavenumber in cm -1

Frequency in MHZ
 7

Figure 10

Frequency in MHz

Figure 11

pll 32.5 32.7 32.9 33.1 313 3u 317 333 34.1

Frequency in MHZ

Table 1. Parameters o f BQR before and a f t e r crosslinking

i n polgchloroprene.

Band width, kHz Peak frequency, MHz

before 32.8 33-07

after 760 32.6 33-10
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distinct disadvantages can be partially overcome. Today, I

want to describe some interesting results obtained on
polychloroprene rubbers with the use of 35Cl NQR.
Polychloroprenes have been studied by many people over the
years and their structures are well understood in terms of
H-H vs H-T structures as well as cis vs trans conformations.
These different structures in the uncured state can be
examined readily by Proton and I3C NMR. In the cured state
they are less available for examination but with the use of
solid state NMR they have become more readily available for
examination. NQR on the other hand can examine them in the
solid state at different states of cure and can measure the
relative amount of the common structures in polychloroprene.
Figure 9 shows a 35Cl NQR spectrum of an uncured
polychloroprene(Neoprene W which is a commercial product).
Two lines are observed. The relatively narrow line is
attributed to the ordered fraction and the broad line is
attributed to the disordered fraction. The ratio of the
areas of the lines attributed to the ordered versus the
disordered fractions is determined to be 27:73. Figure 10
shows the NQR spectrum of a partially cured polychloroprene.
Here the intensity of the narrow line is decreased relative
to the broad line in comparison with the uncured
polychloroprene. The intensity of the narrow line relative
to the broad line is seen to be 19:81. Then, for the
completely cured polychloroprene material, we see an overall
broad line which upon deconvolution barely shows much of an
ordered fraction. The integrated intensity ratios then
become about 2:98. Because it is difficult to make the
deconvolution of these two curves into that shown in Figure
11, the above estimate is about the best that can be done
under the circumstances. Obviously, the overall curve is
asymmetric and some portion of it can be attributed directly
to the ordered phase. Table I shows the effect of
crosslinking on the ordered and disordered phases. Most of
the effect is seen in the band width of the ordered phase
upon going from 120 kHz to 350 kHz. There is only a slight
shift of peak frequency of the ordered phase and it is seen
to shift from 32.8 to 32.6 MHz. For the disordered phase
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the peak shift is slightly in the other direction to higher

frequencies. From these above data we see that the
crosslinking of polychloroprene results in a particular kind
of r1solvation98
of the ordered fraction into the disordered
one. These findings indicate that 35Cl NQR can be used for
controlling the microstructure of different chloroprene
rubbers in production and that this method can be used to
control the product's quality.

It is hoped that these two examples of some uncommon

spectroscopic methods of analysis illustrate the power and
usefulness of these relatively unknown methods. Perhaps,
they will come to be more widely used in the future.

ACKNOWLEDGMENT
The NQR work reported here was performed in collaboration
with G. K. Semin and his group at the Institute of Element-
Organ0 Compounds in Moscow. The work was supported by the
National Academy of Sciences and the Soviet Academy of
Sciences.

REFERENCES
D. J. Johnson and D.A.C. Compton, American Laboratory,
-
37 January (1991) "Quantitative Analysis of
Nitrocellulose and Pulp in Gunpowder Using TGA-FTIR"

T. A. Babushkina and G. K. Semin, Bull. Acad. of

Science, Physical Series 45, (3) 508 (1981)
"NQR of Polychloroprenes"

T. A. Babushkina, L. N. Grozdeva, and G. K. Semin,

-
J. Molecular Structure n, 215 (1981) "NQR Study of the
Structure and Structural Transitions in Chloroprene
Rubbers"