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IR spectroscopy is a technique which could be utilize to measure number-average


molecular weight of a polymer. This is done on the assumption that the chain of the molecule is
linear. This limit the number of end-groups of a given polymer to a few molecules only. For
polymer which posses branching (polymers which mainly produce from addition
polymerization), IR measurement is only a relative number-average molecular weight of the
system. To determine the molecular weight of fluorocarbons, IR spectroscopy is the standard
method as IR spectroscopy is particularly useful for measuring the number-average molecular
weight of an insoluble system.

In determination of end-group and molecular weight of polybutylenes terephtalete,


molecular weight, Mn, of the polymer is


Mn =


Where

E1 = equivalents per gram of alcoholic end groups


E2 = equivalents per gram of acid end groups

This equation presumes that no other end groups are present and that no grafting or degradation
has occurred.

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‘ The composition of copolymer can be measured by ratioing an infrared band of A-


copolymer (which is not influenced by sequencing effects) to an internal thickness band (which
corrects for variations in thickness). The same measurement also is performed on B-copolymer
component though not compulsory. For example, the composition of polyethylene- -vinyl
acetate, EVA can be determined by ratioing the 1740 cm-1 band for vinyl acetate to the 1460 cm-1
internal thickness band.

Vibrational coupling complicates the IR analysis of copolymers. The difficulty of the IR


analysis is a function of the size of the comonomer repeat units. The magnitude of the vibrational
coupling between units is a function of the intramolecular distance. When the repeat units are
small, the coupling is large and is a function of the type of vibrational motion. When the repeat
units are large, the coupling between units will be zero or very small. For example, the spectrum
of the trimer of poly(ethylene terephthalate) (PET) is essentially the same as that of high-
molecular-weight PET because the length of the PET repeat unit is so long that the
intramolecular interactions between repeat units is essentially zero. When the repeat units are
small (i.e., contain only two carbons, as is the case for vinyl monomers), vibrational coupling can
occur between the repeat units. This coupling results in spectral bands that have frequency and
absorptivity depending on the length of the ordered sequence. This intensity perturbation by the
coupling factor must be taken into consideration when developing a method of spectral analysis.
For large comonomer repeating units, the IR analysis is simplified because the analysis of only
the composition is possible, and the copolymer can be considered, from an IR point of view, to
be simply a mixture of the two comonomers. Unfortunately, for the case of large repeating units,
IR spectroscopy will not yield information about the copolymer sequence distribution. Consider
the case when vibrational coupling occurs; in this case, IR spectroscopy can yield connectivity
information about the microstructure of the copolymer. For the spectra of ethylene-propylene (E-
P) copolymers (Drushel , 1968). The structure of the various sequences of this copolymer is
shown in the following scheme, Figure 2.1 illustrating the expected origin of the different
segments of methylene units.

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The extent of crosslinking in the Nadic methyl anhydride isomers or NMA and diglycidyl
ether of bisphenol-A based epoxy, EPON 828 (with 0.5 wt% benzyldimethyl amine as a curative
in each mixture) can be determined by using IR spectroscopy (Antoon  , 1981). The least-
squares method was used to fit the spectra of the mixture of NMA and EPON 828. In order to
determine the degree of crosslinking, a difference spectrum was calculated by subtracting the
spectrum of a stoichiometric mixture of NMA and EPON 828 crosslinked for 37 min at 80°C
from the spectrum of the same reactant mixture crosslinked for 83 min at 80°C

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The relative geometric arrangement of the chemical groups along the polymer chain, that is, the
conformation of the chain is also of interest. Polymer chains have a number of possible rotational
isomers, depending on the temperature and thermal history of the sample. Rotational potentials for
single bonds joining chemical groups such as methylene units are necessarily threefold and symmetric
(Fig. 4.1). The energy minima occur when the substituents of the groups, hydrogens in this case, are in
the staggered conformations, but maxima occur at the eclipsed conformations. In molecules possessing

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maxima. However, rapid interconversion is possible among the various forms. The  form is a
staggered conformation in which the internal rotation angle X-C-C-X is 180 °C

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Polymers generally have several different conformations in the solid state depending on their
thermal history. In the crystalline state, the regular structure results in a repeating polymer conformation.
This repeating conformation is usually determined by X-ray or electron diffraction methods, but for
amorphous and glassy polymers, these diffraction methods are not applicable. Vibrational spectroscopic
methods are useful because the vibrational modes are sensitive to differences in internal bond angles.
When the polymer chains exhibit extended order, specific vibrational selection rules apply, and these
rules can be used to determine the conformation of the isomer

To study rotational isomerism in polymers, the spectroscopic technique must be able to


distinguish the spectral features of each identifiable conformer. The vibrational spectrum of a mixture of
conformers will exhibit bands arising from the molecular vibrations of all conformers. In general, the
conformer bands in a polymer system are observed in pairs that correspond to modes of similar form but
slightly different frequencies in the high- and low-energy conformers. When the spectra are obtained as
a function of temperature, pairs of bands with one band intensity increasing and the other band intensity
decreasing will often be observed. For polymers, there is usually considerable overlap of these band
pairs.

Polyethylene (PE) is the most-studied example of rotational isomerism. The crystalline domains
are made up of the all-trans conformer structure. Bands that are characteristic of rotamers in the
amorphous phase are also present. The most intense of the amorphous absorptions are the methylene
 
wagging modes at 1303, 1353 and 1369 cm -1 . The TG conformation is correlated with the bands
observed at 1303 and 1369 cm -1. The 1353-cm -1 absorption band is assigned to the wagging of the GG
structure. When PE is heated through its melting point, the concentration of the TG and GG
conformations increases. However, the concentration of the TG conformation increases well below the
melting point, and this increase indicates the formation of localized conformational defects in the
crystalline polymer.

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‘‘ IR spectroscopy can be used to study the effects of applied mechanical stress on highly oriented
samples. The goal is to obtain the `  
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for determining the stress relaxation moduli‘ or creep compliances. Shifts in the peak frequencies are
observed and an attempt is‘ made to determine the molecular stress distribution by deconvolution
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(Bretzlaff  , 1983). The shifts‘ as a function of stress for the 1168-cm band of oriented isotactic
polypropylene‘(Lee , 1984) are shown in Fig. 5.1.

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Vibrational spectroscopy can be used to study intermolecular effects in the solid state and the
changes produced by temperature effects. If the intermolecular forces are sufficient, the fundamental
modes of the single chain are split into different spectral components in the crystal. The number of
theoretically expected bands depends on the number of molecules in the unit cell. Polyethylene (PE) has
a planar conformation and an orthorhombic unit cell containing two molecules. Each group mode of the
isolated PE molecule is predicted to be split into two components for crystalline PE. This crystal field
splitting has been observed for the methylene rocking mode at 720 cm-1 and for the methylene bending
mode at 1460 cm-1 in spectra of crystalline PE. Although other modes should also exhibit such splitting,
their inherent bandwidth prevents the observation of separate components. When PE is melted, the
crystal field splitting disappears. Consequently, a measure of the relative intensities of the 720- to 730-
cm -1 bands can be used to rank the relative crystallinity of PE samples.

The problem is that very few polymers exhibit the crystal field splittings observed for PE. The
explanation is that the crystal field splitting is very sensitive to the distance of separation of the polymer
chains. The intermolecular interaction forces fall off at a rate of r 6, where r is the distance between


chains. A very small difference in separation results in a large difference in the magnitude of the
interactions, and consequently, in the frequency separation of the bands. In fact, the PE chains are closer
together than chains of any other polymer, so the crystal field splitting is the largest for PE. For
polypropylene (PP), on the other hand, it has not been possible to observe any IR splittings resulting
from intermolecular or crystalline packing. In fact, there are many features in the PP spectrum that look
like pairs of bands, and indeed they are. However, the band pairs arise from `    
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Actually, intermolecular packing influences the IR spectrum of PP very little. In Fig. 4.42, the X-ray
patterns of the monoclinic ot phase and the smectic 6 phase are shown. The monoclinic oe phase
consists of well-ordered crystalline 31 helices, while the smectic 6 phase consists of 31 helices that are
out of register with each other. The smectic phase will convert with time to the monoclinic oe phase at a
rate that is a function of temperature. The IR spectra of these two phases are also shown in Fig. 6.1, and
the spectra are strikingly similar. Only minor differences in intensities are observed in the IR spectra, yet
from the X-ray point of view, the smectic phase is noncrystalline. The reason for these small differences
is that the helices are far apart (relative to the distance in PE), and consequently, the intermolecular
forces are much lower, and the intermolecular splitting is below the resolution of the instrument.
Unfortunately, the spectral results for PP are typical for most semicrystalline polymers.

ü
 ‘

Antoon, M.K., Zehner, B.E., Koenig, J.L., Polym. Compos. 2 (1981) 81

Bretzlaff, R.S., Wool, R.E, Macromolecules 16 (1983) 1907

Drushel, H.V., Ellerbe, J.J., Cos, R.C., Love, L.H., Anal. Chem. 40 (1968) 370

Koenig, J. L.,Spectroscopy of Polymer 2nd Ed.(1999)147-206

Lee, Y.-L., Bretzlaff, R.S., Wool, R.E, J. Polym. Sci., Part B: Polym. Phys. 22 (1984) 681

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