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molecular weight. IR measurement is only a relative number-average molecular weight of the system.‘ IR spectroscopy is a technique which could be utilize to measure number-average molecular weight of a polymer. To determine the molecular weight of fluorocarbons. 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. ˜ . 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. In determination of end-group and molecular weight of polybutylenes terephtalete. Mn. IR spectroscopy is the standard method as IR spectroscopy is particularly useful for measuring the number-average molecular weight of an insoluble system. For polymer which posses branching (polymers which mainly produce from addition polymerization).

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the IR analysis is simplified because the analysis of only the composition is possible. Consider the case when vibrational coupling occurs. For example. for the case of large repeating units. the coupling is large and is a function of the type of vibrational motion.. EVA can be determined by ratioing the 1740 cm-1 band for vinyl acetate to the 1460 cm-1 internal thickness band. When the repeat units are small (i. For large comonomer repeating units.‘ ‘ ‘ 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). from an IR point of view. The magnitude of the vibrational coupling between units is a function of the intramolecular distance. 1968). The structure of the various sequences of this copolymer is shown in the following scheme. as is the case for vinyl monomers). the coupling between units will be zero or very small. vibrational coupling can occur between the repeat units. Vibrational coupling complicates the IR analysis of copolymers.1 illustrating the expected origin of the different segments of methylene units. the composition of polyethylene- -vinyl acetate. The same measurement also is performed on B-copolymer component though not compulsory. For example. Figure 2. Ñ . 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. IR spectroscopy can yield connectivity information about the microstructure of the copolymer. IR spectroscopy will not yield information about the copolymer sequence distribution. For the spectra of ethylene-propylene (E- P) copolymers (Drushel . to be simply a mixture of the two comonomers. in this case. When the repeat units are small. The difficulty of the IR analysis is a function of the size of the comonomer 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. Unfortunately. When the repeat units are large. and the copolymer can be considered. contain only two carbons.e.

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EPON 828 (with 0. 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 ‘$c ‘& ‘ ‘ ‘  ‘ ‘  ‘  . In order to determine the degree of crosslinking.5 wt% benzyldimethyl amine as a curative in each mixture) can be determined by using IR spectroscopy (Antoon  .‘‘ The extent of crosslinking in the Nadic methyl anhydride isomers or NMA and diglycidyl ether of bisphenol-A based epoxy. The least- squares method was used to fit the spectra of the mixture of NMA and EPON 828. 1981).

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

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 ‘#c ‘ . However.C-C bonds. the rotation angle values near the potential minima are strongly favored over those near the maxima.

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the spectroscopic technique must be able to distinguish the spectral features of each identifiable conformer.and low-energy conformers. Bands that are characteristic of rotamers in the amorphous phase are also present. In the crystalline state. Vibrational spectroscopic methods are useful because the vibrational modes are sensitive to differences in internal bond angles. pairs of bands with one band intensity increasing and the other band intensity decreasing will often be observed. there is usually considerable overlap of these band pairs. but for amorphous and glassy polymers. Polyethylene (PE) is the most-studied example of rotational isomerism. When the polymer chains exhibit extended order. In general. these diffraction methods are not applicable.   ‘*‘ ‘*‘c/‘ ‘  c‘ ‘ Polymers generally have several different conformations in the solid state depending on their thermal history. the regular structure results in a repeating polymer conformation. and these rules can be used to determine the conformation of the isomer To study rotational isomerism in polymers. This repeating conformation is usually determined by X-ray or electron diffraction methods. The most intense of the amorphous absorptions are the methylene   . For polymers. When the spectra are obtained as a function of temperature. The vibrational spectrum of a mixture of conformers will exhibit bands arising from the molecular vibrations of all conformers. The crystalline domains are made up of the all-trans conformer structure. 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. specific vibrational selection rules apply.

the concentration of the TG and GG conformations increases. 1353 and 1369 cm -1 . The TG conformation is correlated with the bands observed at 1303 and 1369 cm -1. and this increase indicates the formation of localized conformational defects in the crystalline polymer. However. ‘ ‘#˜ ‘1. The 1353-cm -1 absorption band is assigned to the wagging of the GG structure.wagging modes at 1303. the concentration of the TG conformation increases well below the melting point. When PE is heated through its melting point.

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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 `    .

Shifts in the peak frequencies are observed and an attempt is‘ made to determine the molecular stress distribution by deconvolution -1 (Bretzlaff  . The shifts‘ as a function of stress for the 1168-cm band of oriented isotactic polypropylene‘(Lee . 1984) are shown in Fig. 5. r .1. 1983).  ‘  which is an important quantity for determining the stress relaxation moduli‘ or creep compliances.

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The number of theoretically expected bands depends on the number of molecules in the unit cell. If the intermolecular forces are sufficient. 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 explanation is that the crystal field splitting is very sensitive to the distance of separation of the polymer chains. Although other modes should also exhibit such splitting. Each group mode of the isolated PE molecule is predicted to be split into two components for crystalline PE. the fundamental modes of the single chain are split into different spectral components in the crystal. Polyethylene (PE) has a planar conformation and an orthorhombic unit cell containing two molecules. When PE is melted. their inherent bandwidth prevents the observation of separate components. the crystal field splitting disappears. 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. where r is the distance between  . Consequently.‘ Vibrational spectroscopy can be used to study intermolecular effects in the solid state and the changes produced by temperature effects. The intermolecular interaction forces fall off at a rate of r 6. The problem is that very few polymers exhibit the crystal field splittings observed for PE.

so the crystal field splitting is the largest for PE. the PE chains are closer together than chains of any other polymer. 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 consequently. the band pairs arise from `       not from `        ‘4c ‘‘   ‘ ‘ ‘‘  ‘‘ ‘7 ‘  ‘ ‘ ‘ ‘   . A very small difference in separation results in a large difference in the magnitude of the interactions. In fact. and indeed they are. in the frequency separation of the bands. For polypropylene (PP). on the other hand. However.chains.

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while the smectic 6 phase consists of 31 helices that are out of register with each other. 6. the X-ray patterns of the monoclinic ot phase and the smectic 6 phase are shown.‘  Actually. the spectral results for PP are typical for most semicrystalline polymers. 4. and the intermolecular splitting is below the resolution of the instrument. and the spectra are strikingly similar. the smectic phase is noncrystalline. and consequently. Unfortunately. The smectic phase will convert with time to the monoclinic oe phase at a rate that is a function of temperature. yet from the X-ray point of view. the intermolecular forces are much lower.1. The monoclinic oe phase consists of well-ordered crystalline 31 helices. ü . The reason for these small differences is that the helices are far apart (relative to the distance in PE). In Fig. intermolecular packing influences the IR spectrum of PP very little.42. Only minor differences in intensities are observed in the IR spectra. The IR spectra of these two phases are also shown in Fig.

Ellerbe. R.H.(1999)147-206 Lee.E. 40 (1968) 370 Koenig.. J... Anal. Cos. Bretzlaff. Phys.E. Chem.  ‘ Antoon.J.. J. R. Part B: Polym. J. Polym.S. 22 (1984) 681 ‘ c . 2 (1981) 81 Bretzlaff. Compos.C.V. L. R. Zehner.Spectroscopy of Polymer 2nd Ed. H. Koenig... Sci.E. Polym. M. L. B.. Wool.S.-L..K.. R. Y. Love.. Macromolecules 16 (1983) 1907 Drushel.L. Wool. R.. J..