Homopolymer calibration

Similarly, estimation of chemical composition of soluble polymer was also dependent on selectivity of the UV detector. Polymerized acrylonitrile has no significant UV absorbance at 230 and 254 nm. Thus, UV chromatograms were used to estimate amounts of polymerized methylacrylate and styrene In each resin system. The refractometer detector was sensitive to polymerized methylacrylate and styrene, as well as to polymerized acrylonitrile. It was therefore necessary to calculate comonomer contribution to refractometer peak areas In order to estimate concentration of polymerized acrylonitrile. This was done by obtaining a refractometer calibration for all three homopolymers. Quantity of polymerized comonomers measured by UV were then converted to equivalent refractometer peak areas. Peak areas due to polymerized acrylonitrile were then calculated by difference, and used to calculate amount of polymerized acrylonitrile. 

All three monomers were soluble In the chromatographic mobile phase and standard analytical techniques were used for calibration. Solutions containing known quantities of monomer were chromatographed to establish a peak area concentration relationship for the appropriate detector. The homopolymer of methylacrylate was also soluble In the mobile phase. Thus, both UV and refractometer detectors were calibrated for polymerized methylmethacrylate by chromatographing solutions of PM ... 

The homopolymers of styrene and acrylonitrile were not soluble In the acetonitrile mobile phase. Calibration factors thus had to be derived from a combination of literature data and experimental measurements. To calibrate the UV detector for polystyrene, 254 nm absorbance of both monomer and polymer was measured with a conventional spectrophotometer, using chloroform... 

Published refractive index data for the mobile phase, polystyrene, polyacrylonitrile, and the two monomers were used to calculate refractive index detector calibrations for the two homopolymers. The published data were used to determine relationship between refractive index increments of monomer and corresponding homopolymer. Chromatographic refractometer calibrations for the two homopelymers were then calculated from experimentally measured calibration data for the two monomers. 

B. Direct SEC-[n] Calibration. Because the SEC separation process is directly related to the size of the solvated molecules, and for a homopolymer series the molecular size is directly related to MW as well as [n]/ it is not necessary to proceed through MW calculations to study polymer intrinsic viscosity. Since... 

In analysis of homopolymers the critical interpretation problems are calibration of retention time for molecular weight and allowance for the imperfect re >lution of the GPC. In copolymer analysis these interpretation problems remain but are ven added dimensions by the simultaneous presence of molecular weight distribution, copolymer composition distribution and monomer sequence length distribution. Since, the GPC usu y separates on the basis of "molecular size" in solution and not on the basB of any one of these particular properties, this means that at any retention time there can be distributions of all three. The usual GPC chromatogram then represents a r onse to the concentration of some avera of e h of these properties at each retention time. 

Usually (e.g. 4, 2 the ratio equivalent to A254/A235 is plotted versus as shown in Figure 13. However, a plot of A235/A254 versus (1/W ) is also useful. From Equation (3) and (4) the deviation from the straight line derived from the pure homopolymers can then be used to reveal their adequacy of homopolymers for composition calibration and the presence of other variables. Figure 14 shows such a plot. 

Figure 12 were superimposable on those for detector 2. Therefore, when the plot shown in Figure 14 is linear over the range of compositions involved in the sample, then (according to equations (1-4) ) the composition of the sample is the same at each retention volume. If the variation with retention volume is negligible the copolymer can then possibly be treated as is a homopolymer in GPC interpretation. In particular, intrinsic viscosity measurements could then lead to estimates of molecular weight via the universal calibration curve. 

Figure 14. Area ratios plotted to compare with homopolymer calibration...

Simple homopolymers, where monodisperse standards and suitable solvents are available, are easily characterized by SEC. Homopolymers for which no monodisperse standards are available additionally require some more elaborate detection system for transformation of the retention time into molecular weight. This can be done by, e.g., universal calibration. Alternatively, an absolute molar mass detector, like an on-line light scattering detector or mass spectrometer, can be used. 

A more complex but faster and more sensitive approach is polarization modulation (PM) IRLD. For such experiments, a photoelastic modulator is used to modulate the polarization state of the incident radiation at about 100 kHz. The detected signal is the sum of the low-frequency intensity modulation with a high-frequency modulation that depends on the orientation of the sample. After appropriate signal filtering, demodulation, and calibration [41], a dichroic difference spectrum can be directly obtained in a single scan. This improves the time resolution to 400 ms, prevents artifacts due to relaxation between measurements, and improves sensitivity for weakly oriented samples. However, structural information can be lost since individual polarized spectra are not recorded. Pezolet and coworkers have used this approach to study the deformation and relaxation in various homopolymers, copolymers, and polymer blends [15,42,43]. For instance, Figure 7 shows the relaxation curves determined in situ for miscible blends of PS and PVME [42]. The (P2) values were determined... 

As explained in Sections 16.3.4, 6.4.1, and 16.4.2, SEC is a nonabsolute method, which needs calibration. The most popular calibration materials are narrow molar mass distribution polystyrenes (PS). Their molar mass averages are determined by the classical absolute methods—or by SEC applying either the absolute detection or the previously calibrated equipment. The latter approach may bring about the transfer and even the augmentation of errors. Therefore, it is recommended to apply exclusively the certified well-characterized materials for calibrations. These are often called PS calibration standards and are readily available from numerous companies in the molar mass range from about 600 to over 30,000,000g moL. Their prices are reasonable and on average (much) lower than the cost of other narrow MMD polymers. Other available homopolymer calibration materials include various poly(acrylate)s and poly(methacrylate)s. They are, similar to PS, synthesized by anionic polymerization. Some calibration materials are prepared by the methods of preparative fractionation, for example, poly(isobutylene)s and poly(vinylchloride)s. 

It is to be stressed again (Section 16.4) that the molar masses of homopolymers different from PS, as well as the molar masses of copolymers determined by SEC directly from the polystyrene calibration dependences should be designated polystyrene equivalent values. The latter more or less differ from the actual values and should be used only for the assessments of tendencies. 

These materials, however, as a rule exhibit rather broad chemical composition distribution. Block copolymers may contain important amounts of parent homopolymer(s) [232,244,269], In any case, it is to be kept in mind that practically all calibration materials contain the end groups that differ in the chemical composition, size, and in the enthalpic interactivity from the mers forming the main chain. In some cases, also the entire physical architecture of the apparently identical calibration materials and analyzed polymers may differ substantially. The typical example is the difference in stereoregularity of poly(methyl and ethyl methacrylate)s while the size of the isotactic macromolecules in solution is similar to their syndiotactic pendants of the same molar mass, their enthalpic interactivity and retention in LC CC may differ remarkably [258,259]. 

The HPLC system is calibrated with a glucose homopolymer standard that separates oligosaccharides consisting of 3 to at least 20 monosaccharide residues. 

The GPC analysis of block copolymers is handicapped by the difficulty in obtaining a calibration curve. A method has recently been suggested to circumvent this difficulty by using the calibration curves of homopolymers. This method has been extended so that the calibration curves of block copolymers of various compositions can be constructed from the calibration curve of one-component homopolymers and Mark-Houwink parameters. The intrinsic viscosity data on styrene-butadiene and styrene-methyl methacrylate block polymers were used for verification. The average molecular weight determined by this method is in excellent agreement with osmometry data while the molecular weight distribution is considerably narrower than what is implied by the polydispersity index calculated from the GPC curve in the customary manner. 

This is the case of parallel calibration curves discussed in the previous paper. Equation 4 shows that when the calibration curves are parallel, the equivalence ratio, r, is constant to the elution volume V. It varies with the latter when aA aB—i.e., the calibration curves are not parallel. For that case Equation 3 would have to be used. Equation 4 also shows that the equivalence ratio can be calculated from the Mark-Houwink parameters K and a. It offers a way to determine r in addition to obtaining it from the GPC calibration curves of homopolymers. 

Sequential Oxidation of DMP and DPP. The usual approach to formation of block copolymers is by the sequential polymerization of two or more monomers or by linking together preformed homopolymer blocks. In view of the importance of the redistribution process in the oxidative coupling of phenols there can be no assurance that successive polymerization of two phenols will yield block copolymers under any conditions. It is certain, however, that block copolymers can be formed only if the conditions are such that polymerization of the second monomer is much faster than redistribution of the added monomer with the polymer previously formed from the first. The extent of redistribution is followed conveniently by noting the effect of added monomer on solution viscosity, as indicated by the efflux time from a calibrated pipet. 

Size exclusion chromatography is the premier polymer characterization method for determining molar mass distributions. In SEC, the separation mechanism is based on molecular hydrodynamic volume. For homopolymers, condensation polymers and strictly alternating copolymers, there is a correspondence between elution volume and molar mass. Thus, chemically similar polymer standards of known molar mass can be used for calibration. However, for SEC of random and block copolymers and branched polymers, no simple correspondence exists between elution volume and molar mass because of the possible compositional heterogeneity of these materials. As a result, molar mass calibration with polymer standards can introduce a considerable amount of error. To address this problem, selective detection techniques have to be combined with SEC separation. 

It is clear that the interpolation between the calibration lines cannot be applied to mixtures of polymers (polymer blends). If the calibration lines are different, different molar masses of the homopolymers will elute at the same volume. The universal calibration is also not capable of eliminating the errors which originate from the simultaneous elution of two polymer fractions with the same hydrodynamic volume, but different composition and molar mass. Ogawa [33] has shown by a simulation technique that the molar masses of polymers eluting at the elution volume Ve are given by the corresponding coefficients K and a in the Mark-Houwink equation. 

Figure 7. Calibration curve relating experimentally measured C-ls/O-ls intensity ratios to the known carbon-to-oxygen stoichiometries of a series of oxygen-containing homopolymers POM, PVAc, PEO, and PMMA.

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