Polystyrene separations, calibration

Hexafluoroisopropanol is able to dissolve most polyesters and polyamides (nylons) at room temperature in about 4-8 hr. Sodium trifluoroacetate (NATFAT) is typically added to suppress any polyelectrolyte effects that could occur in HFIP. GPC columns made from cross-linked polystyrene-divinylbenzene are typically used to perform the separation. " Calibration is generally performed using poly(methyl methacrylate) standards instead of polystyrene standards, due to solubility constraint. ... 

Figure 6.3 shows a comparison of elution patterns of standard polystyrene between a linear-type column and a standard-type column. Because of the high linearity of its calibration curve, the linear series has improved the efficiency of oligomer domain separation. 

Figures 13.8 and 13.9 show the separation of polystyrene standards using a typical mixed-bed column and its calibration plot, respectively. The major advantages of using a large i.d. 10-mm column are low hack pressure and relatively short run times. As seen in Fig. 13.8,10 standards from toluene thru 8.4 X 10 MW can be resolved in a mere 21 min. Because of the large 10-mm i.d. columns, 1.5-ml/min flow rates give a linear velocity equivalent to that of only 0.9 ml/min using a 7.6-mm i.d. column. Also, the gel volume contained in one 10 mm i.d. X 500 mm column is 39.3 ml, whereas a 7.6 mm i.d. X 300 mm column contains only 13.6 ml of gel volume. This bulk volume factor, combined with the large pore volumes of gels, obtains essentially the same resolution as that obtained on three standard 7.6 X 300-mm columns in series, but in about one-half the usual time required using the smaller columns.

The most widely used molecular weight characterization method has been GPC, which separates compounds based on hydrodynamic volume. State-of-the-art GPC instruments are equipped with a concentration detector (e.g., differential refractometer, UV, and/or IR) in combination with viscosity or light scattering. A viscosity detector provides in-line solution viscosity data at each elution volume, which in combination with a concentration measurement can be converted to specific viscosity. Since the polymer concentration at each elution volume is quite dilute, the specific viscosity is considered a reasonable approximation for the dilute solution s intrinsic viscosity. The plot of log[r]]M versus elution volume (where [) ] is the intrinsic viscosity) provides a universal calibration curve from which absolute molecular weights of a variety of polymers can be obtained. Unfortunately, many reported analyses for phenolic oligomers and resins are simply based on polystyrene standards and only provide relative molecular weights instead of absolute numbers. 

Calculations for Rp as a function of the relevant experimental parameters (eluant ionic species concentration-including surfactant, packing diameter, eluant flow rate) and particle physical and electrochemical properties (Hamaker constant and surface potential) show good agreement with published data (l8,19) Of particiilar interest is the calculation which shows that at very low ionic concentration the separation factor becomes independent of the particle Hamaker constant. This result indicates the feasibility of xmiversal calibration based on well characterized latices such as the monodisperse polystyrenes. In the following section we present some recent results obtained with our HDC system using several, monodisperse standards and various surfactant conditions. 

The GPC of a local crude (Bryan, Texas) sample spiked with a known mixture of n-alkanes and aromatics is shown in Figure 5 and the GPC of the crude is shown in Figure 6. The hydrocarbon mixture is used to calibrate the length of the species which separates as a function of retention volume. Ttie molecular length is expressed as n-alkane carboa units although n-alkanes represent only a fraction of the hydrocarbons in the crude. In addition to n-alkanes, petroleum crude is composed of major classes of hydrocarbons such as branched and cyclic alkanes, branched and cyclic olefins and various aromatics and nonvolatiles namely asphaltenes. Almost all of the known aromatics without side chains elute after n-hexane (Cg). If the aromatics have long side chains, the linear molecular size increases and the retention volume is reduced. Cyclic alkanes have retention volumes similar to those of aromatics. GPC separates crude on the basis of linear molecular size and the species are spread over 10 to 20 ml retention volume range and almost all of the species are smaller than the polystyrene standard (37A). In other words, the crude has very little asphaltenes. The linear... 

Eq. (5a) with v(T) = 1 and Eo(T) = 0 i.e. r0(T) = rv is identical with Eq. (2a), obtained previously by Casper and Schulz and proposed for the mathematical description of the PDC-calibration curves. It was shown above that this is not possible even in the vicinity of the theta point, if a large range of P is considered. Independently, the same result was obtained by Wolf and Breitenbach 10) from static separation experiments on the system polystyrene/cyclohexane (PS/CHX). In their notation... 

Figure 5 SEEC calibration curves used for the determination of the pore flow ratio co. Polystyrene standards separated in DMF with 1 mM (a) or 10 mM (b) LiCI. Stationary phase Lichrosorb 100-10. or O, experimental values ---------, prediction using model -------, prediction for pressure-driven SEC (P).

For polymer systems without UV activity the combination of a RI detector with a density (D) detector can be used. The working principle of the density detector is based on the mechanical oscillator method. Since this detector yields a signal for every polymer, provided that its density is different from the density of the mobile phase, this detector can be regarded as universal [29,30,36]. The separation of mixtures of polystyrene and polybutadiene by SEC with dual den-sity-RI detection is presented in Figs. 7 and 8. In a first set of experiments, the response factors of both polymers in both detectors have to be determined. Then from the intensity of each slice of the elution curves in both detectors, the mass distribution of both polymers across the elution volume axis can be calculated. As can be seen in Fig. 7, a separation into the component peaks is obtained due to the fact that the molar masses of PS and PB are sufficiently different. For both components the individual elution profiles can be determined and using corresponding calibration curves for PS and PB the individual MMDs can be calculated. The same information can be extracted from an experiment where the molar masses of the components are similar and SEC separation does not work (see Fig. 8). Again the individual mass distributions are obtained and the MMDs for PS and PB can be determined. 

If the Mark-Houwink coefficients are not available, a universal calibration curve is established using polystyrene calibration standards and the SEC-vis-cometer combination. The basic steps involved in the MMD analysis are summarized in Fig. 11. First, the universal calibration curve of the SEC separation system has to be established by using narrow molar mass standards as indicated by the top arrow pointing to the right. Once the universal calibration curve is established, the procedure can then be reversed, by going from right to left following the bottom arrow, to obtain the molar mass calibration curve of any unknown... 

---