High-MW samples

The comparison among these techniques is tabulated in Table 22.1. In summary, HdC is a separation technique with low selectivity however, the efficiency can be very high. Especially in PCHdC, high analysis speed can be achieved over a wide MW range. ThFFF performs best for the separation of high MW samples. SEC has an intermediate selectivity between FldC and ThFFF. Practicality makes SEC the most suitable method for the common MW range of synthetic polymers. SEC is by far the most commonly used technique for molecular weight distribution determinations. However, HdC is better for the fast analysis purpose. 

The main characteristics of electrospray ionisation are given in Table 6.21. Electrospray ionisation is a suitable technique for producing accurate molecular mass information on a wide range of low-MW samples. ESI-MS is particularly appealing for polar, high-MW samples (more than ca. 1000 Da), where the multiply charged ions formed have m/z values within the range of the spectrometer. However, ESI presents some problems in the identification of unknowns ... 

The application range of cSFC-DFI-MS (Table 7.41) appears to be restricted either to the analysis of low-MW substances or to problems related to high-MW samples where low detection limits are not needed [124,444,445], The analysis of surfactants [446] by SFC-MS is frequently performed to demonstrate the feasibility of newly developed interface technology for practical applications. A rugged cSFC-MS method has been developed for the analysis of ethoxylated alcohols (AEs), which are non-ionic surfactants incorporated into a wide variety of industrial and consumer products [447]. cSFC-DFT-DFS was used for the analysis of low-MW, thermally unstable peroxides, and the higher-MW surfactants Triton X-100 and... 

As field desorption (FD) refers to an experimental procedure in which a solution of the sample is deposited on the emitter wire situated at the tip of the FD insertion probe, it is suited for handling lubricants as well as polymer/additive dissolutions (without precipitation of the polymer or separation of the additive components). Field desorption is especially appropriate for analysis of thermally labile and high-MW samples. Considering that FD has a reputation of being difficult to operate and time consuming, and in view of recent competition with laser desorption methods, this is probably the reason that FD applications of polymer/additive dissolutions are not frequently being considered by experimentalists. 

The high viscosity of some high MW samples is known to cause flow rate upsets as the sample passes through the SEC column frits. Such flow rate upsets often occur at the time of elution of the sample. While the flow rate upsets like this are likely to cause viscosity detection errors in most other SEC viscosity detectors, the signal of the present viscosity detector, however, will remain true, cind unaffected by the high sample viscosity problem. 

Since polymers with different molecular weights (MWs) usually have different thermodynamic parameters and crystallization kinetics, MW is a key factor affecting polymorphism of polymers. For example, at relatively low T (e.g., 100 °C), low-MW nylon-6 samples predominantly develop the more stable a-form crystals, while high-MW samples mainly crystallize in the less stable y-form aystals [129], The 5-form crystals of PHP are only generated by low-MW samples, but not by high-MW samples [130]. 

Sample Time (hrs) % Polymer % High MW Oligomers % Intermediate MW Oligon rs % Total Conversion... 

SEC analysis shows that some samples have a blmodal MWD. At this time it is not possible to tell whether the bimodallty is an artifact of the polymerization mechanism or, perhaps, a consequence of partial hydrolysis of the polymer i.e., the high MW shoulder in Figure 5 may be due to the formation of aggregates through Intermolecular dipolar interactions of P-OH side groups or to polymer molecules crosslinked by P-O-P bonds. 

Many of the aforementioned techniques are not appropriate to direct mass-spectrometric analyses of intact high-MW and heat-labile compounds. For such samples, thermal degradation techniques (analytical pyrolysis) can be performed to generate more-volatile compounds of lower molecular weight that are amenable... 

On-line SFE-SFC modes present several distinct advantages that are beyond reach of either technique when used separately (Table 7.13). An obvious advantage of SFE is that it is an ideal way to introduce a sample into an SFC system. Because the injection-solvent is the same as the mobile phase, in this respect the criteria for a successful coupling of different techniques are fulfilled [94], i.e. the output characteristics from the first instrument and the input characteristics of the second instrument are compatible. Supercritical fluid techniques can separate high-MW compounds are significantly faster than classical Soxhlet extractions and require less heat and solvent. SFE-SFC techniques are versatile,... 

The ideal mass-spectrometric interface should allow for a range of ionisation methods (Tables 7.23 and 7.24). The ionisation of organic molecules for use with chromatographic outlets include El, Cl, APCI for samples that can be vaporised prior to ionisation alternative ionisation techniques using TSP, ESP or FAB are needed for labile, high-MW or ionic samples. 

SEC in combination with multidimensional liquid chromatography (LC-LC) may be used to carry out polymer/additive analysis. In this approach, the sample is dissolved before injection into the SEC system for prefractionation of the polymer fractions. High-MW components are separated from the additives. The additive fraction is collected, concentrated by evaporation, and injected to a multidimensional RPLC system consisting of two columns of different selectivity. The first column is used for sample prefractionation and cleanup, after which the additive fraction is transferred to the analytical column for the final separation. The total method (SEC, LC-LC) has been used for the analysis of the main phenolic compounds in complex pyrolysis oils with minimal sample preparation [974]. The identification is reliable because three analytical steps (SEC, RPLC and RPLC) with different selectivities are employed. The complexity of pyrolysis oils makes their analysis a demanding task, and careful sample preparation is typically required. 

Applications Multidimensional SEC techniques can profitably be applied to soluble polymer/additive systems, e.g. PPO, PS, PC - thus excluding polyolefins. A fully automated on-line sample cleanup system based on SEC-HRGC for the analysis of additives in polymers has been described, as illustrated for PS/(200-400ppm Tin-uvin 120/327/770, Irgafos 168, Cyasorb UV531) [982], In this process, the high-MW fractions are separated from the low molecular masses. SEC is often used as a sample cleanup for on-line analysis of additives in food extracts these analyses are usually carried out as on-line LVI-SEC-GC-FPD. 

---