THE CRITICAL MODE IN POLYMER LIQUlD CHROMATOGRAPHYIt is well known that by changing the eluent composition in the liquid chromatographic (LC) analysis of macromolecules, one can go from the exclusion mode to the adsorption mode, resulting in an opposite elution order of the studied macromolecules. In between this exclusion and adsorption region, there is a so-called 'Critical Region' wherc the polymer backbone does not contribute to retention (Entelis et al., 1986). By employing the specific eluent composition and temperature corresponding to this critical region, the retention of macromolecules will be determined by the number and polarity of the chain-endgroups only. The polymer backbone has become 'invisible' to the adsorbent and the macromolecule elutes as if it were a point-like molecule with the endgroups being responsible for retention only. An example of this phenomenon (Entelis et al., 1986), for polystyrene standards in a CHClJCC1, eluent, is given in Fig. 3 .By applying such conditions for a telechelic polymer, the resulting chromatogram will thus show the diversity of the number and nature of functional endgroups attached to the polymer backbones, i.e. the Functionality-type distribution-FTD (Entelis el al., 1986). This distribution, ideally two-dimensionally linked to the molecular weight distribution (MWD), is Exclusion Critical Adsorption IgM t 7.0 6.0 5.6 5.C 5.35 5.3 5.2 %CHC13 3.0) 2 .o 3.0 k.0 V,Id Figure 1. Transition from the exclusion to the adsorption separation mode through critical conditions for polystyrene standards (Entelis et a/., 1993). Column: LiChrosorb Si-100, 0.5 rnUmin; T, 27 "C; UV-275 nrn. / -I Figure 2. (a) Types of macromolecules (Skvortsov and Gorbunov, 1990) which can be studied by critical LC independent of the adsorbent's pore size (R>D or RD (17, macromolecular size; D, pore size).Dashed lines: polymer parts invisible at critical conditions.of key importance as it determines the overall reactivity and performance of a reactive polymer. Besides the determination of the functionality-type distribution, LC in the critical mode has also been applied to separate polymer blends (Pasch, 1993), to study AB and ABA block copolymers (Pasch et al., 1993; Pasch and Augenstein, 1993) to study branching or grafting (Gorschkov et al., 1988) to separate linear macromolecules from cyclic analogous (Entciis et al., 1986;Kruger et al., 1990) o r to separate block from random copolymers (Gorshkov et al., 1990). A pictural overview (Skvortsov and Gorbunov, 1990) of the different types of macromolecules which can be studied with critical LC is shown in Fig. 2. The dashed lines in the figures represent the polymer parts which are being made invisible by applying critical conditions for these