P-DVB

Producing a polystyrene (PS)-DVB copolymer of increasing porosity has been accomplished by dissolving 50-80% styrene, 10-50% divinylbenzene, and 30-70% of an inert organic liquid. Toluene is a solvent for the monomer but is a nonsolvent for the polymerized polymer. The monomer solution is then incorporated into water to form a dispersion of oil droplets followed by the polymerization of the suspended oil droplets from the aqueous medium into the polymer (21). 

The effects of the concentration of divinylbenzene on pore-size distribution and surface areas of micropores, mesopores, and macropores in monosized PS-DVB beads prepared in the presence of linear polymeric porogens have been studied (65). While the total surface area is clearly determined by the content of divinylbenzene, the sum of pore volumes for mesoforms and macropores, as well as their pore-size distribution, do not change within a broad range of DVB concentrations. However, the more cross-linked the beads, the better the mechanical and hydrodynamic properties. 

A novel cross-linked polystyrene-divinylbenzene copolymer has been produced from suspension polymerization with toluene as a diluent, having an average particle size of 2 to 50 /rm, with an exclusive molecular weight for the polystyrene standard from about 500 to 20,000 in gel-permeation chromatography. A process for preparing the PS-DVB copolymer by suspension polymerization in the presence of at least one free-radical polymerization initiator, such as 2,2 -azo-bis (2,4-dimethylvaleronitrile) with a half-life of about 2 to 60 min at 70°C, has been disclosed (78). 

Figure 1.5 shows the cumulative pore volume curve for 5-/rm monosized porous PS-DVB particles with 50, 60, and 70% porosity. The curves were drawn by overlapping the measurements from nitrogen adsorption-desorption and mercury intrusion. A scanning electron micrograph of 5-/rm monosized particles with 50% porosity is shown in Fig. 1.6 (87). 

For organic SEC separations the use of polystyrene/divinylbenzene (PS/ DVB) particles is almost universal throughout the industry. Polymer Laboratories PS/DVB material, PLgel, which is produced in a series of individual pore sizes, formed the basis for the original product line of SEC columns. Developments in the refinement of particle sizing introduced the benefits of smaller particle size and more efficient columns, which significantly reduced SEC analysis time through a reduction in the number of columns required for... 

The use of hexafluoroisopropanol (HFIP) as an SEC eluent has become popular for the analysis of polyesters and polyamides. Conventional PS/DVB-based SEC columns have been widely used for HFIP applications, although the relatively high polarity of HFIP has led to some practical difficulties (1) the SEC calibration curve can exhibit excessive curvature, (2) polydisperse samples can exhibit dislocations or shoulders on the peaks, and (3) low molecular weight resolution can be lost, causing additive/system peaks to coelute with the low molecular weight tail of the polymer distribution... 

Whereas for organic SEC column technology a particular type of bead (PS/ DVB) is used almost universally, in the field of aqueous SEC there have been a variety of approaches to derive polymeric beads suitable for the application. For this reason there is more secrecy about the chemical composition of the packing materials and columns produced by different manufacturers. 

The elution behavior of various polymers near their critical adsorption point with silica gel packings and various eluents has been studied (12). It was of interest to apply hybrid column systems composed of active ( critical ) packings (silica gels) in combination with nonactive (nonadsorptive) PS/DVB and DVB-based gels. Some PS/DVB and DVB gels exhibited rather strong... 

New, unused columns were used to minimize the memory effects known not only with silica gel active packings, but also with PS/DVB materials (13). One single column of each kind (7.5, 7.8, 8, or 10 mm in diameter and 250 or 300 mm in length) was used in each series of experiments. 

Chloroform has lower affinity toward silica gel-based adsorbents than THF. PMMAs were fully retained from this solvent on the nonmodified silica gel even in the presence of a 1% ethanol stabilizer (14). It has been shown that PMMAs were not retained even within the most interactive PS/DVB column using chloroform stabilized with 1% ethanol. Chloroform is considered a weak displacer. 

Toluene was found to have low affinity toward silica gel and strongly promoted the adsorption of PMMA (12,14) on this material. Preliminary experiments revealed that toluene at least moderately promoted the adsorption of PMMA on several PS/DVB and DVB SEC gels. 

Figure 15.6 indicates that this is a relatively noninteractive column. PMMA is eluted in toluene, yet the calibration dependences surprisingly diverge in the area of high molar masses. It has the opposite tendency to that observed for various polymers with PS/DVB columns by Dawkins (5,20) and also contradicts the finding for columns No. 5 and 6. 

It is evident from these results that the interactive properties of the investigated SEC PS/DVB or DVB gels are very different. Because polar electroneutral macromolecules of PMMA were more retained from a nonpolar solvent (toluene) than from polar ones (THF, chloroform), we conclude that the dipol-dipol interactions were operative. Columns No. 1 and No. 2 were very interactive and can be applied successfully to LC techniques that combine exclusion and interaction (adsorption) mechanisms. These emerging techniques are LC at the critical adsorption point (18), the already mentioned LC under limiting conditions of adsorption (15,18), and LC under limiting conditions of desorption (16). In these cases, the adsorptivity of the SEC columns may even be advantageous. In most conventional SEC applications, however, the interactive properties of columns may cause important problems. In any case, interactive properties of SEC columns should be considered when applying the universal calibration, especially for medium polar and polar polymers. It is therefore advisable to check the elution properties of SEC columns before use with the... 

The basic chemical structure of ion exchangers is the same for most of them. They are quite often formed by PS-DVB cross-linked frameworks, with different kind and degree of functionalization, cross-linking degree, specific surface area and porosity. The large-scale industrial production of PS-DVB resins started more than 50 years ago [40]. The ready availability of these materials attracted the attention of chemists interested into chemical synthesis... 

Feedstock Reactions Catalyst References Acetone Condensation-hydrogenation (bifunctional catalysis) Pd on sulfonated PS-DVB [6] Methanol, Raffinate II Condensation, hydrogenation Pd on sulfonated PS-DVB [61] Dioxygen dissolved in water Hydrogenation Pd on sulfonated PS-DVB [8]... 

PS DVB -CH2N(CH2COONa)2 Chelate resins exchanged with metal ions... 

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