Linked Polystyrene

Two classes of micron-sized stationary phases have been encountered in this section silica particles and cross-linked polymer resin beads. Both materials are porous, with pore sizes ranging from approximately 50 to 4000 A for silica particles and from 50 to 1,000,000 A for divinylbenzene cross-linked polystyrene resins. In size-exclusion chromatography, also called molecular-exclusion or gel-permeation chromatography, separation is based on the solute s ability to enter into the pores of the column packing. Smaller solutes spend proportionally more time within the pores and, consequently, take longer to elute from the column. 

A method for the polymerization of polysulfones in nondipolar aprotic solvents has been developed and reported (9,10). The method reUes on phase-transfer catalysis. Polysulfone is made in chlorobenzene as solvent with (2.2.2)cryptand as catalyst (9). Less reactive crown ethers require dichlorobenzene as solvent (10). High molecular weight polyphenylsulfone can also be made by this route in dichlorobenzene however, only low molecular weight PES is achievable by this method. Cross-linked polystyrene-bound (2.2.2)cryptand is found to be effective in these polymerizations which allow simple recovery and reuse of the catalyst. 

Divinylbenzene. This is a specialty monomer used primarily to make cross-linked polystyrene resins. Pure divinylbenzene (DVB) monomer is highly reactive polymericaHy and is impractical to produce and store. Commercial DVB monomer (76—79) is generally manufactured and suppHed as mixtures of m- and -divinylbenzenes and ethylvinylbenzenes. DVB products are designated by commercial grades in accordance with the divinylbenzene content. Physical properties of DVB-22 and DVB-55 are shown in Table 10. Typical analyses of DVB-22 and DVB-55 are shown in Table 11. Divinylbenzene [1321 -74-0] is readily polymerized to give britde insoluble polymers even at ambient temperatures. The product is heavily inhibited with TBC and sulfur to minimize polymerization and oxidation. 

The monomer 4-styrenesulfonic acid was prepared by dehydrohalogenation of -bromoethjibenzene—sulfonyl chloride. The potassium salt can be polymerized in aqueous solution (222). The sulfonation of cross-linked polystyrene beads is being carried out in industry with concentrated sulfuric acid. 

The anion-selective (AX) membranes (Eig. 2b) also consist of cross-linked polystyrene but have positively charged quaternary ammonium groups chemically bonded to most of the phenyl groups in the polystyrene instead of the negatively charged sulfonates. In this case the counterions are negatively... 

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). 

Size exclusion was first noted in the late fifties when separations of proteins on columns packed with swollen maize starch were observed (Lindqvist and Storgards, 1955 Lathe and Ruthven, 1956). The run time was typically 48 hr. With the advent of a commercial material for size separation of molecules, a gel of cross-linked dextran, researchers were given a purposely made material for size exclusion, or gel filtration, of solutes as described in the classical work by Porath and Flodin (1959). The material, named Sephadex, was made available commercially by Pharmacia in 1959. This promoted a rapid development of the technique and it was soon applied to the separation of proteins and aqueous polymers. The work by Porath and Flodin promoted Moore (1964) to apply the technique to size separation, gel permeation chromatography of organic molecules on gels of lightly cross-linked polystyrene (i.e., Styragel). 

High-performance size exclusion chromatography is used for the characterization of copolymers, as well as for biopolymers (3). The packings for analyses of water-soluble polymers mainly consist of 5- to 10-/Am particles derived from deactivated silica or hydrophilic polymeric supports. For the investigation of organosoluble polymers, cross-linked polystyrene beads are still the column packing of choice. 

An intramolecular palladium(o)-catalyzed cross-coupling of an aryl iodide with a trans vinylstannane is the penultimate maneuver in the Stille-Hegedus total synthesis of (S)-zearalenone (142) (see Scheme 38).59 In the event, exposure of compound 140 to Pd(PPh3)4 catalyst on a 20% cross-linked polystyrene support in refluxing toluene brings about the desired macrocyclization, affording the 14-membered macrolide 141 in 54% yield. Acid-induced hydrolysis of the two methoxyethoxymethyl (MEM) ethers completes the total synthesis of 142. 

Strongly basic anion exchange resins, e.g. a cross-linked polystyrene containing quaternary ammonium groups, are largely ionised in both the hydroxide and the salt forms. Some of their typical reactions may be represented as ... 

The polymer-bound catalysts A-C. (Table 31) are prepared by reaction of the corresponding amino alcohols with partially chloromethylated 1 -2% cross-linked polystyrene. In the case of A, the enantioselectivity of the addition of dialkylzincs to aldehydes is higher than with the corresponding monomeric ephedrine derivatives (vide supra). Interesting insights into the mechanism of the alkylation of aldehydes by dialkylzinc reagents can be obtained from the experi-... 

Organic traps contain isoporous, macroporous, or other specifically designed resins (such as reticulated, cross-linked polystyrene resins devoid of ionic function) and take up organics by a combination of ion exchange, adsorption, and other mechanisms. They typically are installed to precede the DI plant. 

The pore structure of most cross-linked polystyrene resins are the so called macro-reticular type which can be produced with almost any desired pore size, ranging from 20A to 5,000A. They exhibit strong dispersive type interaction with solvents and solutes with some polarizability arising from the aromatic nuclei in the polymer. Consequently the untreated resin is finding use as an alternative to the C8 and Cl8 reverse phase columns based on silica. Their use for the separation of peptide and proteins at both high and low pH is well established. 

There are two types of stationary phases commonly used in exclusion chromatography silica gel and micro-reticulated cross-linked polystyrene gels. A third type of exclusion media is comprised of the Dextran gels. Dextran gels are produced by the action of certain bacteria on a sucrose substrate. They consist of framework of glucose units that can form a gel in aqueous solvents that have size exclusion properties. Unfortunately the gels are mechanically weak and thus, cannot tolerate the high pressures necessary for HPLC and, as a consequence, are of very limited use to the analyst. 

Exclusion Chromatography Employing Micro-Reticulated Cross-Linked Polystyrene Gels... 

Linear non-cross-linked polystyrene has been used for organic synthesis since it is readily soluble in common organic solvents (i.e., dichloromethane, chloroform, tetrahydrofuran, toluene, ethyl acetate, and pyridine) but precipitates upon addition of water or methanol [123-126]. However, no examples of the use of this polymer in conjunction with microwave chemistry have been reported. 

The catalysts mentioned above are soluble. Certain cross-linked polystyrene resins, as well as alumina and silica gel, have been used as insoluble phase-transfer catalysts. These, called triphase catalysts, have the advantage of simplified product work up and easy and quantitative catalyst recovery, since the catalyst can easily be separated from the product by filtration. 

Figure 1. Sketch of the primary structure (vide infra) of cross-linked polystyrene (a) and of a typical cross-linked poly-vinyil co-monomer-functional co-monomer-cross-linker (b) [14].

More recently 233) it has been reported that cross-linked polystyrene containing imidazole ligands did not provide a support rigid enough to prevent dimerization, and that the p-oxo dimer was benzene extracted from oxygenated tetraphenyl porphyrin iron(ll), Fe(TPP), which had been attached to the modified polystyrene. A discussion of model synthetic porphyrins, from which definitive structural and other physical data are obtained, is given in section V.C. 

There are a large number of literature references that refer the use of SPE cartridges for the extraction of pesticides from water. There are several comprehensive reviews of the use of SPE, including that by Soriano et al. who discussed the advantages and limitations of a number of sorbents for the analysis of carbamates. Hennion reviewed the properties and uses of carbon based materials for extraction of a wide multiclass range of pesticides. Thorstensen et al. described the use of a high-capacity cross-linked polystyrene-based polymer for the SPE of phenoxy acids and bentazone, and Tanabe et al reported the use of a styrene-divinylbenzene copolymer for the determination of 90 pesticides and related compounds in river water. SPE cartridges are also widely used for the cleanup of solvent extracts, as described below. 

The most common methods for trapping pesticide vapors from air use adsorbents. Common air sampling adsorbents include charcoal (derived from petroleum or coconut) and synthetic polymeric materials, such as cross-linked polystyrene and open-cell polyurethane foam. Charcoal has been used for the cumulative sampling of volatile... 

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