Poly 1,4-divinylbenzene polymerization

A typical mobile-phase composition is an acetonitrile-water gradient with a fixed concentration of trifluoroacetic acid (TFA), formic, or acetic acid (typically 0.05-0.5%). TFA acts as an ion-pairing agent and masks secondary interactions with the silica-based stationary phase. TFA may significantly suppress the ESI response in positive-ion mode. To avoid this, either formic acid is preferred or a mixture of 0.02% TFA and 0.5% acetic acid can be used. Some silica-based RPLC materials can be used with a lower TFA concentration (PepMap ). Alternatively, poly(styrene-divinylbenzene) polymeric materials (PS-DVB) can be applied. With a monolithic PS-DVB column, only a small decrease in separation efficiency on the monolithic column was observed when the TFA concentration was reduced from 0.2%to0.05%[51]. 

In addition to true ion exchange, other interactions can take place between the sample solutes and the resin. Adsorption is one of the commonest of these interactions. For example, the benzoate anion appears to be adsorbed somewhat by the poly-styrene-divinylbenzene polymeric matrix of organic ion exchangers. This may be due to an attraction of the k electrons of the aromatic polymer for the benzoate. Benzoic acid, which exists mostly in the molecular form, is absorbed to a much greater degree than benzoate salts. 

Synthesis of monodispersed poly(divinylbenzene) by precipitation polymerization in acetonitrile [88]. 

Barner, L. Li, C.E. Hao, X. Stenzel, M.H. Barner-Kowollik, C. Davis, T.P. Synthesis of core-shell poly(divinylbenzene) microspheres via reversible addition fragmentation chain transfer graft polymerization of styrene. J. Polym. Sci. A 2004,42 (20), 5067-5076. 

A parallel study has reported the synthesis of crosslinked polymer microspheres in supercritical carbon dioxide [54]. Heterogeneous free-radical polymerization of divinyl benzene and ethyl benzene were carried out at 65 C and 310 bar using AIBN initiator to form the crosslinked polymer. It is shown that in the absence of surfactants as stabilizers, polymerization of the mixture containing 80 % divinyl benzene + 20 % ethyl benzene leads to poly(divinylbenzene) microspheres of about 2.4 micron diameter [Figure 14]. In the presence of a carbon dioxide-soluble diblock copolymer as a stabilizer, polymerization of the mixture with the same monomer ratio proceeds as an emulsion and lead to smaller crosslinked particles (ca. 0.3 micron). Thermal analysis shows that the crosslinked polymer that is formed from these polymerizations is stable up to 400 C. 

Okubo et al. examined the penetration/release behavior of various solvents in-to/from the interior of micron-sized monodisperse cross-linked polystyrene/poly-divinylbenzene composite particles [63]. The hollow particles were produced by the seeded polymerization utilizing the dynamic swelling method [64], Itou et al. prepared crosslinked hollow polymer particles of submicron size by means of a seeded emulsion polymerization [65]. The morphology of the particles depends on the composition of divinylbenzene and methyl methacrylate. 

Finally, poly(divinylbenzene) (PDVB) was synthesized by dispersion polymerizations in CO2 (54). The stabilizer was a block copolymer of MMA and lH,lH,2H,2H-perfluorooctyl methacrylate. The absence of added stabilizer to the reaction (310 bar, 65°C) resulted in a precipitated polymer however, increasing the stabilizer concentration to 3 wt % resulted in 95% yield of uniform... 

Earner et al. [174] recently reported the synthesis of core-shell poly(divinylbenzene) (PDVB) microspheres via the RAFT graft polymerization of styrene. Cross-linked PDVB core microspheres containing double bonds on the particle surface were used directly to attach polymers from the surface by RAFT without prior modification of the core microspheres. The RAFT agent 1-phenyl-ethyl dithiobenzoate (PEDB) was used. PEDB controlled the particle weight gain, the particle volume, and the molecular weight of the soluble polymer. 

Jiang group developed silica/poly(divinylbenzene)-based polymeric microcapsules (PMCs) modified with three kinds of functional groups as carboxylic acid (PMC-C), sulfonic acid (PMC-S), and pyridyl groups (PMC-N), about which the PMCs displayed enhanced water retention capability even under low RH of 20%. The PMCs were well designed to have core-shell structure with controllable shell thickness, and then composite polyelectrolytes were fabricated from PMCs and chi-tosan (CS). Figure 9.9 displays the TEM images of the functionalized PMCs. 

FIG. 20-92 SEM image of a poly(styrene-co-divinylbenzene) gigaporous particle synthesized from suspension polymerization and schematic of a gigaporous particle showing through-pores and diffusion pores [Gu et al., China Partic-uology, 3, 349 (2005)]. 

Hyperbranched polymers have also been prepared via living anionic polymerization. The reaction of poly(4-methylstyrene)-fo-polystyrene lithium with a small amount of divinylbenzene, afforded a star-block copolymer with 4-methylstyrene units in the periphery [200]. The methyl groups were subsequently metalated with s-butyllithium/tetramethylethylenediamine. The produced anions initiated the polymerization of a-methylstyrene (Scheme 109). From the radius of gyration to hydrodynamic radius ratio (0.96-1.1) it was concluded that the second generation polymers behaved like soft spheres. 

Polymeric particles can be constructed from a number of different monomers or copolymer combinations. Some of the more common ones include polystyrene (traditional latex particles), poly(styrene/divinylbenzene) copolymers, poly(styrene/acrylate) copolymers, polymethylmethacrylate (PMMA), poly(hydroxyethyl methacrylate) (pHEMA), poly(vinyltoluene), poly(styrene/butadiene) copolymers, and poly(styrene/vinyltoluene) copolymers. In addition, by mixing into the polymerization reaction combinations of functional monomers, one can create reactive or functional groups on the particle surface for subsequent coupling to affinity ligands. One example of this is a poly(styrene/acrylate) copolymer particle, which creates carboxylate groups within the polymer structure, the number of which is dependent on the ratio of monomers used in the polymerization process. 

Poly(l,4-naphthylenevinylenes) have been prepared by metathesis polymerization of benzobarrelenes [181,182] and the photoluminescence properties of homopolymers and block-copolymers have been studied in some detail [183]. PPV also has been prepared via ROMP of [2.2]paracyclophane-l,9-diene [184] and ROMP of a paracyclophene that contains a solubilizing leaving group [185]. The resulting polymer is converted to PPV upon acid catalysis at room temperature. ADMET of 2,5-dialkyl-l,4-divinylbenzenes using Mo or W catalysts has... 

Zhang developed a monolithic poly(styrene-co-divinylbenzene) CEC column in which the EOF is supported by carboxyl groups of polymerized methacrylic acid [ 133]. Using benzene as a probe, column efficiencies of 90,000 -150,000 were observed within a flow velocity range of l-10cm/min (0.2-1.7 mm/s). Different families of compounds such as phenols, anilines, chlorobenzenes, phenylendi-amines, and alkylbenzenes were well separated typically in less than 5 min using 20 cm long columns. 

A high internal phase liquid-liquid emulsion (HIPE) is one where the internal or dispersed phase droplets occupy >74% of the total volume of the emulsion. At this point the droplets contact each other and beyond this volume % the droplets are forced into distorted polyhedra. If for example styrene and divinylbenzene are employed as the continuous phase and water droplets dispersed in this oil phase using a suitable surfactant to form a HIPE, the comonomers can be polymerized to form a poly(styrene-divinylbenzene) polyHIPE. Typically the water droplets are... 

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