Polymerization cross-linking effect

Santora BP, Gagne MR, Moloy KG, Radu NS. Porogen and cross-linking effects on the surface area, pore volume distribution, and morphology of macroporous polymers obtained by bulk polymerization. Macromolecules 2001 34 658-661. 

Cross-linking Effect on Polymerization. The general cross-linking reaction that occurs during polymerization and involves components with a functionality greater than one (two or more double bonds, divinyl monomer) has been studied extensively. The statistical analysis of molecular distributions in such reactions is due to Flory (36). 

In all cases, the films were obtained by oxidative electropolymerization of the cited substituted complexes from organic or aqueous solutions. The mechanism of metalloporphyrin Him formation was suggested to be a radical-cation induced polymerization of the substituents on the periphery of the macrocycle. As it was reported for the case of polypyrrole-based materials ", cyclic voltammetry and UV-visible spectroscopy with optically transparent electrodes were extensively used to provide information on the polymeric films (electroactivity, photometric properties, chemical stability, conductivity, etc.). Based on the available data, it appears that the electrochemical polymerization of the substituted complexes leads to well-structured multilayer films. It also appears that the low conductivity of the formed films, combined with the cross-linking effects due to the steric hindrance induced by the macrocyclic Ugand, confers to these materials a certain number of limitations such as the limited continuous growth of the polymers due to the absence of electronic conductivity of the films. Indeed, the charge transport in many of these films acts only by electron-hopping process between porphyrin sites. 

From this work, it is clear that the cross-link density and hence the magnitude of G should be determined by the number of intermolecular cross-links. Effective cross-linking should therefore be favored by a homogeneous distribution of cross-linking monomer throughout the copolymer. Therefore, we studied how the polymerization pH affected the properties of chromium ion gels prepared from 50 mole % AMPS/AA copolymers. 

Elastomeric Modified Adhesives. The major characteristic of the resins discussed above is that after cure, or after polymerization, they are extremely brittie. Thus, the utility of unmodified common resins as stmctural adhesives would be very limited. Eor highly cross-linked resin systems to be usehil stmctural adhesives, they have to be modified to ensure fracture resistance. Modification can be effected by the addition of an elastomer which is soluble within the cross-linked resin. Modification of a cross-linked resin in this fashion generally decreases the glass-transition temperature but increases the resin dexibiUty, and thus increases the fracture resistance of the cured adhesive. Recendy, stmctural adhesives have been modified by elastomers which are soluble within the uncured stmctural adhesive, but then phase separate during the cure to form a two-phase system. The matrix properties are mosdy retained the glass-transition temperature is only moderately affected by the presence of the elastomer, yet the fracture resistance is substantially improved. 

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. 

An excellent review of composite RO and nanofiltration (NE) membranes is available (8). These thin-fHm, composite membranes consist of a thin polymer barrier layer formed on one or more porous support layers, which is almost always a different polymer from the surface layer. The surface layer determines the flux and separation characteristics of the membrane. The porous backing serves only as a support for the barrier layer and so has almost no effect on membrane transport properties. The barrier layer is extremely thin, thus allowing high water fluxes. The most important thin-fHm composite membranes are made by interfacial polymerization, a process in which a highly porous membrane, usually polysulfone, is coated with an aqueous solution of a polymer or monomer and then reacts with a cross-linking agent in a water-kniniscible solvent. 

N,]S2-diaHyltartardiamide (DATD) [58477-85-3] (37). The cross-linking of polymerized monomer with the comonomer is what controls the pore size of the gel polymer mesh. This level of pore size control makes polyacrylamide gel electrophoresis an effective analytical tool. 

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. 

An aqueous ethanol solution of acrylamide, 2,2 -methylenebisacrylamide as cross-linked agent and third acrylamide derivative, is dispersed in an n-alkane. Then three monomers are polymerized to spherical porous gels. The effect of the composition of the third monomer on the exclusion limits of the gel in size-exclusion chromatography has been investigated (82). 

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