Journal of the American Chemical Society, Vol.119, No.39, 9166-9174, 1997
Ring-opening-metathesis polymerization for the preparation of carboxylic-acid-functionalized, high-capacity polymers for use in separation techniques
Ring-opening-metathesis polymerization (ROMP) was used for the modular, molecular design of stationary phases. New materials for solid-phase extraction (SPE) as well as for air and water clean-up have been prepared by ring-opening-metathesis suspension polymerization of 1,4,4a,5,8,8a-hexahydro-1,4,5,8-exo, endo-dimethanonaphthalene (I) and its copolymerization with the functional monomer endo,endo[2.2.1.]bicyclohept-2-ene-5,6-dicarboxylic anhydride (II), using the weil-defined Schrock catalyst Mo(N-2,6-i-Pr-2-C6H3)CHCMe2Ph(OCMe(CF3)(2))(2) (III). The resulting cross-linked polymers have been investigated in terms of influence of the polymerization sequence as well as of the stoichiometries I/II and II/III on swelling behavior, surface area, capacity, accessability of the functional groups, and their possible use in SPE, respectively. In order to obtain further information about the new resins, the microstructure of poly(II) was determined by NMR techniques. investigations revealed that it represents an all cis, atactic polymer. Due to the polymerization technique employed, capacities of the different weak cation exchangers are entirely predeterminable and may be varied over many orders of magnitudes (up to 10 mequiv/g). The materials have been used successfully for solid-phase extraction of 15 different substituted anilines and lutidines from water as well as for the sampling of volatile, airborne aliphatic amines. The unambigous advances of the new SPE materials are discussed in detail.