Polymer-bound catalysts, advantages

Catalysis with water-soluble polymer-bound catalysts in a single homogeneous aqueous phase, the subject to this section, can be of interest for the conversion of water-soluble organic substrates. With a view to applications, the use of water as a nonhazardous, environmentally benign solvent can be advantageous. 

Soluble polymer-bound catalysts can be expected to receive continued attention as they offer specific advantages. By comparison to aqueous two-phase catalysis, a range of substrates much broader with respect to their solubility can be employed. By comparison to heterogenization on solid supports, the selectivity and activity of homogeneous complexes can be retained better. However, it must also be noted that to date no system has been unambiguously proven to meet the stability and recovery efficiency required for industrial applications. 

Polymer-bound Catalysts Various quaternary phosphonium salts are known to be excellent catalysts for trans-esterification and condensation polymerizations, e.g. melt polymerization of polycarbonates and polyesters. The ionomers from Exxpro elastomer can be used in those applications with added advantages such as solubility in the melt, ease of recovery and thermal stability. 

Non-cross-linked polymers can be used in this way just as cross-linked polymers can. For example, we have used polyethylene supports with surface grafts to support Pd(0) catalysts [133,134]. In these cases, the polymer-immobilized catalyst is used in exactly the same way as an insoluble polymer-bound catalyst. Such supported catalysts do require that the insoluble polymer be swollen or permeable to substrates or that the catalysts be within a solvent-permeable, thin immobilized graft. While this approach can be useful, it takes no advantage of the polymer s solubility. It is an approach that conceptually is no different than that used with insoluble inorganic supports or with polymers that are by design insoluble by virtue of cross-linking, and is an approach to catalyst immobilization that is not further discussed since this review is focused on polymer-immobilized catalysts that are used under solution-state conditions. 

The use of soluble polymers as catalysts was also explored by Bayer. His group showed that both diphenylphosphinated polystyrene and diphenylphosphinated poly(ethylene glycol) could be used as recoverable, reusable hydroformylation catalysts. Separation of the catalyst and the reaction products in these cases was achieved by taking advantage of the properties of the polymer chain. Solvent precipitation or membrane filtration both proved to be acceptable techniques to isolate products free from the polymer-bound catalyst. 

For lariat ethers to be effective as polymer-bound phase transfer catalysts, sidearm and macroring cooperation must be intramolecular. It is unlikely that two lariat ethers will be close enough on a polymer backbone or other support for the ring of one compound to interact with the sidearm donors of another. The mechanical attributes of lariat ethers will be independent of spacing but for any advantage in cation binding and anion activation to be realized, the macroring and its attached sidearm must cooperate to envelop the cation, solvate it, and shield it from the counteranion. 

Catalytic asymmetric alkylations of 28 have also been carried out with polymer-bound glycine substrates [43], or in the presence of polymer-supported cinchona alkaloid-derived ammonium salts as immobilized chiral phase-transfer catalysts [44], both of which feature their practical advantages especially for large-scale synthesis. 

The homogeneous chiral phosphine/DPEN-Ru catalyst can be immobilized by use of polymer-bound phosphines such as polystyrene-anchored BINAP (APB-BINAP) [57, 98], Poly-Nap [99], and poly(BINOL-BINAP) [100], poly(BINAP) [101]. These complexes hydrogenate T-acetonaphthone and acetophenone with S/C of 1000-10 000 under 8 10 atm H2 to give the corresponding secondary alcohols in 84-98% e.e. The recovered complexes are repeatedly used without significant loss of reactivity and enantioselectivity. Immobilization allows the easy separation of catalyst from reaction mixture, recovery, and reuse. These advantages attract much attention in combinatorial synthesis. 

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