Polymer-bound substrates, homogeneity

CoUman JP, Kosydar KM, Bressan M, Lamanna W, Garrett T (1984) Polymer-bound substrates a method to distinguish between homogeneous and heterogeneous catalysis. J Am Chem Soc 106 2569... 

Soluble polymer-bound substrates have also been used as part of an experimental protocol to probe the homogeneity of a catalyst (37). In these experiments, the reactivity of a substrate bound to a soluble or insoluble polymer is compared to the reactivity of the same substrr not hmmd to a polymer. No reaction of an insoluble polymer-bound substrate with a catalyst under conditions where a soluble polymer-bound substrate or a nonpolymer-bound substrate did react with the same catalyst would... 

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. 

Another procedure for preparation of valuable heterocyclic scaffolds involves the Biginelli condensation on a PEG Support [75, 76]. Polymer-bound acetoacetate was prepared by reacting commercially available PEG 4000 with 2,2,6-trimethyl-4H-l,3-dioxin-4-one in toluene under reflux (Scheme 16.52). The microwave-assisted cyclocondensation was performed with nonvolatile polyphosphoric acid (PPA) as a catalyst in a domestic microwave oven [76]. During microwave heating the PEG-bound substrate melted, ensuring a homogeneous reaction mixture. After the reaction diethyl ether was added to precipitate the polymer bound products. The desired compounds were released by treatment with sodium methoxide in methanol at room temperature. All dihydropyrimidines were obtained in high yield purification was achieved by recrystallization from ethanol. 

The system consists of solvent mixture that is biphasic at room temperature and becomes homogeneous when heated (e.g., heptane and 90% DMA/water become miscible in all proportions above 65°C). After completion of the reaction and cooling to room temperature the reaction products are staying in the nonpolar phase and can be isolated by simple phase separation. The polar phase that contains the polymer bound catalyst can be reused in further runs by adding fresh substrate solution in heptane. 

The primary methods for analysis were usually gravimetric, thermal, and spectroscopic in nature but not necessarily correlated with in situ analysis (XPS, AFM, TEM, etc.) or ex situ analysis of surface-bound polymers by de-grafting (NMR, MW, polydispersity, etc.). Colloidal stability and homogeneity of the grafting process is a primary concern. A range of these systems were analogous to what has been done in solution and in bulk and should be thoroughly examined in terms of chemistry on flat substrate surfaces. Several examples follow. 

Reproducibility problems in the production of polymer layers as described above can sometimes occur. Since washing steps and drying procedures are often incorporated to remove loosely bound material, and changes in intensity or duration of these steps can result in different layers. Thus the amoimt of the immobilised protein will be different and reduce the reproducibility of the sensors response. The use of thick organic films produced by this method can also lead to frequency instabihty and loss of sensitivity. It is also difficult to control film thickness and homogeneity, which also effect the reproducibility of the surface produced. Weak adhesion between the polymer and the substrate can also be a problem. Methods, such as plasma polymerisation and electropolymerisation, have been developed to overcome these problems and to gain more control over the layer parameters. 

Our work on latent biphasic systems has focused on linear polymers [165]. Initially these studies focused on poly(JV-alkylacrylamide)s like PNODAM because we had earlier shown that these lipophilic materials are very phase-selectively soluble in heptane [158,165]. This initial work used the PNODAM-bound SCS-Pd catalyst 116 in a DMA-heptane mixture with iodobenzene and acrylic acid as substrates and triethylamine as a base. This catalyst mixture was initially homogeneous at 25 On heating, Heck chemistry occurred to form cinnamic acid. Subsequent cooling of this reaction mixture formed a biphasic mixture even without addition of water because the reaction had formed some triethyl ammonium iodide, and this ammonium salt functioned as the perturbant. 

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