Surface-bound reactive polymers

Side Chain and Surface-Bound Reactive Polymers... 

Surface-bound reactive polymers Surfactants, conventional 51 Suspension copolymerization 13 Swelling behavior 26... 

In a highly favorable medium, containing a reactive redox-initiating pair, transfer is likely to occur either in the aqueous phase or at the particle surface. In either case, the surfactant will reside at a particle surface bound to the polymer by one or more covalent bonds (see Figure 4). 

The first step Is to ensure that the macromolecules are bound to the surfaces. For this purpose they can be grafted chemically however this Is an expensive process, requiring the use of reactive polymers or tailor made surface active species such as block copolymers. A less expensive method Is to use macromolecules which spontaneously adsorb to the surfaces. Then experimental wisdom states that surfaces which are each completely saturated with macromolecules will repel each other (stabilisation of the suspension), while surfaces which are unsaturated will attract each other because the macromolecules will bridge them together (flocculation) (1). 

The use of a synthetic model system has provided valuable mechanistic insights into the molecular catalytic mechanism of P-450. Groves et al. [34]. were the first to report cytochrome P-450-type activity in a model system comprising iron meso-tetraphenylporphyrin chloride [(TPP)FeCl] and iodosylbenzene (PhIO) as an oxidant which can oxidize the Fe porphyrin directly to [(TPP)Fe =0] + in a shunt pathway. Thus, (TPP)FeCl and other metalloporphyrins can catalyze the monooxygenation of a variety of substrates by PhIO [35-40], hypochlorite salts [41, 42], p-cyano-A, A -dimethylanihne A -oxide [43-46], percarboxylic acids [47-50] and hydroperoxides [51, 52]. Catalytic activity was, however, rapidly reduced because of the destruction of the metalloporphyrin during the catalytic cycle [34-52]. When (TPP)FeCl was immobilized on the surface of silica or silica-alumina, catalytic reactivity and catalytic lifetime both increased significantly [53]. There have been several reports of supported catalysts based on such metalloporphyrins adsorbed or covalently bound to polymers [54-56]. Catalyst lifetime was also significantly improved by use of iron porphyrins such as mew-tetramesitylporphyrin chloride [(TMP)FeCl] and iron mcA o-tetrakis(2,3,4,5,6-pentafluorophenyl)por-phyrin chloride [(TPFPP)FeCl], which resist oxidative destruction, because of steric and electronic effects and thereby act as efficient catalysts of P-450 type reactions [57-65]. 

Quaternary ammonium and phosphonium ions bound to insoluble polystyrene present an even more complicated mechanistic problem. Polystyrene beads lacking onium ions (or crown ethers, cryptands, or other polar functional groups) have no catalytic activity. The onium ions are distributed throughout the polymer matrix in most catalysts. The reactive anion must be transferred from the aqueous phase to the polymer, where it exists as the counter ion in an anion exchange resin, and the organic reactant must be transferred from the external organic phase into the polymer to meet the anion. In principle, catalysis could occur only at the surface of the polymer beads, but kinetic evidence supports catalysis within the beads for most nucleophilic displacement reactions and for alkylation of phenylacetonitrile. 

The reactivity modification or the reaction rate control of functional groups covalently bound to a polyelectrolyte is critically dependent on the strength of the electrostatic potential at the boundary between the polymer skeleton and the water phase ( molecular surface ). This dependence is due to the covalent bonding of the functional groups which fixes the reaction sites to the molecular surface of the polyelectrolyte. Thus, the surface potential of the polyion plays a decisive role in the quantitative interpretation of the reactivity modification on the molecular surface. 

Properly functionalised additives can react with polymer substrates to produce polymer-bound functions which are capable of effecting the desired modification in polymer properties, hence the use of the term reactive modifiers. As an integral part of the polymer backbone, reactive modifiers are useful vehicles for incorporating the desired chemical functions to suit the specialised application. Being molecularly dispersed, the problem of solubility expressed under 2 above is avoided. Implicitly, the bound-nature of the function is not subjected to the normal problems of the loss of additives from the surface which are common with both high and low molecular mass additives. The bound nature of the function must be fully defined for the conditions of service. 

Another approach to producing latexes with chemically bound surface-active groups is to use a reactive surfactant—a surfactant with a polymerizable double bond, such as sodium dodecyl allyl sulfosuccinate [Wang et al., 2001a,b,c]. Copolymerization of the reactive surfactant with the monomer of interest binds the surface active groups into the polymer chains. 

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