Materials design, polyphosphazenes

These materials are generally more elastomeric and rubber-like in appearance than either of the corresponding homopolymers. Such systems indicate that it should be possible to "custom design" polyphosphazenes by choosing precursors with desirable substituents. 

This account will summarise results in the development of n-conjugated materials incorporating phosphorus moieties with emphasis on the conceptual design and specific properties that result directly from the presence of the P-atom. Polyphosphazenes, which are the most familiar synthetic polymers incorporating phosphorus [8], will not be included in this review since they do not display the type of n-conjugation as sought in systems (A)-(D). 

In conclusion, all these types of light-induced reactions involving polyphosphazenes readily account for the great importance assumed by this topic in the phosphazene domain and for the remarkable application potentials of especially designed phosphazene materials. 

Understanding the relationship between molecular structure and materials piroperties or biological activity is one of the most important facets of biomaterials synthesis and new-drug design. This is especially true for polyphosphazenes, where the molecular structure and properties can be varied so widely by small modifications to the substitutive method of synthesis. 

It has been demonstrated that a variety of different polyphosphazenes can be developed as biomaterials, membranes or hydrogels, bioactive polymers, and bioerodible polymers. As with most new areas of polymer chemistry and biomaterials science, molecular design forms the basis of most new advances, but the rate-controlling step is the testing and evaluation of the materials in both in vitro and in vivo environments. This is particularly true for polyphosphazenes where the availability of research quantities only has limited the... 

In the rest of this chapter an attempt will be made to describe how this field developed, how polyphosphazenes are synthesized, how the system provides almost unprecedented opportunities for the design of new macromolecules, and how the molecular structure-property relationships have been developed to produce a wide range of advanced materials. 

First, we will consider the design of polyphosphazenes as side-chain liquid-crystalline materials.241 248 Side-chain liquid-crystalline polymers are a subclass of species described earlier as structure 3.72. Liquid crystallinity occurs when the rigid side groups become organized, usually in the semi-liquid state. The organization may be nematic (oriented but unlayered) or smectic (layered) as illustrated in Figure 3.25. 

The design of single-component polymer transport materials continues to interest researchers in this field. The use of such materials will completely eliminate solvent extraction, diffusional instability, and crystallization of the small molecules. One obvious route that has not been successful to date is the design of yet another aromatic-amine-containing carbon-backbone polymer. An alternative may be to explore the large class of glassy silicon-backbone polymers, such as polysilylenes (14) and polyphosphazenes (iS). 

This basic structure provides for considerable flexibility in the design of biomaterials, as described in a recent review [27]. By selection of the side groups on the polymer chain, both hydrophobic and hydrophilic polymers can be produced. Hydrophobic polyphosphazenes may be useful as the basis of implantable biomaterials, such as heart valves. The hydrophilic polymers can be used to produce materials with a hydrophilic surface or, when the polymer is so hydrophilic that it dissolves in water, cross-linked to produce hydrogels or solid implants. In addition, a variety of bioactive compounds can be linked to polyphosphazene molecules allowing the creation of bioactive water-soluble macromolecules or polymer surfaces with biological activity. 

The design of amphiphilic polyphosphazenes with self assembled morphologies for thermosensitive and micelle forming materials is another topic of current interest... 

The synthetic flexibility of poly(organo)phosphazenes, combined, when required, with a tunable degradability, can be used to prepare speciality materials with precisely designed functions. With intelligent design and structural modifications, it is envisaged that many advanced biomedical materials of the future could be derived from polyphosphazenes. As the many reports summarised in this book confirm, progress in this direction is indeed already well underway ... 

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