Group 15 systems polyphosphazenes

Gel electrolytes were also prepared by Allcock [605] from co-substituted polyphosphazenes with various ratios of methoxyethoxyethoxy and trifluo-roethoxy side groups, lithium triflate and propylene carbonate. These gel electrolyte systems have a better mechanical stability than MEEP. The highest ionic conductivity obtained was 7.7x10" S cm" at 25 °C for a gel containing 37.5% of polymer with 80% and 20% of methoxyethoxyethoxy and trifluoro ethoxy... 

The purpose of this chapter is to introduce a new class of polymers for both types of biomedical uses a polymer system in which the hydrolytic stability or instability is determined not by changes in the backbone structure, but by changes in the side groups attached to an unconventional macromolecular backbone. These polymers are polyphosphazenes, with the general molecular structure shown in structure 1. 

Finally, a new water-soluble polyphosphazene was recently synthesized that has the structure shown in 36 (46). This polymer has two attributes as a biomedical macromolecule. First, the pendent carboxylic acid groups are potential sites for condensation reactions with amines, alcohols, phenols, or other carboxylic acid units to generate amide, ester, or anhydride links to polypeptides or bioactive small molecules. Second, polymer forms ionic crosslinks when brought into contact with di- or trivalent cations such as Ca or Ai3+. The crosslinking process converts the water-soluble polymer to a hydrogel, a process that can be reversed when the system... 

Cyclophosphazenes are a fascinating group of inorganic heterocyclic compounds whose chemistry is multi-faceted, well developed and reasonably well understood. They are closely related to the linear poly-phosphazenes this relationship is unlike any other existing between ring-polymer systems. Although cyclic siloxanes and polysiloxanes have a close interrelationship, the number and types of cyclophospha-zene derivatives that are known, together with their exact counterparts in polyphosphazenes, underscore the utility of cyclophosphazenes as models for the more complex polyphosphazenes. The literature on cyclophosphazenes has appeared earlier in the form of books (1,2), chapters of books (3-5), authoritative compilations of data (6,7), and several reviews (8-21). The current literature on this subject is reported annually in the Specialist Periodic Reports published by the Royal Society of chemistry (22). This review deals mostly with chlorocyclo-... 

With this synthetic and molecular structural diversity, polyphosphazene chemistry has developed into a field that rivals many areas of organic polymer chemistry with respect to the tailored synthesis of polymers for specific experimental or technological uses. Indeed, hybrid systems are also available in which organic polymers bear phosphazene units as side groups. This is discussed in another Chapter. 

Second, as a logical development of the first approach, polyphosphazenes have been synthesized that bear phosphine units connected to aryloxy side groups (37). The phosphine units bind organometallic compounds, such as those of iron, cobalt, osmium, or ruthenium (38). In several cases, the catalytic activity of the metal is retained in the macromolecular system (39). A similar binding of transition metals has been accomplished through nido carboranyl units linked to a polyphosphazene chain (40). 

Third, metallocene units, such as ferrocene or ruthenocene, have been linked to phosphazene cyclic trimers or tetramers and these were polymerized and substituted to give polymers of the type mentioned previously (41). Polyphosphazenes with ferrocenyl groups can be doped with iodine to form weak semiconductors. Polymer chains that bear both ruthenocenyl and ferrocenyl side groups are prospective electrode mediator systems. 

Worthy of attention are the attempts to produce LC polymers on the basis of inorganic polymers those are polyphosphazenes with mesogenic side groups (cholesterol) although the first results to have been published were not promising40. A broad class of heterocyclic compounds could have probably contributed to the synthesis of new systems. The synthetic possibilities of this approach are quite evidently far from being exhausted. 

Polymer 3.87 has been evaluated as a matrix for the controlled release of progesterone.197 It was first shown that the rate of release of this steroid and of bovine serum albumen can be controlled by variations in the ratio of aryloxy to imidazolyl side groups atached to the polyphosphazene chain. In vitro and in vivo studies were conducted to examine the release rate of labelled steroid from devices implanted subcutaneously in rats. Typical data are shown in Figure 3.22. The biocompatibility of this system, at least in rats, was found to be good. 

Optical Materials. The polyphosphazene skeleton is electron-rich, which means that it provides a refractive index increment compared to conventional saturated organic backbones. In addition, the macromolecular substitution synthesis aUows highly unsaturated organic side groups to be linked to the skeleton in ways that allow the refractive index, the color, the liquid crystalline, and nonlinear optical characteristics of the polymer to be finely tuned. Thus, the use of these polymers in opto-electronic (photonic) switches and lens systems is a subject of growing interest. 

The biomedical use of polyphosphazenes for drug delivery and controlled release systems still draws considerable attention. It has been demonstrated for the degradable polymer [NP(NHCH2C02Et)2]n that the rate of degradation increases by partially replacement of the ethyl glycinate groups by small amounts... 

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