Polyphosphazene backbone, formation

When the substituent groups in the polyphosphazenes were azobenzene [719] or spiropyran [720] derivatives, photochromic polymers were obtained, showing reversible light-induced trans-cis isomerization or merocyanine formation, respectively. Only photocrosslinking processes by [2+2] photo-addition reactions to cyclobutane rings could be observed when the substituent groups on the phosphazene backbone were 4-hydroxycinnamates [721-723] or 4-hydroxychalcones [722-724]. 

The final class of polymers containing carboranyl units to be mentioned here is the polyphosphazenes. These polymers comprise a backbone of alternating phosphorous and nitrogen atoms with a high degree of torsional mobility that accounts for their low glass-transition temperatures (-60°C to -80°C). The introduction of phenyl-carboranyl units into a polyphosphazene polymer results in a substantial improvement in their overall thermal stability. This is believed to be due to the steric hindrance offered by the phenyl-carborane functionality that inhibits coil formation, thereby retarding the preferred thermodynamic pathway of cyclic compound formation (see scheme 12). 

A related synthetic strategy by Allcock and Welker65 is illustrated in reaction (19). Here, borazine side groups are linked to a polyphosphazene chain. This reduces the volatility of the borazine and allows facile fabrication of the linear high polymer. Subsequent pyrolysis at temperatures up to 1,000 °C results in breakdown of the phos-phazene carrier backbone (possibly via the formation of volatile phosphorus nitride) and formation of boron nitride. 

Polyphosphazenes are a relatively new class of biodegradable polymers. Their 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. Synthetic flexibility and versatile adaptability of polyphosphazenes make them unique for drug delivery applications. For example, Veronese et al.18 prepared polyphos-phazene microspheres with phenylalanine ethyl ester as a phosphorous substituent and loaded it with succinylsulphathiazole or naproxen. The kinetics of release from these matrices were very convenient in yielding local concentrations of the two drugs that are useful per se or when mixed with hydroxyapatite for better bone formation. Polyphosphazene matrices are also considered as potential vehicles for the delivery of proteins and vaccines.19... 

The presence of phosphorus in the polymer backbone has a veiy practical consequence, quite apart from the structural issues. Phosphorus is one of the most important elements that prevent the combustion of organic materials. The presence of both phosphorus and nitrogen is synergistic. Thus, the phosphorus-nitrogen backbone in polyphosphazenes ensures that many poly(organophosphazenes) are not only nonflammable but also quench combustion of other compounds with which they are in contact. The mechanism of this fire suppression is believed to be both an interruption of the free radical processes that occur in a flame and the formation of an intumescent char that shields the material from the ingress of oxygen. 

Monomer 89 (Scheme 10) is a ferrocenyl-substituted cyclic phosphazene, which is ring-opened to give a polyphosphazene with ferrocenyl moieties attached as side-chains to two positions on the polymer backbone. Attempted polymerization at 250°C resulted in no polymer formation however, a catalytic amount of a perchlorinated cychc phosphazene monomer under the same conditions resulted in the isolation of polymer 90. 

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