High-temperature polymer polyphosphazene

Applications. Polymers with small alkyl substituents, particularly (13), are ideal candidates for elastomer formulation because of quite low temperature flexibiUty, hydrolytic and chemical stabiUty, and high temperature stabiUty. The abiUty to readily incorporate other substituents (ia addition to methyl), particularly vinyl groups, should provide for conventional cure sites. In light of the biocompatibiUty of polysdoxanes and P—O- and P—N-substituted polyphosphazenes, poly(alkyl/arylphosphazenes) are also likely to be biocompatible polymers. Therefore, biomedical appHcations can also be envisaged for (3). A third potential appHcation is ia the area of soHd-state batteries. The first steps toward ionic conductivity have been observed with polymers (13) and (15) using lithium and silver salts (78). 

Such hybrid molecules and supramolecular solids offer the promise of systems with the flexibility, strength, toughness, and ease of fabrication of polymers, with the high temperature oxidative stability of ceramics, and the electrical or catalytic properties of metals. Polyphosphazene chemistry provides an illustration of what is possible in one representative hybrid system. 

The conventional route to prepare I generally involves a high temperature melt polymerization of hexachlorocyclotriphosphazene, or trimer (IV). Recent studies have demonstrated the effectiveness of various acids and organometalllcs as catalysts for the polymerization of IV (8). Alternate routes for the preparation of chloro-polymer which do not involve the ring opening polymerization of trimer have been reported in the patent literature (9. 10). These routes involve a condensation polymerization process and may prove to be of technological importance for the preparation of low to moderate molecular weight polyphosphazenes. 

Some of the latest work on high refractive index polyphosphazenes makes use of polymers that contain both fluoroalkoxy and di- or tri-chlorophenoxy side groups.261 These amorphous glasses are thermally stable up to 400 °C, show a large variation of refractive index with temperature, and refractive index values that vary from 1.39-1.56 depending on composition. Thus, they are candidates for uses in thermo-optical switching devices. 

Polyphosphazene synthesis provides additional possibilities for preparing liquid crystal polymers with different properties. As noted above, the substitution process (Figure 2) enables one to synthesize a wide variety of polymers. The phosphazene inorganic backbone Is a highly flexible polymer chain glass transition temperatures can... 

Properties. One of the characteristic properties of the polyphosphazene backbone is high chain dexibility which allows mobility of the chains even at quite low temperatures. Glass-transition temperatures down to —105° C are known with some alkoxy substituents. Symmetrically substituted alkoxy and aryloxy polymers often exhibit melting transitions if the substituents allow packing of the chains, but mixed-substituent polymers are amorphous. Thus the mixed substitution pattern is deUberately used for the synthesis of various phosphazene elastomers. On the other hand, as with many other flexible-chain polymers, glass-transition temperatures above 100°C can be obtained with bulky substituents on the phosphazene backbone. 

Unique combinations of properties continue to be discovered in inorganic and organometallic macromolecules and serve to continue a high level of interest with regard to potential applications. Thus, Allcock describes his collaborative work with Shriver (p. 250) that led to ionically conducting polyphosphazene/salt complexes with the highest ambient temperature ionic conductivities known for polymer/salt electrolytes. Electronic conductivity is found via the partial oxidation of unusual phthalocyanine siloxanes (Marks, p. 224) which contain six-coordinate rather than the usual four-coordinate Si. 

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). 

Closely related to polyphosphazenes is the class of polymers known as polyheterophosphazenes, where one or more of the P atoms per repeat unit is substituted by an atom of a heteroelement. The first well-characterised example of such materials involved carbon as the replacement for phosphorus the resulting macromolecules, polycarbophosphazenes, were prepared via ROP, but at a dramatically lower temperature than for (NPCl2)3 [eqn (11.37)]. Subsequently, polymers with three-coordinate sulfur(IV) and four-coordinate sulfur(VI) centres were obtained and these materials were termed poly-thiophosphazenes and polythionylphosphazenes, respectively. The latter polymers [eqn (11.38)] are much more stable than the sulfur(IV) analogues after halogen replacement and several have been explored as matrices for gas sensors as a consequence of their high permeability. 

---