Polyphosphazenes

Abstract

Polyphosphazenes comprise by far the largest class of inorganic macromolecules. At least 700 different polymers of this type have been synthesized, with a range of physical and chemical properties that rivals that known hitherto only for synthetic organic macromolecules. Most polyphosphazenes have the general molecular structure. The polymer backbone consists of alternating phosphorus and nitrogen atoms, with two side groups, R, being attached to each phosphorus. The side groups may be organic, organometallic, or inorganic units. Each macromolecule typically contains from 100 to 15,000 or more repeating units linked end to end, which means that (depending on the organic side groups) the highest molecular weights are in the range of 2 million to 10 million. The bonding structure in the backbone is formally represented as a series of alternating single and double bonds. However, this formulation is misleading. Structural measurements suggest that all the bonds along the chain are equal or nearly equal in length, but without the extensive conjugation found in organic polyunsaturated materials. This anomaly will be discussed later. In addition to linear polyphosphazenes with one type of side group, other molecular architectures have also been assembled. These include polyphosphazenes in which two or more different side groups, R1 and R2, are arrayed along the chain in random, regular, or block distributions. Other species exist with short phosphazene branches linked to phosphorus atoms in the main chain. Also available are macromolecules in which carbon or sulfur replace some of the phosphorus atoms in the skeleton. Star-geometry structures, using the symbolism defined, are also accessible. A new and growing area is the field of phosphazene-organic and phosphazene-polysiloxane hybrid linear copolymers, and comb copolymers of the types. In addition, polymers are known in which six-membered phosphazene rings are side groups linked to organic polymers, and where phosphazene rings are linked by organic connector groups to form cyclolinear or cyclomatrix materials.