Polyphosphazines and polymeric sulfur nitride

Polyphosphazines

Phosphonitrilic compounds (phosphazenes) contain the –N=PX₂– unit (X = Cl, F, Br, OR, NR₂) and are formed as cyclic oligomers (NPX₂)₃, (NPX₂)₄ and long chain polymers (NPX₂)ₙ.

Preparation of phosphonitrilic chloride

1. Phosphorus pentachloride is heated with ammonium chloride at about 120–150 °C in a solvent (chlorobenzene or sym-tetrachloroethane): n PCl₅ + n NH₄Cl → (NPCl₂)ₙ + 4n HCl The main product is the cyclic trimer (NPCl₂)₃ with some tetramer.
2. On heating the trimer at about 250 °C in a vacuum (or sealed tube), ring-opening polymerisation gives the high polymer, polydichlorophosphazene (NPCl₂)ₙ, a rubber-like substance called "inorganic rubber".

        N
     /     \
  Cl₂P       PCl₂      (NPCl₂)₃ trimer:
     |       |         six-membered ring of
     N       N         alternating N and P
      \     /
       PCl₂

The P–Cl bonds are very reactive. Replacing Cl by organic groups gives stable polyorganophosphazenes:

(NPCl₂)ₙ + 2n NaOCH₃ → [NP(OCH₃)₂]ₙ + 2n NaCl (polydimethoxyphosphazene) (NPCl₂)ₙ + 2n NaOC₂H₅ → [NP(OC₂H₅)₂]ₙ + 2n NaCl (polydiethoxyphosphazene)

The repeating units (monomers) are therefore N=P(OCH₃)₂ and N=P(OC₂H₅)₂.

Uses:

• Flame-resistant and non-burning materials and coatings.
• Elastomers (fluoroalkoxy phosphazene rubber) that stay flexible from –60 °C to 180 °C: seals, O-rings, fuel hoses and gaskets in aircraft and the oil industry.
• Biomedical uses: biodegradable implants, drug delivery, artificial skin, dental materials.
• Solid polymer electrolytes for lithium batteries; membranes for gas separation.
• Water-repellent coatings, lubricants, hydraulic fluids and low-temperature insulation.

Polymeric sulphur nitride

Polythiazyl (polymeric sulphur nitride), (SN)ₓ. Preparation:

1. S₄N₄ is made by passing NH₃ into a solution of S₂Cl₂ (6S₂Cl₂ + 16NH₃ → S₄N₄ + 8S + 12NH₄Cl).
2. S₄N₄ vapour is passed over hot silver wool at 250–300 °C to give S₂N₂ crystals: S₄N₄ → 2S₂N₂ (Ag).
3. S₂N₂ polymerises in the solid state at room temperature: n S₂N₂ → 2 (SN)ₙ (golden, lustrous fibres).

Structure: chains of alternating S and N atoms, –S=N–S=N–. (SN)ₓ conducts electricity like a metal along the chain direction and becomes superconducting at about 0.3 K.

Uses: an example of a conducting polymer without carbon, used in studies of one-dimensional conductors, microelectronic and photoconducting devices.