Sulfur-nitrogen-phosphorus polymers

I. Manners, Sulfur-Nitrogen-Phosphorus Polymers, Coord. Chem. Rev., 137, 109 (1994). 

Condensation Routes to Sulfur-Nitrogen-Phosphorus Polymers. . 158... 

Sulfur-nitrogen-phosphorus polymers possess backbones which can be regarded as compositional hybrids of those present in sulfur-nitrogen polymers, such as the solid state polymer poly(sulfur nitride) [SN]X or polyoxothiazenes... 

Sulfur-nitrogen-phosphorus polymers possess backbones that can be regarded as compositional hybrids of those present in sulfur-nitrogen polymers, such as the solid-state polymer poly(sulfur nitride) [SNh or polyoxothiazenes [RS(0)=N]n and classical polyphosphazenes, [R2P=N] (1) (92). Poly(sulfur nitride), [SNh, possesses remarkable properties such as electrical conductivity at room temperature and superconductivity below 0.3 K (93). [SNh is insoluble and has a polymeric structure in the solid state with interchain S - S interactions. As these interactions are crucial to the properties of the material, [SNl is best regarded as a solid-state polymer rather than a polymeric material with discrete macromolecu-lar chains of the type discussed in this article. 

The first well-characterized examples of sulfur-nitrogen-phosphorus materials, polythiophosphazenes, were reported in 1990 (94). These polymers were prepared via the thermal ROP of a cyclothiophosphazene (eq. 25). This yielded the hydrolytically sensitive polythiophosphazene (26) with a backbone of three-coordinate sulfur(IV), nitrogen, and phosphorus atoms. Although reaction of (26) with nucleophiles such as aryloxides yielded materials (27) with improved hydrolytic stability, degradation was still rapid except where very bulky substituents such as o-phenylphenoxy were present. 

Part 2 includes chapters on specific classes of cyclic monomers and their polymerization mechanisms and kinetics, their main (co)polymer architectures and related products, as well as current and future applications. Hence, siloxane-con-taining and sulfur-nitrogen-phosphorus-containing polymers are described in Chapters 3 and 4, respectively, while the polymerization of cyclic depsipeptides, ureas and urethanes, of polyethers and polyoxazolines, and of polyamides are detailed in Chapters 5, 6 and 7, respectively. Chapters 9, 10, 11 and 12 include details of polyesters prepared from either P-lactones, from dilactones, from larger lactones and from polycarbonates, while the polymerization of cycloalkanes is described in Chapter 13. It should be noted that, slightly out of place . Chapter 8 covers the subject of ring-opening metathesis polymerizahon. 

Step 1 Analysis of the components for known toxic or harmful substances search for polymers which biodegrade slowly or are not biodegradable (theoretical approach from the product data sheet) search for heteroatoms (chlorine, nitrogen, phosphorus, sulfur and so on) and aromatic hydrocarbons (again a theoretical approach but analysis is possible). 

HPLC is one of the most universal methods for determining the enantiomeric composition of substances and mixtures in a short time frame. Its application is not restricted to molecules in which chirality is based on a quaternary carbon atom with four different substituents it can also be employed for compounds containing a chiral silicon, nitrogen, sulfur, or phosphorus atom. Likewise, asymmetric sulfoxides or aziridines, the chirality of which is based on a lone electron pair, can be separated. Chirality can also be traced back to helical structures, as in the case of polymers and proteins to the existence of atropiso-merism, the hindered rotation about a single bond, as observed, for example, in the case of binaphthol, or to spiro compounds. 

Combustion in a Parr Bomb with sodium peroxide, sucrose and benzoic acid in a gelatine capsule is the basis of a method for determining silica in polymers. Boron, halogens, nitrogen, phosphorus, and sulfur do not interfere. 

This qualitative oxygen flask combustion method [29] enables nitrogen, fluorine, chlorine, bromine, iodine, sulfur and phosphorus to be identified in polymers in amounts down to 0.01%. 

Nitrogen, fluorine, chlorine, bromine and iodine, sulfur and phosphorus are quantitatively detected in polymers in the solution resulting from a single oxygen combustion. Semi quantitative data can be obtained on the same solntions for nitrogen, fluorine, chlorine, sulfur and phosphorus. 

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