Macromolecular and Materials Design Using Polyphosphazenes

Abstract

A 279 781 .ENTAT0704N0188I ~ ~ut qf q~c fl~ D~Cu~m q tle IMO tOE r.. nq -flhtfli cisoet s Saeeci nq *%.Sungq eatsa vn LA7 a ma *qtte tro COII."IIOA ou tnst iO .ree, iM W aralq but* oM tm ate OC 4ft Ottwsl a 0oe l o s tp4.% ou'et onto vv41n*qton meoooo-Aat-r $4"voee, otrectorate for infformatiOqN O{4WI49M•AeI, •t$ 1&04 "00"sl~r "te cfficeIt mf anaqqm" t aa s get. 0 -100twOtt Retf tn Pr la`tt (0 ?04. Reproduction in whole or in part is permitted for any purpose of the United States Government. This document has been approved for public release; distribution is unlimited. ABSTRACT (Maximum 200 words)Polyphosphazenes are among the most versatile of all polymers. This is a consequence of the unique properties of the phosphorus-nitrogen backbone and the ease with which a wide range of different side groups can be introduced mainly by macromolecular substitution, but also by the polymerization of different "monomers". This field has reached a stage where the fundamental chemistry now allows the design and synthesis of a broad range of new materials that are valuable for properties such as elasticity, high refractive index, liquid crystallinity, ferroelectric-, NLO-, and photochromic attributes, and for uses as solid ionic conductors, biomedical microencapsulation polymers, and materials with controlled surface properties. Polyphosphazenes are among the most versatile of all polymers. This is a consequence of the unique properties of the phosphorus-nitrogen backbone and the ease with which a wide range of different side groups can be introduced mainly by macromolecular substitution, but also by the polymerization of different "monomers". This field has reached a stage where the fundamental chemistry now allows the design and synthesis of a broad range of new materials that are valuable for properties such as elasticity, high refractive index, liquid crystallinity, ferroelectric-, NLO-, and photochromic attributes, and for uses as solid ionic conductors, biomedical microencapsulation polymers, and materials with controlled surface properties. Inorganic-Organic Polymers as Components of New MaterialsMaterials science covers a very broad range of substances within the four main classical categories of ceramics, metals, semiconductors/electro-optical solids, and petrochemical polymers.Most of the examples in the first three categories are inorganic ip composition, while the last is mainly organic.All four have advantages and disadvanges. For example, the totally inorganic materials are heavy, often britttle, and difficult to fabricate. On the other hand, conventional polymers are tough and easy to fabricate but are unstable at elevated temperatures and lack many of the interesting electrical and optical properties of the inorganic materials.The main concept behind the current interest in inorganic or inorganic-organic polymers is that they may provide a means for the preparation of new materials that combine the advantages and minimize the disadvantages of the classical materials. Thus, the long term interest lies in the d...

The synthesis of functional polyphosphazenes and their surfaces

“…The first step involves the preparation of poly(dichlorophosphazene) (3), and the second requires the replacement of the chlorine atoms in 3 by reactions with organic or organome-tallic nucleophiles. [5][6][7][8][9][10][11][12][13] The overall sequence is shown in Scheme 1.…”

Recent Research Progress in the Synthesis of Polyphosphazene and Their Applications

“…8. Other catalysts such as sulfamic acids, ammonium sulfamate, p-toluene sulfonic acid or benzene sulfonic acid were used at lower temperature (210 • C) to increase the reaction rate [16,20,31,32].…”

“…There are many methods for the synthesis of polyphosphazenes due to presence of different substituents, but an easy route for the synthesis of polyphosphazenes at controlled temperature is living cationic polymerization [5,31,34,35]. By this method, polyphosphazene block co-polymers are synthesized conveniently and polyphosphazenes are produced with wide range of different macromolecule block structures; for example, polyphosphazene-block-polyphosphazene copolymers [5], poly(ethylene oxide)-block-polyphosphazene co-polymers [36,37] and polystyrene-block polymer phosphazene co-polymers [38,39].…”

The Chemistry of Phosphazenes. Synthetic Applications of Cα-Lithiated Derivatives

“…Keeping the temperature low, allowed to isolate the expected βhydroxyphosphazenes (112) and (113) in high yield and stereoselectivity. For that purpose, metalated (106) was treated with an aldehyde at -80 ºC during 2h.…”