Cyclic and high polymeric phosphazenes have been synthesized with aminosiloxane side groups either as the sole substituent or with cosubstituents such as OCH2CF3, OCH2CH2OCH2CH2OCH3, or OC6H5. Small-molecule model compound reactions were first carried out between N3P3(OPh)5Cl and H2N(CH2)3SiMe2OSiMe3 or H2N(CH2)3Si(OSiMe3)3 to yield the pentaphenoxymonoaminosiloxy derivatives N3P3(OPh)5NH(CH2)3SiMe2OSiMe3 and N3P3(OPh)5NH(CH2)3Si(OSiMe3)3. Following the structural identification of these species, similar reactions were carried out between the high polymeric phosphazenes [NP(R)xCly]", where R = OCH2CF3, OPh, or OCH2CH2OCH2CH2OCH3, x = 0, 0.5, or 1.5, y = 2x, and = 15 000, and the same two aminosiloxanes. The molecular structures of the final polymers were deduced from a combination of elemental analysis and 1H NMR integration. The substituent distribution and thermal-, surface-, and solid-state properties of the aminosiloxyphosphazene polymers are described.The synthesis of new polymers with a phosphazene backbone and organosilicon side groups offers the prospect of access to new materials with unusual characteristics.2'8 Such polymers may combine the advantages of poly-siloxanes9 with those of polyphosphazenes.10 Their behavior as membranes, elastomers, and biomaterials is of considerable interest.

No abstract

A series of poly(organophosphazenes) with the general structure [NPtRhtOCeHsh.,],,, wherex < 2 and R = OCeRUSiMes, OCeH4SiMe2Ph, OCeH4SiMePh2, OCeH4Br, and OCH2CF3, and the ferrocenyl polymer [NsPstOC^CFsMij-CsH^Fe] were synthesized. Molecular structural characterization for these polymers was achieved by and 31P NMR, gel permeation chromatography, elemental microanalysis, and differential scanning calorimetry. Films of these polymers were examined with respect to their permeability to O2, N2, C02, He, and CH4, and selectivity ratios were established. The effect of cross-linking on both the permeation and selectivity values for films of the silyl-bearing polymers was also investigated. The change in permeability and selectivity as a function of side group structure variations, free volume effects, gas pressure, and glass transition temperature (Tt) is discussed. Poly[bis(trifluoroethoxy)phosphazene] was found to have oxygen permeabilities comparable to those of poly(dimethylsiloxane) but with higher permselectivities.

No abstract

Price, T. R.; Cozzens, R. F.; Echols, W. H. Macromoles 1974, 7, 937. Shirota, Y.; Yoshimura, M.; Matsumoto, A.; Mikawa, H. Macromolecules 1974, 7, 4. Wang, Y.-G.; Morawetz, H. Makromol. Chem. Suppl. 1975,1, 283. Morishima, Y.; Lim, H. S.; Nozakura, S.; Sturtevant, J. L.ABSTRACT (Lithioary1oxy)phosphazenes have been used as reaction intermediates for the synthesis of phosphazenes that bear organosilicon side groups. The synthetic pathways were developed at two levels, first with the use of small-molecule cyclic phosphazenes as reaction models and second with high polymeric phosphazenes. The cyclic small molecule N3P3(OPh),0C6H4Br-p was first lithiated to N3P3(OPh),0C$I,Li-p, and this compound was allowed to react with a range of organochlorosilanes or with hexamethylcyclotrisiloxane to yield the species N3P3(OPh)50C6H4R-p, where R is SiMe,, SiMe'Ph, SiMePh', SiMe2CH=CH2, SiMe2-(OSiMe2)20SiMe2Bu, and SiMe2(OSiMe2)20SiMe3. At the high polymer level, the macromolecule [ NP-(OC&,Fk)2]n was subjected to partial lithiation followed by coupling to chlorosilanes or to ring-opening addition of (OSiMe2)3 to generate polymers with OC6H5 and OC6H4Br-p side groups as well as OC,H4R'-p units, where R' is SiMe3, SiMe2Ph, SiMePh2, or SiMe2(OSiMe&OSiMe3. Molecular structural characterization was obtained by NMR, IR, microanalytical, and mass spectrometric methods. Glass transition temperatures for the high polymers were in the range +45 to -68 "C.The synthesis of new macromolecules derived from the inorganic elements provides opportunities for the extension 0024-9297/89/2222-3571$01.50/0 of both polymer chemistry and inorganic chemistry into fields as diverse as solid-state science, electronics research, ABSTRACT It has been so far reported that some polymer blends containing random copolymers can be miscible in a certain range of copolymer compositions even though the combinations of their corresponding homopolymers are immiscible. On the other hand, according to theory, there may exist some copolymer blends that are immiscible in a certain range of copolymer compositions even though their corresponding homopolymers are miscible with each other. For real blends with a possibility of such an immiscibility region, the dependence of miscibility on the copolymer composition was observed at the blend ratio 1/1. Poly(viny1 chloride-co-vinyl acetate) copolymers (VC-VAc) were immiscible with poly(n-butyl methacrylate-co-isobutyl methacrylate) copolymers (nBMAiBMA) in a certain range of copolymer compositions of nBMASiBMA, though every pair of VC-VAc copolymer/nBMA homopolymer, VC-VAc copolymer/iBMA homopolymer, and nBMA homopolymer/iBMA homopolymer was miscible.