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.
