Organosilylphosphazene oligomers and polymers: synthesis via (lithioaryloxy)phosphazenes

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.

New Polyphosphazenes with Unsaturated Side Groups: Use as Reaction Intermediates, Cross-Linkable Polymers, and Components of Interpenetrating Polymer Networks

“…Hybrid organophosphazene/organosilicon polymers have been prepared by several routes in the past. − The method described here involves the addition of dimethylethoxysilane (to form 14 ) or heptamethyltrisiloxane followed by dimethylethoxysilane (to yield 15 ) to the allyl double bond of 13 , both reactions being carried out in the presence of platinum divinyltetramethyldisiloxane complex as a coupling agent. Polymer 14 is a transparent, beige, amorphous material with a T g of +42 °C.…”

Synthesis and Characterization of Aminoorganosiloxane-Bearing Polyphosphazenes: New Properties by the Elimination of Hydrogen Bonding

“…Synthesis of N 3 P 3 (OPh) 5 Cl (5). The synthesis of compound 5 followed the literature procedure. , …”

“…The uses of such polymers in membranes and in hydrophobic surfaces are subjects of additional interest. Several research groups have explored the possibility that hybrid systems of this type may be accessible. − However, until recently, relatively few successful macromolecular syntheses have been described. − …”

Synthesis and Characterization of Organometallic Polyphosphazenes and Their Applications in Nanonoscience

“…The difficulty of preparing polyphosphazene containing anchored silicon groups has been pointed out by Allcock et al [49][50][51][52][53][54][55]. Previous attempts [55].…”