Portal de Periódicos da CAPES

Deprotonation−Substitution Reactions of Poly(Methylalkylphosphazenes) and Their N -Silylphosphoranimine Precursors

1998; American Chemical Society; Volume: 31; Issue: 6 Linguagem: Inglês

10.1021/ma9711194

1520-5835

Patty Wisian‐Neilson, Cuiping Zhang, Karl A. Koch,

Ferrocene Chemistry and Applications

Diethyl ether solutions of the phosphoranimines, Me3SiNP(OPh)(CH3)(R) {R = n-Bu, n-Hex} and tetrahydrofuran (THF) solutions of the polymers [Et(Ph)PN]n, [Me(n-Bu)PN]n, and [Me(n-Hex)PN]n were sequentially treated with n-BuLi and appropriate electrophiles to afford new phosphoranimines, Me3SiNP(OPh)(CH2SiMe3)(R) {R = n-Bu, n-Hex} and Me3SiNP(OPh)(CH2PPh2)(n-Bu), and new copolymers, [Et(Ph)PN]x{[(CH3)(Me3Si)CH](Ph)PN}y, [Me(R)PN]x{[(Me3Si)CH2](R)PN}y, and [Me(R)PN]x{[(η5−C5H5)Fe(η5−C5H4)CH(OH)CH2](R)PN}y. The new phosphoranimines were characterized by elemental analysis and 1H, DEPT 13C, and 31P NMR spectroscopy. The new polymers were characterized by elemental analysis, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), 1H and 31P NMR spectroscopy, contact angle measurements, and density measurements. The range of substitution of the polymers {i.e., [y/(x + y)] × 100} was 30−70% as determined by elemental analysis. Glass transition temperatures and molecular weights of the derivatives were both higher than the parent polymers. Measurements of Young's contact angles (θY) indicated that the incorporation of Me3Si and ferrocene groups into the polymers increased the hydrophobicity relative to unsubstituted poly(dialkylphosphazenes).