Synthesis of Poly(alkyl/arylphosphazenes) via the Ambient Temperature Phosphite-Mediated Chain-Growth Polycondensation of (<i>N</i>-Silyl)bromophosphoranimines
作者:Thomas J. Taylor、Alejandro Presa Soto、Keith Huynh、Alan J. Lough、Anthony C. Swain、Nicholas C. Norman、Christopher A. Russell、Ian Manners
DOI:10.1021/ma100876z
日期:2010.9.28
polymerizations were complete within 18 h. The polymers prepared include poly(dialkylphosphazenes) (e.g., [nBu2P═N]n1b), poly(alkylarylphosphazenes) (e.g., [PhMeP═N]n1d), new materials featuring unsaturated substituents (e.g., [nHexH2C═C(H)CH2}P═N]n1n), and random copolymers (e.g., [PhMeP═N]x−[PhnBuP═N]y} where x:y = 2:1, 7a). The precursor silylaminophosphines RR′P−N(SiMe3)2 (5a−q) and bromo(silylamino)phosphoranimines
室温加入化学计算量的亚磷酸三甲酯,P(OME)的3,以ñ -甲硅烷(卤代)organophosphoraniminesBrRR'P═NSiMe 3中导致直接形成高分子量聚磷腈的[RR'P═N氯化溶剂] n。大多数聚合反应在18小时内完成。制备的聚合物包括聚(dialkylphosphazenes)(例如,[ Ñ卜2 P = N] Ñ 1B),聚(alkylarylphosphazenes)(例如,[PhMeP═N] Ñ 1D),新材料设有不饱和取代基(例如,[ Ñ十六进制H 2 C = C(H)CH 2 } P = N] ñ1N),和无规共聚物(例如,[PhMeP═N] X - [PH Ñ BuP═N] ý }其中X:Ý = 2:1,图7a)。前体silylaminophosphines RR'P-N(森达3)2(5A - q)和溴(甲硅烷)phosphoraniminesBrRR'P═NSiMe