Synthesis of Norbornenyl Telechelic Polyphosphazenes and Ring-Opening Metathesis Polymerization Reactions

Abstract

Mono- and ditelechelic linear polyphosphazenes, functionalized with a norbornene end group, were synthesized through the termination of living poly(dichlorophosphazene) with norbornenyl phosphoranimines. These materials were employed as macromonomers for the synthesis of graft copolymers via the ring-opening metathesis polymerization (ROMP) of the terminal norbornenyl component. Norbornenyl monotelechelic polyphosphazenes with various molecular weights yielded un-cross-linked graft copolymers when subjected to ROMP. The ditelechelic polyphosphazenes yielded branched or cross-linked materials due to the multiple reactive sites. In addition, the 5-norbornene-2-methoxy phosphoranimine was polymerized via ROMP to yield materials that consisted of a polynorbornene backbone with phosphoranimine pendent side groups.

Ruthenium‐based metathesis initiators: Development and use in ring‐opening metathesis polymerization

“…Unfortunately, this leads to a decreased device performance 255. ROMPs of poly(phosphazene)s with one norbornenyl end group using 11b yielded noncrosslinked graft copolymers 256…”

Determination of 31P,31P coupling constants in cyclotriphosphazenes and their influence on 1H and 13C NMR spectra of phosphorus substituents

“…In 1992, Chapuis 34 described another chiral CTP and measured 2 J(P,P) (69.1 Hz) between two P(OPh) 2 groups. Other chiral cyclotriphosphazenes have been described 35 but no indication of any 31 P anisochrony was given.…”

Chain‐End‐Functionalized Polyphosphazenes via a One‐Pot Phosphine‐Mediated Living Polymerization

“…[12] Other studies, however, have shown that R 3 P = N–SiMe 3 bearing alkoxy or aryloxy groups did not form a stable cationic species to induce the polymerization of Cl 3 P = N–SiMe 3 , and were only able to quench the polymerization. [13] The preparation of functional organophosphoranimines also often requires multiple step synthesis, for example, via a bromophosphoranimine precursor, [14] and the repeated vacuum distillations required for purification lead to extensive and time-consuming preparation and extensive handling of toxic phosphoranimines. In an alternative approach, it has been shown that, in the absence of PCl 5 , dichlorophosphoranes can also initiate the polymerization of Cl 3 P = N–SiMe 3 [15] and that this could be exploited to prepare organometallic-inorganic block copolymers.…”