A method for the synthesis of well-defined mono-, di-, and mixed-telechelic polyphosphazenes produced via a living cationic polymerization of phosphoranimines is described. Amino phosphoranimines R-NH(CF3CH2O)2P=NSiMe3 (R = Ph-, p-BrPh-, p-H3CPh-, CH2=CHCH2-, and CH2=CHPh-) were synthesized via a reaction between a bromophosphoranimine and the appropriate organic amine. Ditelechelic polymers [R-NH]2-[Cl2P=N]n were prepared by quenching living poly(dichlorophosphazene) chains, [Cl3P=N(Cl2P=N)n-PCl3] +[PCl6]- with small quantities of the amino phosphoranimines. Cationic initiators of the amino phosphoranimines were also generated using PCls and were used to polymerize Cl3P=NSiMe3, to give monotelechelic poly(dichlorophosphazenes). In addition, a mixed telechelic system was produced by the termination of an allylamino monotelechelic poly(dichlorophosphazene) chain with a bromoanilino phosphoranimine. In all cases, displacement of the chlorine atoms with sodium trifluoroethoxide yielded hydrolytically stable telechelic polymers with controlled molecular weights and low polydispersities.
All Science Journal Classification (ASJC) codes
- Organic Chemistry
- Polymers and Plastics
- Inorganic Chemistry
- Materials Chemistry