Dehydrocoupling Polymerization: Poly(silylether) Synthesis by Using an Iron β‐Diketiminate Catalyst

We describe the iron‐catalyzed polymerizations of diol and silane monomers to obtain fourteen different poly(silylether) products with number average molecular weights ( M n ) up to 36.3 kDa. The polymerization reactions developed in this study are operationally simple and applicable to 1° and 2° silane monomer substrates and a range of benzylic and aliphatic diol substrates as well as one polyol example. The polymers were characterized by IR spectroscopy, DSC and TGA and, where solubility allowed, 1 H, 13 C{ 1 H}, 29 Si{ 1 H} NMR spectroscopies, GPC and MALDI‐TOF were also employed. The materials obtained displayed low T g values (−70.6 to 19.1 °C) and were stable upon heating up to T –5%,Ar 421.6 °C. A trend in T –5%,Ar was observed whereby use of a 2° silane leads to higher T –5%,Ar compared to those obtained using a 1° silane. Reaction monitoring was undertaken by in situ gas evolution studies coupled with GPC analysis to follow the progression of chain‐length growth which confirmed a condensation polymerization‐type mechanism.