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Dehydrocoupling Polymerization: Poly(silylether) Synthesis by Using an Iron β‐Diketiminate Catalyst
Author(s) -
FarcaşJohnson Mirela A.,
Kyne Sara H.,
Webster Ruth L.
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202201642
Subject(s) - silane , polymerization , monomer , polymer chemistry , polyol , polymer , catalysis , condensation reaction , diol , condensation polymer , chemistry , condensation , materials science , organic chemistry , polyurethane , physics , thermodynamics
Abstract 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.