TY - JOUR
T1 - Dehydrocoupling Polymerization: Poly(silylether) Synthesis by Using an Iron β-Diketiminate Catalyst
AU - Farcas-Johnson, Mirela A.
AU - Kyne, Sara H.
AU - Webster, Ruth L.
N1 - Funding Information:
We thank the University of Bath and Monash University for a joint PhD studentship from the Bath Monash Global PhD Programme in Sustainable & Circular Technologies (awarded to MAFJ). RLW thanks the EPSRC for funding. We gratefully acknowledge discussions and assistance provided by Dr. Maciej Kopeć, along with analysis help from Dr. Rémi Castaing (MC2) and Dr. Martin Levere (MC2). Dr. Muhammad Kamran is thanked for provision of 2,5-bis(hydroxymethyl)furan.
Funding Information:
We thank the University of Bath and Monash University for a joint PhD studentship from the (awarded to MAFJ). RLW thanks the EPSRC for funding. We gratefully acknowledge discussions and assistance provided by Dr. Maciej Kopeć, along with analysis help from Dr. Rémi Castaing (MC) and Dr. Martin Levere (MC). Dr. Muhammad Kamran is thanked for provision of 2,5‐bis(hydroxymethyl)furan. Bath Monash Global PhD Programme in Sustainable & Circular Technologies 2 2
PY - 2022/11/7
Y1 - 2022/11/7
N2 - 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,
1H,
13C{
1H},
29Si{
1H} 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.
AB - 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,
1H,
13C{
1H},
29Si{
1H} 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.
KW - dehydrocoupling
KW - homogeneous catalysis
KW - iron
KW - poly(silylether)s
KW - polymerizations
UR - http://www.scopus.com/inward/record.url?scp=85137582370&partnerID=8YFLogxK
U2 - 10.1002/chem.202201642
DO - 10.1002/chem.202201642
M3 - Article
SN - 0947-6539
VL - 28
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 62
M1 - e202201642
ER -