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

Mirela A. Farcas-Johnson; Sara H. Kyne; Ruth L. Webster

doi:10.1002/chem.202201642

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

Mirela A. Farcas-Johnson, Sara H. Kyne, Ruth L. Webster

Monash University

Research output: Contribution to journal › Article › peer-review

8 Citations (SciVal)

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, 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.

Original language	English
Article number	e202201642
Journal	Chemistry - A European Journal
Volume	28
Issue number	62
Early online date	20 Jul 2022
DOIs	https://doi.org/10.1002/chem.202201642
Publication status	Published - 7 Nov 2022

Bibliographical note

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

Keywords

dehydrocoupling
homogeneous catalysis
iron
poly(silylether)s
polymerizations

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/chem.202201642Licence: CC BY

Cite this

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title = "Dehydrocoupling Polymerization: Poly(silylether) Synthesis by Using an Iron β-Diketiminate Catalyst",

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, 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. ",

keywords = "dehydrocoupling, homogeneous catalysis, iron, poly(silylether)s, polymerizations",

author = "Farcas-Johnson, {Mirela A.} and Kyne, {Sara H.} and Webster, {Ruth L.}",

note = "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 Kope{\'c}, along with analysis help from Dr. R{\'e}mi 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 Kope{\'c}, along with analysis help from Dr. R{\'e}mi 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 ",

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doi = "10.1002/chem.202201642",

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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

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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

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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 -

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

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

EC Fellowship - Cast Iron Catalysis: New Protocols for the Synthesis of Carbon-Phosphorus Bonds

Cite this

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

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

EC Fellowship - Cast Iron Catalysis: New Protocols for the Synthesis of Carbon-Phosphorus Bonds

Cite this