Accessing Siloxane Functionalized Polynorbornenes via Vinyl-Addition Polymerization for CO2 Separation Membranes

Kevin R. Gmernicki; Eunice Hong; Christopher R. Maroon; Shannon M. Mahurin; Alexei P. Sokolov; Tomonori Saito; Brian K. Long

doi:10.1021/acsmacrolett.6b00435

Accessing Siloxane Functionalized Polynorbornenes via Vinyl-Addition Polymerization for CO₂ Separation Membranes

Kevin R. Gmernicki, Eunice Hong, Christopher R. Maroon, Shannon M. Mahurin, Alexei P. Sokolov, Tomonori Saito, Brian K. Long

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

50 Scopus citations

Abstract

The vinyl addition polymerization of norbornyl-based monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans-[Ni(C₆F₅)₂(SbPh₃)₂]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxane-substituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability (T_d ≥ 362 °C) and were cast into membranes that displayed high CO₂ permeability and enhanced CO₂/N₂ selectivity as compared to related materials.

Original language	English
Pages (from-to)	879-883
Number of pages	5
Journal	ACS Macro Letters
Volume	5
Issue number	7
DOIs	https://doi.org/10.1021/acsmacrolett.6b00435
State	Published - Jul 19 2016

Funding

The authors acknowledge the UTK/ORNL Science Alliance Joint Directed Research and Development program for their financial support of this work. T.S., S.M.M., and A.P.S. were sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U.S. Department of Energy.

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10.1021/acsmacrolett.6b00435

Cite this

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title = "Accessing Siloxane Functionalized Polynorbornenes via Vinyl-Addition Polymerization for CO2 Separation Membranes",

abstract = "The vinyl addition polymerization of norbornyl-based monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans-[Ni(C6F5)2(SbPh3)2]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxane-substituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability (Td ≥ 362 °C) and were cast into membranes that displayed high CO2 permeability and enhanced CO2/N2 selectivity as compared to related materials.",

author = "Gmernicki, {Kevin R.} and Eunice Hong and Maroon, {Christopher R.} and Mahurin, {Shannon M.} and Sokolov, {Alexei P.} and Tomonori Saito and Long, {Brian K.}",

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AU - Gmernicki, Kevin R.

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AU - Mahurin, Shannon M.

AU - Sokolov, Alexei P.

AU - Saito, Tomonori

AU - Long, Brian K.

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AB - The vinyl addition polymerization of norbornyl-based monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans-[Ni(C6F5)2(SbPh3)2]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxane-substituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability (Td ≥ 362 °C) and were cast into membranes that displayed high CO2 permeability and enhanced CO2/N2 selectivity as compared to related materials.

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