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Updated: Sep 22, 2025
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A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes
Published on: February 27, 2017
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Accessing Siloxane Functionalized Polynorbornenes via Vinyl-Addition Polymerization for CO2 Separation Membranes
Kevin R Gmernicki1, Eunice Hong1, Christopher R Maroon1
1Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996-1600, United States.
ACS Macro Letters
|May 26, 2022
Summary
A novel nickel catalyst enables efficient synthesis of high molecular weight siloxane-substituted norbornyl polymers. These polymers exhibit excellent thermal stability and superior CO2 permeability for membrane applications.
Area of Science:
- Polymer Chemistry
- Organometallic Catalysis
- Materials Science
Background:
- Vinyl addition polymerization of norbornyl monomers with polar groups often results in low molecular weight polymers and poor yields.
- Developing efficient polymerization methods for functionalized norbornyl monomers is crucial for advanced material applications.
Purpose of the Study:
- To demonstrate the effectiveness of a specific nickel catalyst, trans-[Ni(C6F5)2(SbPh3)2], for the addition-type homopolymerization of siloxane-substituted norbornyl-based monomers.
- To characterize the synthesized polymers for molecular weight, thermal stability, and gas separation properties.
Main Methods:
- Utilized the trans-[Ni(C6F5)2(SbPh3)2] catalyst for vinyl addition polymerization of siloxane-substituted norbornyl monomers.
- Conducted polymerizations under optimized conditions and analyzed reaction kinetics.
- Characterized polymer properties including molecular weight (GPC), thermal stability (TGA), and gas permeability/selectivity (membrane testing).
Main Results:
- Achieved moderate to high monomer conversion in as little as 5 minutes of polymerization.
- Synthesized siloxane-substituted polymers with molecular weights exceeding 100 kg/mol.
- Obtained polymers with excellent thermal stability (decomposition temperature, Td ≥ 362 °C).
Conclusions:
- The trans-[Ni(C6F5)2(SbPh3)2] catalyst provides a highly effective route for synthesizing high molecular weight siloxane-substituted norbornyl polymers.
- These novel polymers demonstrate promising properties for membrane applications, including high CO2 permeability and enhanced CO2/N2 selectivity.
- This work establishes a proof-of-principle for a new catalytic system in polymer synthesis with potential for gas separation materials.
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