Hydrogen Bond Donor Catalyzed Cationic Polymerization of Vinyl Ethers
Veronika Kottisch
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorJanis Jermaks
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorJoe-Yee Mak
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorRyan A. Woltornist
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorCorresponding Author
Tristan H. Lambert
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorCorresponding Author
Brett P. Fors
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorVeronika Kottisch
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorJanis Jermaks
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorJoe-Yee Mak
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorRyan A. Woltornist
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorCorresponding Author
Tristan H. Lambert
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorCorresponding Author
Brett P. Fors
Department of Chemistry and Chemical Biology, Baker Lab, Cornell University, Ithaca, NY, 14853 USA
Search for more papers by this authorAbstract
The synthesis of high-molecular-weight poly(vinyl ethers) under mild conditions is a significant challenge, since cationic polymerization reactions are highly sensitive to chain-transfer and termination events. We identified a novel and highly effective hydrogen bond donor (HBD)–organic acid pair that can facilitate controlled cationic polymerization of vinyl ethers under ambient conditions with excellent monomer compatibility. Poly(vinyl ethers) of molar masses exceeding 50 kg mol−1 can be produced within 1 h without elaborate reagent purification. Modification of the HBD structure allowed tuning of the polymerization rate, while DFT calculations helped elucidate crucial intermolecular interactions between the HBD, organic acid, and polymer chain end.
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