Polymer, volume 260, pages 125371
Alternating copolymerization of carbon dioxide with alicyclic epoxides using bimetallic nickel(II) complex catalysts containing benzotriazole-based salen-type derivatives: Catalysis and kinetics
Publication type: Journal Article
Publication date: 2022-11-01
Materials Chemistry
Organic Chemistry
Polymers and Plastics
Abstract
A series of dinuclear nickel complexes based on hexadentate bis(benzotriazole iminophenolate) derivatives with the 1,4-butylene diimine bridging backbone have been synthesized and characterized by single crystal x-ray crystallography. Dinickel complex 1 was demonstrated to be an efficient catalyst for alternating copolymerization of carbon dioxide (CO 2 ) with cyclohexene oxide (CHO) or 4-vinyl-1,2-cyclohexene oxide (VCHO), affording CO 2 -based polycarbonates with >99% carbonate linkages under the optimized conditions. Particularly, not only the effective catalytic property of binickel complex 1 for CO 2 -copolymerization of alicyclic epoxides is enabled, but also 1 has been demonstrated to reveal an “immortal” manner in the CO 2 /VCHO copolymerization. Using the dinickel catalyst 1 in combination with excess diol derivatives as the chain transfer agents could produce very narrowly distributed poly(vinylcyclohexene carbonate) polyols having molecular weights ranging from 5000 to 12000 g/mol. In addition, detailed kinetic studies of the CO 2 /CHO copolymerization by Ni catalyst 1 were investigated. The results showed that such copolymerization follows a first-order kinetics on both catalyst 1 and CHO concentrations. New structurally well-defined dinickel complex 1 was developed to investigate its catalysis and kinetics for CO 2 -copolymerization of alicyclic epoxides. • ►New dinickel complexes based on BT-derived salen-type ligands were synthesized. • ►Catalysis and kinetics of CO 2 /CHO copolymerization by dinickel 1 were studied. • ► 1 could effectively mediate CO 2 /VCHO copolymerization in an immortal manner. • ►Copolymerization is first order in both catalyst 1 and CHO concentrations.
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Dalton Transactions
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Russian Chemical Reviews
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Royal Society of Chemistry (RSC)
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Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii
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Liu G., Ko B. Alternating copolymerization of carbon dioxide with alicyclic epoxides using bimetallic nickel(II) complex catalysts containing benzotriazole-based salen-type derivatives: Catalysis and kinetics // Polymer. 2022. Vol. 260. p. 125371.
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Liu G., Ko B. Alternating copolymerization of carbon dioxide with alicyclic epoxides using bimetallic nickel(II) complex catalysts containing benzotriazole-based salen-type derivatives: Catalysis and kinetics // Polymer. 2022. Vol. 260. p. 125371.
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TY - JOUR
DO - 10.1016/j.polymer.2022.125371
UR - https://doi.org/10.1016/j.polymer.2022.125371
TI - Alternating copolymerization of carbon dioxide with alicyclic epoxides using bimetallic nickel(II) complex catalysts containing benzotriazole-based salen-type derivatives: Catalysis and kinetics
T2 - Polymer
AU - Liu, Guanlin
AU - Ko, Bao-Tsan
PY - 2022
DA - 2022/11/01 00:00:00
PB - Elsevier
SP - 125371
VL - 260
SN - 0032-3861
ER -
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@article{2022_Liu,
author = {Guanlin Liu and Bao-Tsan Ko},
title = {Alternating copolymerization of carbon dioxide with alicyclic epoxides using bimetallic nickel(II) complex catalysts containing benzotriazole-based salen-type derivatives: Catalysis and kinetics},
journal = {Polymer},
year = {2022},
volume = {260},
publisher = {Elsevier},
month = {nov},
url = {https://doi.org/10.1016/j.polymer.2022.125371},
pages = {125371},
doi = {10.1016/j.polymer.2022.125371}
}