Mechanistic Insights of BHT-Mg-Catalyzed Ethylene Phosphate’s Coordination Ring-Opening Polymerization: DFT Modeling and Experimental Data
Abstract
:1. Introduction
2. Materials and Methods
3. Results
3.1. DFT Modeling of the Formation of the Catalytic Species
3.2. DFT Modeling of the Mononuclear ROP Mechanism
3.2.1. Initiation Stage
3.2.2. Propagation Stage
3.3. DFT Modeling of the Binuclear ROP Mechanism
3.3.1. Initiation Stage
3.3.2. Propagation Stage
3.4. Polymerization Experiments
4. Discussion
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Molecule | MI-1 | MTS-12 | MI-2 | MTS-23 | MI-3 | MI-4 | MI-1m |
ΔGMI-1, kcal/mol | 0.0 | 6.6 | −2.8 | 8.5 | −3.7 | −7.0 | −2.3 |
ΔHMI-1, kcal/mol | 0.0 | 3.5 | −6.0 | 3.6 | −7.1 | −8.9 | −12.4 |
Molecule | MTS-45 | MI-5 | MI-5m | MTS-56 | MI-6 | MI-6m | MI-4m |
ΔGMI-1, kcal/mol | −6.8 | −7.6 | −0.2 | 2.7 | −11.4 | −1.7 | −5.7 |
ΔHMI-1, kcal/mol | −10.2 | −9.9 | −17.7 | −2.9 | −13.8 | −17.6 | −16.8 |
Molecule | DI-1 | DI-1i | DTS-12 | DTS-12i | DTS-12r | DI-2i | DI-2r |
ΔGMI-1, kcal/mol | 0.0 | −3.2 | 13.1 | 12.5 | 17.4 | 10.7 | 9.5 |
ΔHMI-1, kcal/mol | 0.0 | 13.4 | 9.4 | 23.8 | 28.6 | 21.5 | 22.8 |
Molecule | DTS-23i | DI-3i | DI-3 | DTS-34a | DTS-34b | DI-4a | DI-4b |
ΔGMI-1, kcal/mol | 10.7 | −6.1 | −14.7 | 3.8 | 8.4 | 2.7 | 6.5 |
ΔHMI-1, kcal/mol | 21.5 | 6.8 | −13.1 | 0.9 | 5.1 | −0.8 | 5.3 |
Molecule | DI-5 | DI-6 | DTS-67 | DI-7 | DTS-78 | DI-8 | DI-5m |
ΔGMI-1, kcal/mol | −21.1 | −9.6 | −1.8 | −9.9 | 4.1 | 4.1 | −16.6 |
ΔHMI-1, kcal/mol | −19.2 | −21.6 | −15.5 | −25.1 | −13.4 | −10.0 | −24.1 |
Run | Monomer | Reac. time, (a) min | Reac. T, °C | Conv., % (b) | Mntheo × 103 (c) | MnNMR × 103 (d) | MnSEC × 103 | ÐM | ΔG≠ kcal/mol |
---|---|---|---|---|---|---|---|---|---|
1 | εCL | 10 | 5 | 54 | 6.3 | 6.8 | 6.44 (e) | 1.18 | 21.7 (f) |
2 | rac-LA | 10 | 5 | 67 | 9.8 | 10.1 | 9.65 (e) | 1.24 | 21.6 (f) |
3a | L-LA | 10 | 5 | 9 | 1.5 | n.d. (g) | n.d. | n.d. | 31.2 (f) |
3b | L-LA | 45 | 5 | 37 | 5.4 | 5.7 | 5.55 (e) | 1.21 | 29.4 (f) |
3c | L-LA | 240 | 5 | 98 | 14.5 | 15.3 | 15.28 (e) | 1.20 | 29.4 (f) |
4 | MeOEP | 10 | 5 | >99 | 13.9 | 13.7 | 9.8 (h) | 1.35 | ~14 |
5 | MeOEP | 10 | −20 | 96 | 13.9 | 13.2 | 10.0 (h) | 1.32 | ~14 |
6 | MeOEP | 10 | −50 | 81 | 11.2 | 11.4 | 8.8 (h) | 1.26 | ~14 |
7 | MeOEP/rac-LA | 10 | 5 | >99/82 | 13.2 | 15.9 | 19.5 (h) | 1.62 | ~14/18.2 (i) |
8 | MeOEP/L-LA | 10 | 5 | >99/62 | 10.3 | 12.5 | 15.7 (h) | 1.71 | ~14/22.7 (i) |
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Nifant’ev, I.; Shlyakhtin, A.; Kosarev, M.; Karchevsky, S.; Ivchenko, P. Mechanistic Insights of BHT-Mg-Catalyzed Ethylene Phosphate’s Coordination Ring-Opening Polymerization: DFT Modeling and Experimental Data. Polymers 2018, 10, 1105. https://doi.org/10.3390/polym10101105
Nifant’ev I, Shlyakhtin A, Kosarev M, Karchevsky S, Ivchenko P. Mechanistic Insights of BHT-Mg-Catalyzed Ethylene Phosphate’s Coordination Ring-Opening Polymerization: DFT Modeling and Experimental Data. Polymers. 2018; 10(10):1105. https://doi.org/10.3390/polym10101105
Chicago/Turabian StyleNifant’ev, Ilya, Andrey Shlyakhtin, Maxim Kosarev, Stanislav Karchevsky, and Pavel Ivchenko. 2018. "Mechanistic Insights of BHT-Mg-Catalyzed Ethylene Phosphate’s Coordination Ring-Opening Polymerization: DFT Modeling and Experimental Data" Polymers 10, no. 10: 1105. https://doi.org/10.3390/polym10101105