Citation: Tian-Wen Bai, Xu-Feng Ni, Jun Ling, Zhi-Quan Shen. Mechanism of Janus Polymerization: A DFT Study[J]. Chinese Journal of Polymer Science, ;2019, 37(10): 990-994. doi: 10.1007/s10118-019-2318-9 shu

Mechanism of Janus Polymerization: A DFT Study

Ministry of Education Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China

Corresponding author: Jun Ling, lingjun@zju.edu.cn
Received Date: 26 March 2019
Revised Date: 12 June 2019
Available Online: 19 August 2019

Janus polymerization is featured as a combination of cationic and anionic growing ends in one living polymer chain. In the copolymerization of THF and CL catalyzed by lutetium triflates and initiated by propylene oxide, three stages are identified by kinetic study including (1) fast cationic polymerization with slow anionic one, (2) fast anionic polymerization with dormant cationic one, and (3) reactivation of cationic polymerization with coupling of anionic and cationic chain ends. In this work, density functional theory (DFT) calculation is employed to investigate the reaction details of ionic polymerization and dormancy. A " tripedal crow” configuration is proposed to illustrate the unique high-coordinated ligand exchange configuration in anionic polymerization in different stages. The trigger of dormancy is determined as chain structures rather than concentration of triflate anion according to both calculation and experimental results.
- Rare earth metal catalysts,
- Ring-opening polymerization,
- Ionic polymerization,
- Reaction mechanism,
- Quantum chemical computation
1. [1]
  You, L. X.; Ling, J. Janus Polymerization. Macromolecules 2014, 47, 2219-2225. doi: 10.1021/ma500173c
2. [2]
  Qiu, H.; Yang, Z.; Shah, M. I.; Mao, Z.; Ling, J. [PCL-b-P(THF-co-CL)]_m multiblock copolymer synthesized by Janus polymerization. Polymer 2017, 128, 71-77. doi: 10.1016/j.polymer.2017.08.040
3. [3]
  Shah, M. I.; Yang, Z.; Li, Y.; Jiang, L.; Ling, J. Properties of electrospun nanofibers of multi-block copolymers of [poly-ε-caprolactone-b-poly(tetrahydrofuran-co-ε-caprolactone)]_m synthesized by Janus polymerization. Polymers 2017, 9, 559. doi: 10.3390/polym9110559
4. [4]
  Li, Y.; Bai, T.; Li, Y.; Ling, J. Branched polytetrahydrofuran and poly(tetrahydrofuran-co-ε-caprolactone) synthesized by Janus polymerization: A novel self-healing material. Macromol. Chem. Phys. 2017, 218, 1600450. doi: 10.1002/macp.v218.3
5. [5]
  Li, Y.; von der Lühe, M.; Schacher, F. H.; Ling, J. 3-miktoarm star terpolymers via Janus polymerization: One-step synthesis and self-assembly. Macromolecules 2018, 51, 4938-4944. doi: 10.1021/acs.macromol.8b00949
6. [6]
  Li, Y.; Schacher, F. H.; Ling, J. Synthesis of polypeptoid-polycaprolactone-polytetrahydrofuran heterograft molecular polymer brushes via a combination of Janus polymerization and ROMP. Macromol. Rapid Comm. 2019, 1800905.
7. [7]
  Qiu, H.; Yang, Z. N.; Ling, J. Facile synthesis of functional poly(ε-caprolactone) via Janus polymerization. Chinese J. Polym. Sci. 2019, 37, DOI: 10.1007/s10118-019-2242-z. doi: 10.1007/s10118-019-2242-z
8. [8]
  Devlin, F.; Finley, J.; Stephens, P.; Frisch, M. Ab-initio calculation of vibrational absorption and circular-dichroism spectra using density-functional force-fields-a comparison of local, nonlocal, and hybrid density functionals. J. Phys. Chem. 1995, 99, 16883-16902. doi: 10.1021/j100046a014
9. [9]
  Kim, K.; Jordan, K. Comparison of density-functional and MP2 calculations on the water monomer and dimer. J. Phys. Chem. 1994, 98, 10089-10094. doi: 10.1021/j100091a024
10. [10]
  Fukui, K. The path of chemical reactions-the IRC approach. Acc. Chem. Res. 1981, 14, 363-368. doi: 10.1021/ar00072a001
11. [11]
  Bai, T. W.; Ling, J. NAM-TMS mechanism of α-amino acid N-carboxyanhydride polymerization: A DFT study. J. Phys. Chem. A 2017, 121, 4588-4593. doi: 10.1021/acs.jpca.7b04278
12. [12]
  He, B. Z.; Su, H. F.; Bai, T. W.; Wu, Y. W.; Li, S. W.; Gao, M.; Hu, R. R.; Zhao, Z. J.; Qin, A. J.; Ling, J.; Tang, B. Z. Spontaneous amino-yne click polymerization: A powerful tool toward regio- and stereospecific poly(β-aminoacrylate)s. J. Am. Chem. Soc. 2017, 139, 5437-5443. doi: 10.1021/jacs.7b00929
13. [13]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16 Rev. B.01, Gaussian, Inc,; Wallingford, CT, 2016.
14. [14]
  Legault, C. Y. CYLview, 1.0b, Université de Sherbrooke, 2009 (http://www.cylview.org).
15. [15]
  Ling, J.; Shen, J. G.; Hogen-Esch, T. E. A density functional theory study of the mechanisms of scandium-alkoxide initiated coordination-insertion ring-opening polymerization of cyclic esters. Polymer 2009, 50, 3575-3581. doi: 10.1016/j.polymer.2009.06.006
16. [16]
  Liu, J.; Ling, J.; Li, X.; Shen, Z. Monomer insertion mechanism of ring-opening polymerization of ε-caprolactone with yttrium alkoxide intermediate: A DFT study. J. Mol. Catal. A-Chem. 2009, 300, 59-64. doi: 10.1016/j.molcata.2008.10.038
17. [17]
  You, L. X.; Shen, Z. Q.; Kong, J.; Ling, J. A novel approach to RE-OR bond from in situ reaction of rare earth triflates and sodium alkoxides: A versatile catalyst for living ring-opening polymerization of ε-caprolactone. Polymer 2014, 55, 2404-2410. doi: 10.1016/j.polymer.2014.03.032
1. [1]
  Huixin Chen , Chen Zhao , Hongjun Yue , Guiming Zhong , Xiang Han , Liang Yin , Ding Chen . Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(1): 109650-. doi: 10.1016/j.cclet.2024.109650
2. [2]
  Qin Cheng , Ming Huang , Qingqing Ye , Bangwei Deng , Fan Dong . Indium-based electrocatalysts for CO₂ reduction to C1 products. Chinese Chemical Letters, 2024, 35(6): 109112-. doi: 10.1016/j.cclet.2023.109112
3. [3]
  Tingting Liu , Pengfei Sun , Wei Zhao , Yingshuang Li , Lujun Cheng , Jiahai Fan , Xiaohui Bi , Xiaoping Dong . Magnesium doping to improve the light to heat conversion of OMS-2 for formaldehyde oxidation under visible light irradiation. Chinese Chemical Letters, 2024, 35(4): 108813-. doi: 10.1016/j.cclet.2023.108813
4. [4]
  Hailong He , Wenbing Wang , Wenmin Pang , Chen Zou , Dan Peng . Double stimulus-responsive palladium catalysts for ethylene polymerization and copolymerization. Chinese Chemical Letters, 2024, 35(7): 109534-. doi: 10.1016/j.cclet.2024.109534
5. [5]
  Yue Sun , Liming Yang , Yaohang Cheng , Guanghui An , Guangming Li . Pd(I)-catalyzed ring-opening arylation of cyclopropyl-α-aminoamides: Access to α-ketoamide peptidomimetics. Chinese Chemical Letters, 2024, 35(6): 109250-. doi: 10.1016/j.cclet.2023.109250
6. [6]
  Rong-Nan Yi , Wei-Min He . Visible light/copper catalysis enabled radial type ring-opening of sulfonium salts. Chinese Chemical Letters, 2025, 36(4): 110787-. doi: 10.1016/j.cclet.2024.110787
7. [7]
  Xianxu Chu , Lu Wang , Junru Li , Hui Xu . Surface chemical microenvironment engineering of catalysts by organic molecules for boosting electrocatalytic reaction. Chinese Chemical Letters, 2024, 35(8): 109105-. doi: 10.1016/j.cclet.2023.109105
8. [8]
  Fei Yin , Erli Yang , Xue Ge , Qian Sun , Fan Mo , Guoqiu Wu , Yanfei Shen . Coupling WO₃₋_x dots-encapsulated metal-organic frameworks and template-free branched polymerization for dual signal-amplified electrochemiluminescence biosensing. Chinese Chemical Letters, 2024, 35(4): 108753-. doi: 10.1016/j.cclet.2023.108753
9. [9]
  Qinghong Zhang , Qiao Zhao , Xiaodi Wu , Li Wang , Kairui Shen , Yuchen Hua , Cheng Gao , Yu Zhang , Mei Peng , Kai Zhao . Visible-light-induced ring-opening cross-coupling of cycloalcohols with vinylazaarenes and enones via β-C-C scission enabled by proton-coupled electron transfer. Chinese Chemical Letters, 2025, 36(2): 110167-. doi: 10.1016/j.cclet.2024.110167
10. [10]
  Bing Niu , Honggao Huang , Liwei Luo , Li Zhang , Jianbo Tan . Coating colloidal particles with a well-defined polymer layer by surface-initiated photoinduced polymerization-induced self-assembly and the subsequent seeded polymerization. Chinese Chemical Letters, 2025, 36(2): 110431-. doi: 10.1016/j.cclet.2024.110431
11. [11]
  Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
12. [12]
  Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
13. [13]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
14. [14]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
15. [15]
  Yong Wang , Yingying Zhao , Boshun Wan . Analysis of Organic Questions in the 37th Chinese Chemistry Olympiad (Preliminary). University Chemistry, 2024, 39(11): 406-416. doi: 10.12461/PKU.DXHX202403009
16. [16]
  Mingyang Men , Jinghua Wu , Gaozhan Liu , Jing Zhang , Nini Zhang , Xiayin Yao . 液相法制备硫化物固体电解质及其在全固态锂电池中的应用. Acta Physico-Chimica Sinica, 2025, 41(1): 2309019-. doi: 10.3866/PKU.WHXB202309019
17. [17]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
18. [18]
  Zihan Lin , Wanzhen Lin , Fa-Jie Chen . Electrochemical Modifications of Native Peptides. University Chemistry, 2025, 40(3): 318-327. doi: 10.12461/PKU.DXHX202406089
19. [19]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
20. [20]
  Guowen Xing , Guangjian Liu , Le Chang . Five Types of Reactions of Carbonyl Oxonium Intermediates in University Organic Chemistry Teaching. University Chemistry, 2025, 40(4): 282-290. doi: 10.12461/PKU.DXHX202407058

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(820)
HTML views(48)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142