Citation: Chen-Yang Hu, Ran-Long Duan, Jing-Wei Yang, Shu-Jun Dong, Zhi-Qiang Sun, Xuan Pang, Xian-Hong Wang, Xue-Si Chen. Enolic Schiff Base Zinc Amide Complexes: Highly Active Catalysts for Ring-Opening Polymerization of Lactide and ε-Caprolactone[J]. Chinese Journal of Polymer Science, ;2018, 36(10): 1123-1128. doi: 10.1007/s10118-018-2129-4 shu

Enolic Schiff Base Zinc Amide Complexes: Highly Active Catalysts for Ring-Opening Polymerization of Lactide and ε-Caprolactone

a.
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China
c.
Department of Materials Science and Engineering, Jilin University, Changchun 130025, China
d.
VIP Department, Stomatological Hospital of Jilin University, Changchun 130021, China

Corresponding author: Xuan Pang, xpang@ciac.ac.cn (X.P.) Xue-Si Chen, xschen@ciac.ac.cn (X.S.C.)
Received Date: 23 January 2018
Accepted Date: 13 February 2018
Available Online: 16 April 2018

A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and ε-caprolactone, exhibiting notably high activity at ambient temperature. The influence of imine bridge length and substituents of diketone over the course of polymerization was investigated in details. Remarkably, 4a was confirmed to be a rare example of exceedingly active and robust zinc catalysts, achieving major transformation of lactide under extremely low loading (0.025 mol%) within 18 min. The influence of various monomers as well as the polymerization mechanism have also been discussed.
- Zinc,
- β-Diketone,
- Ring-opening polymerization,
- Lactide,
- ε-Caprolactone
1. [1]
  Pang, X.; Zhuang, X.; Tang, Z.; Chen, X. Polylactic acid (PLA): research, development and industrialization. Biotechnol. J. 2010, 5, 1125−1136 doi: 10.1002/biot.v5.11
2. [2]
  Auras, R. A.; Lim, L. T.; Selke, S. E.; Tsuji, H. Poly(lactic acid): synthesis, structures, properties, processing, and applications. John Wiley & Sons (2011).
3. [3]
  Zhang, S. Y.; Chen, Z. F.; Wu, F.; Zhu, X. Y.; Liu, Z. Y.; Feng, J. M.; Yang, M. B. Studies on the effects of four-armed poly(L-lactide) on the crystallization behavior of four-armed poly(L-lactide)/linear poly(L-lactide) blends. Acta Polymerica Sinica (in Chinese) 2016, (5), 679−684
4. [4]
  Chen, Q.; Du, J.; Xie, H.; Zhao, Z.; Zheng, Q. Studies on preparation and properties of bio-based polymeric monomers and their bio-based polymers. Acta Polymerica Sinica (in Chinese) 2016, (10), 1330−1358
5. [5]
  Yang, J.; Sun, Z.; Duan, R.; Li, L.; Pang, X.; Chen, X. Copolymer of lactide and ε-caprolactone catalyzed by bimetallic Schiff base aluminum complexes. Sci. China Chem. 2016, 59, 1384−1389 doi: 10.1007/s11426-016-0118-9
6. [6]
  Thomas, C. M. Stereocontrolled ring-opening polymerization of cyclic esters: synthesis of new polyester microstructures. Chem. Soc. Rev. 2010, 39, 165−173 doi: 10.1039/B810065A
7. [7]
  Stanford, M. J.; Dove, A. P. Stereocontrolled ring-opening polymerisation of lactide. Chem. Soc. Rev. 2010, 39, 486−494 doi: 10.1039/B815104K
8. [8]
  Xu, T. Q.; Yang, G. W.; Liu, C.; Lu, X. B. Highly robust yttrium bis(phenolate) ether catalysts for excellent isoselective ring-opening polymerization of racemic lactide. Macromolecules 2017, 50, 515−522 doi: 10.1021/acs.macromol.6b02439
9. [9]
  Guillaume, S. M.; Kirillov, E.; Sarazin, Y.; Carpentier, J. F. Beyond stereoselectivity, switchable catalysis: some of the last Frontier challenges in ring-opening polymerization of cyclic esters. Chem. Eur. J. 2015, 21, 7988−8003 doi: 10.1002/chem.201500613
10. [10]
  Cozzi, P. G. Metal-Salen Schiff base complexes in catalysis: practical aspects. Chem. Soc. Rev. 2004, 33, 410−421 doi: 10.1039/B307853C
11. [11]
  Chisholm, M. H.; Gallucci, J. C.; Zhen, H.; Huffman, J. C. Three-coordinate zinc amide and phenoxide complexes supported by a bulky Schiff base ligand. Inorg. Chem. 2001, 40, 5051−5054 doi: 10.1021/ic010560e
12. [12]
  Chen, H. Y.; Tang, H. Y.; Lin, C. C. Ring-opening polymerization of lactides initiated by zinc alkoxides derived from NNO-tridentate ligands. Macromolecules 2006, 39, 3745−3752 doi: 10.1021/ma060471r
13. [13]
  Pang, X.; Chen, X.; Zhuang, X.; Jing, X. Crown-like macrocycle zinc complex derived from β-diketone ligand for the polymerization of rac-lactide. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 643−649 doi: 10.1002/(ISSN)1099-0518
14. [14]
  Baran, J.; Duda, A.; Kowalski, A.; Szymanski, R.; Penczek, S. Intermolecular chain transfer to polymer with chain scission: general treatment and determination of k_p/k_tr in L,L-lactide polymerization. Macromol. Rapid Commun. 1997, 18, 325−333 doi: 10.1002/marc.1997.030180409
15. [15]
  Save, M.; Schappacher, M.; Soum, A. Controlled ring-opening polymerization of lactones and lactides initiated by lanthanum isopropoxide, 1. general aspects and kinetics. 3.0.CO;2-O">Macromol. Chem. Phys. 2002, 203, 889−899 doi: 10.1002/1521-3935(20020401)203:5/6<889::AID-MACP889>3.0.CO;2-O
16. [16]
  Gulli, S.; Daran, J. C.; Poli, R. Synthesis and structure of four-coordinate copper(ii) complexes stabilized by β-Ketiminato ligands and application in the reverse atom-transfer radical polymerization of styrene. Eur. J. Inorg. Chem. 2011, 10, 1666−1672
17. [17]
  Tang, H. Y.; Chen, H. Y.; Huang, J. H.; Lin, C. C. Synthesis and structural characterization of magnesium ketiminate complexes: efficient initiators for the ring-opening polymerization of L-lactide. Macromolecules 2007, 40, 8855−8860 doi: 10.1021/ma071540k
18. [18]
  Shit, S.; Sen, S.; Mitra, S.; Hughes, D. L. Syntheses, characterization and crystal structures of two square-planar Ni(II) complexes with unsymmetrical tridentate Schiff base ligands and monodentate pseudohalides. Transition Met. Chem. 2009, 34, 269−274 doi: 10.1007/s11243-009-9189-9
19. [19]
  Bochmann, M.; Bwembya, G.; Webb, K. J.; Malik, M. A.; Walsh, J. R.; O'Brien, P. Arene chalcogenolato complexes of zinc and cadmium, inorganic syntheses. John Wiley & Sons, Inc. 1997, 19–24.
20. [20]
  Pang, X.; Du, H.; Chen, X.; Wang, X.; Jing, X. Enolic Schiff base aluminum complexes and their catalytic stereoselective polymerization of racemic lactide. Chem. Eur. J. 2008, 14, 3126−3136 doi: 10.1002/(ISSN)1521-3765
21. [21]
  Scheiper, C.; Dittrich, D.; Wölper, C.; Bläser, D.; Roll, J.; Schulz, S. Synthesis, structure, and catalytic activity of tridentate, base-functionalized β-Ketiminate zinc complexes in ring-opening polymerization of lactide. Eur. J. Inorg. Chem. 2014, 2014, 2230−2240 doi: 10.1002/ejic.201301462
22. [22]
  Hong, M.; Chen, E. Y. Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone. Nat. Chem. 2016, 8, 42−49 doi: 10.1038/nchem.2391
23. [23]
  Huang, M.; Pan, C.; Ma, H. Ring-opening polymerization of rac-lactide and α-methyltrimethylene carbonate catalyzed by magnesium and zinc complexes derived from binaphthyl-based iminophenolate ligands. Dalton Trans. 2015, 44, 12420−12431 doi: 10.1039/C5DT00158G
24. [24]
  Wang, H.; Yang, Y.; Ma, H. Stereoselectivity Switch between zinc and magnesium initiators in the polymerization of rac-lactide: different coordination chemistry, different stereocontrol mechanisms. Macromolecules 2014, 47, 7750−7764 doi: 10.1021/ma501896r
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1.
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