Mechanism-inspired Design of Heterodinuclear Catalysts for Copolymerization of Epoxide and Lactone

Wei-Min Ren; Rui-Jing Wang; Bai-Hao Ren; Ge-Ge Gu; Tian-Jun Yue

doi:10.1007/s10118-020-2413-y

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Mechanism-inspired Design of Heterodinuclear Catalysts for Copolymerization of Epoxide and Lactone

ARTICLE | Updated：2020-04-21

- Mechanism-inspired Design of Heterodinuclear Catalysts for Copolymerization of Epoxide and Lactone
- Chinese Journal of Polymer Science Vol. 38, Issue 9, Pages: 950-957(2020)
- Affiliations：
  
  State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China
- Author bio：
  
  wmren@dlut.edu.cn
- Funds：
- DOI：10.1007/s10118-020-2413-y
  CLC：
- Received：13 January 2020，
  
  Revised：2020-2-11，
  
  Accepted：24 February 2020，
  
  Online First：21 April 2020，
  
  Published：2020-09
- Accepted：
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Ren, W. M.; Wang, R. J.; Ren, B. H.; Gu, G. G.; Yue, T. J. Mechanism-inspired design of heterodinuclear catalysts for copolymerization of epoxide and lactone. Chinese J. Polym. Sci. 2020, 38, 950–957

Wei-Min Ren, Rui-Jing Wang, Bai-Hao Ren, et al. Mechanism-inspired Design of Heterodinuclear Catalysts for Copolymerization of Epoxide and Lactone[J]. Chinese Journal of Polymer Science, 2020, 38(9): 950-957.
Ren, W. M.; Wang, R. J.; Ren, B. H.; Gu, G. G.; Yue, T. J. Mechanism-inspired design of heterodinuclear catalysts for copolymerization of epoxide and lactone. Chinese J. Polym. Sci. 2020, 38, 950–957 DOI： 10.1007/s10118-020-2413-y.

Wei-Min Ren, Rui-Jing Wang, Bai-Hao Ren, et al. Mechanism-inspired Design of Heterodinuclear Catalysts for Copolymerization of Epoxide and Lactone[J]. Chinese Journal of Polymer Science, 2020, 38(9): 950-957. DOI： 10.1007/s10118-020-2413-y.

摘要

Abstract

Polyesters

as a class of high-performance and versatile polymer materials

often suffer from some drawbacks

such as hydrophobicity and brittleness due to their single structure nature. Thus

modifications have attracted much attention for enhancing their desirable properties

of which one efficient way is incorporating the aliphatic polyether segment into the main chain of the polyester. However

this approach is of much challenge because the obtained polyesters are problematic in either low alternating degree or low molecular weight. Herein

we describe an efficient strategy to incorporate polyether fragment into polyester by developing a novel Co-Al based heterodinuclear complex for mediating the copolymerization of propylene oxide (PO) with

-caprolactone (CL). The tracking experiments reveal that PO and CL convert into the polymer chain throughout the polymerization process. Especially

the linear increase in the molecular weight with conversion of CL indicates the controllable nature of the copolymerization. The competition polymerization

offering the monomer reactivity ratios of

= 0.96 and

= 1.04

suggests that the tendency of self-propagation or incorporation of monomers is nearly identical. Interestingly

the obtained polymers with different ether contents exhibit tunable thermal properties with enhanced decomposition temperature for the polymer with higher ether content. The newly developed heterodinuclear complex for new polymerization provides an idea to synthesize new functional polymeric materials.

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references

Kutikov, A. B.; Song, J. . Biodegradable PEG-based amphiphilic block copolymers for tissue engineering applications . ACS Biomater. Sci. Eng. , 2015 . 1 463 - 480 . DOI: 10.1021/acsbiomaterials.5b00122 http://doi.org/10.1021/acsbiomaterials.5b00122 .

Xia, Y. N.; Zhao, J. P. . Macromolecular architectures based on organocatalytic ring-opening (co)polymerization of epoxides . Polymer , 2018 . 143 343 - 361 . DOI: 10.1016/j.polymer.2018.03.047 http://doi.org/10.1016/j.polymer.2018.03.047 .

Wang, B. T.; Zhang, Y.; Guo, Z. H.; Cheng, J.; Fang, Z. H. . Biodegradable aliphatic/aromatic copoly(ester-ether)s: the effect of poly(ethylene glycol) on physical properties and degradation behavior . J. Polym. Res. , 2011 . 18 187 - 196 . DOI: 10.1007/s10965-010-9406-4 http://doi.org/10.1007/s10965-010-9406-4 .

Webb, M. A.; Jung, Y.; Pesko, D. M.; Savoie, B. M.; Yamamoto, U.; Goates, G. W.; Balsara, N. P.; Wang, Z. G.; Miller, T. F. . Systematic computational and experimental investigation of lithium-Ion transport mechanisms in polyester-based polymer electrolytes . ACS Cent. Sci. , 2015 . 1 198 - 205 . DOI: 10.1021/acscentsci.5b00195 http://doi.org/10.1021/acscentsci.5b00195 .

Liu, Y. Y.; Wang, X. J.; Li, Z.; Wei, F. L.; Zhu, H.; Dong, H.; Chen, S. M.; Sun, H. R.; Yang, K.; Guo, K. . A switch from anionic to bifunctional H-bonding catalyzed ring-opening polymerizations towards polyether-polyester diblock copolymers . Polym. Chem. , 2018 . 9 154 - 159 . DOI: 10.1039/C7PY01842H http://doi.org/10.1039/C7PY01842H .

Li, H.; Luo, H. T.; Zhao, J. P.; Zhang, G. Z. . Sequence-selective terpolymerization from monomer mixtures using a simple organocatalyst . ACS Macro Lett. , 2018 . 7 1420 - 1425 . DOI: 10.1021/acsmacrolett.8b00865 http://doi.org/10.1021/acsmacrolett.8b00865 .

Romain, C.; Zhu, Y. Q.; Dingwall, P.; Paul, S.; Rzepa, H. S.; Buchard, A.; Williams, C. K. . Chemoselective polymerizations from mixtures of epoxide, lactone, anhydride, and carbon dioxide . J. Am. Chem. Soc. , 2016 . 138 4120 - 4131 . DOI: 10.1021/jacs.5b13070 http://doi.org/10.1021/jacs.5b13070 .

Qi, M.; Dong, Q.; Wang, D. W.; Byers, J. A. . Electrochemically switchable ring-opening polymerization of lactide and cyclohexene oxide . J. Am. Chem. Soc. , 2018 . 140 5686 - 5690 . DOI: 10.1021/jacs.8b02171 http://doi.org/10.1021/jacs.8b02171 .

Hu, C. Y; Duan, R. L.; Yang, S. C.; Pang, X.; Chen, X. S. . CO 2 controlled catalysis: switchable homopolymerization and copolymerization . Macromolecules , 2018 . 51 4699 - 4704 . DOI: 10.1021/acs.macromol.8b00696 http://doi.org/10.1021/acs.macromol.8b00696 .

Quan, S. M.; Wang, X. K.; Zhang, R.; Diaconescu, P. L. . Redox Switchable copolymerization of cyclic esters and epoxides by a Zirconium complex . Macromolecules , 2016 . 49 6768 - 6778 . DOI: 10.1021/acs.macromol.6b00997 http://doi.org/10.1021/acs.macromol.6b00997 .

Zhao, J. P.; Pahovnik, D.; Gnanou, Y.; Hadjichristidis, N. . Sequential polymerization of ethylene oxide, ε -caprolactone and L-lactide: a one-pot metal-free route to tri- and pentablock terpolymers . Polym. Chem. , 2014 . 5 3750 - 3753 . DOI: 10.1039/C4PY00429A http://doi.org/10.1039/C4PY00429A .

Isnard, F.; Carratù, M.; Lamberti, M.; Venditto, V.; Mazzeo, M. . Copolymerization of cyclic esters, epoxides and anhydrides: evidence of the dual role of the monomers in the reaction mixture . Catal. Sci. Technol. , 2018 . 8 5034 - 5043 . DOI: 10.1039/C8CY01174E http://doi.org/10.1039/C8CY01174E .

Yuan, H.; Bin, J.; Pan, L.; Li, Y. S. . One-step access to sequence-controlled block copolymers by self-switchable organocatalytic multicomponent polymerization . Angew. Chem. Int. Ed. , 2018 . 57 16888 - 16892 . DOI: 10.1002/anie.201810083 http://doi.org/10.1002/anie.201810083 .

Liu, S.; Bai, T. W.; Ni, K.; Chen, Y.; Zhao, J. P.; Ling, J.; Ye, X. D.; Zhang, G. Z. . Biased Lewis pairs: a general catalytic approach to ether-ester block copolymers with unlimited ordering of sequences . Angew. Chem. Int. Ed. , 2019 . 58 15478 - 15487 . DOI: 10.1002/anie.201908904 http://doi.org/10.1002/anie.201908904 .

Li, H.; He, G. C; Chen, Y.; Zhao, J. P.; Zhang, G. Z. . One-step approach to polyester-polyether block copolymers using highly tunable bicomponent catalyst . ACS Macro Lett. , 2019 . 8 973 - 978 . DOI: 10.1021/acsmacrolett.9b00439 http://doi.org/10.1021/acsmacrolett.9b00439 .

Huang, H. C.; Li, Z. J.; Wang, B.; Chen, X.; Li, Y. S. . Synthesis of lactide/ ɛ -caprolactone quasi-random copolymer by using rationally designed mononuclear aluminum complexes with modified β -ketiminato ligand . J. Polym., Sci., Part A: Polym. Chem. , 2018 . 56 203 - 212 . DOI: 10.1002/pola.28886 http://doi.org/10.1002/pola.28886 .

Han, B.; Liu, B. Y.; Ding, H. N.; Duan, Z. Y.; Wang, X. H.; Theato, P. . CO 2 -tuned sequential synthesis of stereoblock copolymers comprising a stereoregularity-adjustable polyester block and an atactic CO 2 -based polycarbonate block . Macromolecules , 2017 . 50 9207 - 9215 . DOI: 10.1021/acs.macromol.7b01905 http://doi.org/10.1021/acs.macromol.7b01905 .

Chen, X. H.; Mccarthy, S. P.; Gross, R. A. . Synthesis and characterization of [L]-lactide-ethylene oxide multiblock copolymers . Macromolecules , 1997 . 30 4295 - 4301 . DOI: 10.1021/ma970385e http://doi.org/10.1021/ma970385e .

Xu, J. B.; Yang, J. X.; Ye, X. D.; Ma, C. F.; Zhang, G. Z.; Pispas, S. . Synthesis and properties of amphiphilic and biodegradable poly( ɛ -caprolactone- co -glycidol) copolymers . J. Polym. Sci., Part A: Polym. Chem. , 2015 . 53 846 - 853 . DOI: 10.1002/pola.27515 http://doi.org/10.1002/pola.27515 .

Hu, S. Y.; Zhao, J. P.; Zhang, G. Z. . Noncopolymerization approach to copolymers via concurrent transesterification and ring-opening reactions . ACS Macro Lett. , 2016 . 5 40 - 44 . DOI: 10.1021/acsmacrolett.5b00839 http://doi.org/10.1021/acsmacrolett.5b00839 .

Chwatko, M.; Lynd, N. A. . Statistical copolymerization of epoxides and lactones to high molecular weight . Macromolecules , 2017 . 50 2714 - 2723 . DOI: 10.1021/acs.macromol.7b00410 http://doi.org/10.1021/acs.macromol.7b00410 .

Clayman, N. E.; Morris, L. S.; LaPointe, A. M.; Keresztes, I.; Waymouth, R. M.; Coates, G. W. . Dual catalysis for the copolymerisation of epoxides and lactones . Chem. Commun. , 2019 . 55 6914 - 6917 . DOI: 10.1039/C9CC00493A http://doi.org/10.1039/C9CC00493A .

Darensbourg, D. J.; Chung, W. C. . Relative basicities of cyclic ethers and esters chemistry of importance to ring-opening co- and terpolymerization reactions . Polyhedron. , 2013 . 58 139 - 143 . .

Lu, X. B.; Ren, W. M.; Wu, G. P. . CO 2 copolymers from epoxides: catalyst activity, product selectivity, and stereochemistry control . Acc. Chem. Res. , 2012 . 45 1721 - 1735 . DOI: 10.1021/ar300035z http://doi.org/10.1021/ar300035z .

Herzberger, J.; Niederer, K.; Pohlit, H.; Seiwert, J.; Worm, M.; Wurm, F. R.; Frey, H. . Polymerization of ethylene oxide, propylene oxide, and other alkylene oxides: synthesis, novel polymer architectures, and bioconjugation . Chem. Rev. , 2016 . 116 2170 - 2243 . DOI: 10.1021/acs.chemrev.5b00441 http://doi.org/10.1021/acs.chemrev.5b00441 .

Sarazin, Y.; Carpentier, J. F. . Discrete cationic complexes for ring-opening polymerization catalysis of cyclic esters and epoxides . Chem. Rev. , 2015 . 115 3564 - 3614 . DOI: 10.1021/acs.chemrev.5b00033 http://doi.org/10.1021/acs.chemrev.5b00033 .

Ruan, J. M.; Xiao, A. G.; Wu, H. W.; Yang H. L. . Review-recent development of ring-opening polymerization of cyclic esters using aluminum complexes . Des. Monomers Polym. , 2013 . 17 345 - 355 . .

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 http://doi.org/10.1039/B810065A .

Wu, J. C.; Yu, T. L.; Chen, C. T.; Lin, C. C. . Recent developments in main group metal complexes catalyzed/initiated polymerization of lactides and related cyclic esters . Coord. Chem. Rev. , 2006 . 250 602 - 626 . DOI: 10.1016/j.ccr.2005.07.010 http://doi.org/10.1016/j.ccr.2005.07.010 .

Ajellal, N.; Carpentier, J. F.; Guillaume, C.; Guillaume, S. M.; Helou, M.; Poirier, V.; Sarazina Y.; Trifonov, A . Metal-catalyzed immortal ring-opening polymerization of lactones, lactides and cyclic carbonates . Dalton Trans. , 2010 . 39 8363 - 8376 . DOI: 10.1039/c001226b http://doi.org/10.1039/c001226b .

Labet, M.; Thielemans, W. . Synthesis of polycaprolactone: a review . Chem. Soc. Rev. , 2009 . 38 3484 - 3504 . DOI: 10.1039/b820162p http://doi.org/10.1039/b820162p .

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