Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones

Zhuo-Lun Jiang; Jun-Peng Zhao; Guang-Zhao Zhang

doi:10.1007/s10118-019-2285-1

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Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones

ARTICLE | Updated：2021-02-18

- Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones
- Chinese Journal of Polymer Science Vol. 37, Issue 12, Pages: 1205-1214(2019)
- Affiliations：
  
  Faculty of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China
- Author bio：
  
  msjpzhao@scut.edu.cn
- Funds：
- DOI：10.1007/s10118-019-2285-1
  CLC：
- Received：26 March 2019，
  
  Revised：2019-4-22，
  
  Accepted：25 April 2019，
  
  Online First：26 June 2019，
  
  Published：2019-12
- Accepted：
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Jiang, Z. L.; Zhao, J. P.; Zhang, G. Z. Readily prepared and tunable ionic organocatalysts for ring-opening polymerization of lactones. Chinese J. Polym. Sci. 2019, 37, 1205–1214.

Zhuo-Lun Jiang, Jun-Peng Zhao, Guang-Zhao Zhang. Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones[J]. Chinese Journal of Polymer Science, 2019, 37(12): 1205-1214.
Jiang, Z. L.; Zhao, J. P.; Zhang, G. Z. Readily prepared and tunable ionic organocatalysts for ring-opening polymerization of lactones. Chinese J. Polym. Sci. 2019, 37, 1205–1214. DOI： 10.1007/s10118-019-2285-1.

Zhuo-Lun Jiang, Jun-Peng Zhao, Guang-Zhao Zhang. Readily Prepared and Tunable Ionic Organocatalysts for Ring-opening Polymerization of Lactones[J]. Chinese Journal of Polymer Science, 2019, 37(12): 1205-1214. DOI： 10.1007/s10118-019-2285-1.

摘要

Abstract

Highly potent ionic organocatalyst is developed for room-temperature controlled ring-opening polymerization (ROP) of lactones

including

-valerolactone

-caprolactone

and

-hexalactone. The catalysts are prepared by simply mixing tetra-

-butyl ammonium hydroxide and a (thio)urea at elevated temperature under vacuum

and used in cooperation with an alcoholic initiator. The performance of the catalyst is readily adjusted and optimized through variation of the (thio)urea precursor

catalyst composition

and reaction condition. Urea-derived catalysts are generally superior to thiourea-derived ones. Provided with proper

-substituents

the catalyst affords both high polymerization efficiency and high selectivity for monomer enchainment over macromolecular transesterification

even at high monomer conversion and/or substantially extended reaction time. In addition to acidity

structural symmetry of the urea also proves decisive for the catalytic activity

which enables a catalyst-assisted proton transfer process for the ring-opening of lactone and thus provides a novel mechanistic insight for ROP catalyzed by hydrogen-bonding type bifunctional ionic organocatalysts.

关键词

Keywords

references

Albertsson, A. C.; Varma, I. K . Aliphatic polyesters: Synthesis, properties and applications . Adv. Polym. Sci. , 2002 . 157 1 - 40 . DOI: 10.1007/3-540-45734-8 http://doi.org/10.1007/3-540-45734-8 .

Nair, L. S.; Laurencin, C. T . Biodegradable polymers as biomaterials . Prog. Polym. Sci. , 2007 . 32 762 - 798 . DOI: 10.1016/j.progpolymsci.2007.05.017 http://doi.org/10.1016/j.progpolymsci.2007.05.017 .

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 .

Lecomte, P.; Jérôme, C . Recent developments in ring-opening polymerization of lactones . Adv. Polym. Sci. , 2012 . 245 173 - 217 . .

Williams, C. K . Synthesis of functionalized biodegradable polyesters . Chem. Soc. Rev. , 2007 . 36 1573 - 1580 . DOI: 10.1039/b614342n http://doi.org/10.1039/b614342n .

Kamber, N. E.; Jeong, W.; Waymouth, R. M.; Pratt, R. C.; Lohmeijer, B. G. G.; Hedrick, J. L . Organocatalytic ring-opening polymerization . Chem. Rev. , 2007 . 107 5813 - 5840 . DOI: 10.1021/cr068415b http://doi.org/10.1021/cr068415b .

Kiesewetter, M. K.; Shin, E. J.; Hedrick, J. L.; Waymouth, R. M . Organocatalysis: Opportunities and challenges for polymer synthesis . Macromolecules , 2010 . 43 2093 - 2107 . DOI: 10.1021/ma9025948 http://doi.org/10.1021/ma9025948 .

Ottou, W. N.; Sardon, H.; Mecerreyes, D.; Vignolle, J.; Taton, D . Update and challenges in organo-mediated polymerization reactions . Prog. Polym. Sci. , 2016 . 56 64 - 115 . DOI: 10.1016/j.progpolymsci.2015.12.001 http://doi.org/10.1016/j.progpolymsci.2015.12.001 .

Hu, S.; Zhao, J.; Zhang, G.; Schlaad, H . Macromolecular architectures through organocatalysis . Prog. Polym. Sci. , 2017 . 74 34 - 77 . DOI: 10.1016/j.progpolymsci.2017.07.002 http://doi.org/10.1016/j.progpolymsci.2017.07.002 .

Boileau, S.; Illy, N . Activation in anionic polymerization: Why phosphazene bases are very exciting promoters . Prog. Polym. Sci. , 2011 . 36 1132 - 1151 . DOI: 10.1016/j.progpolymsci.2011.05.005 http://doi.org/10.1016/j.progpolymsci.2011.05.005 .

Liu, S.; Ren, C.; Zhao, N.; Shen, Y.; Li, Z . Phosphazene bases as organocatalysts for ring-opening polymerization of cyclic esters . Macromol. Rapid Commun. , 2018 . 1800485 .

Fevre, M.; Pinaud, J.; Gnanou, Y.; Vignolle, J.; Taton, D . N -Heterocyclic carbenes (NHCs) as organocatalysts and structural components in metal-free polymer synthesis . Chem. Soc. Rev. , 2013 . 42 2142 - 2172 . DOI: 10.1039/c2cs35383k http://doi.org/10.1039/c2cs35383k .

Naumann, S.; Dove, A. P . N -heterocyclic carbenes as organocatalysts for polymerizations: Trends and frontiers . Polym. Chem. , 2015 . 6 3185 - 3200 . DOI: 10.1039/C5PY00145E http://doi.org/10.1039/C5PY00145E .

Gazeau-Bureau, S.; Delcroix, D.; Martín-Vaca, B.; Bourissou, D.; Navarro, C.; Magnet, S . Organo-catalyzed ROP of ε -caprolactone: Methanesulfonic acid competes with trifluoromethanesulfonic acid . Macromolecules , 2008 . 41 3782 - 3784 . DOI: 10.1021/ma800626q http://doi.org/10.1021/ma800626q .

Kakuchi, R.; Tsuji, Y.; Chiba, K.; Fuchise, K.; Sakai, R.; Satoh, T.; Kakuchi, T . Controlled/living ring-opening polymerization of δ -valerolactone using triflylimide as an efficient cationic organocatalyst . Macromolecules , 2010 . 43 7090 - 7094 . DOI: 10.1021/ma100798u http://doi.org/10.1021/ma100798u .

Makiguchi, K.; Satoh, T.; Kakuchi, T . Diphenyl phosphate as an efficient cationic organocatalyst for controlled/living ring-opening polymerization of δ -valerolactone and ε -caprolactone . Macromolecules , 2011 . 44 1999 - 2005 . DOI: 10.1021/ma200043x http://doi.org/10.1021/ma200043x .

Thomas, C.; Bibal, B . Hydrogen-bonding organocatalysts for ring-opening polymerization . Green Chem. , 2014 . 16 1687 - 1699 . DOI: 10.1039/C3GC41806E http://doi.org/10.1039/C3GC41806E .

Pratt, R. C.; Lohmeijer, B. G. G.; Long, D. A.; Waymouth, R. M.; Hedrick, J. L . Triazabicyclodecene: A simple bifunctional organocatalyst for acyl transfer and ring-opening polymerization of cyclic esters . J. Am. Chem. Soc. , 2006 . 128 4556 - 4557 . DOI: 10.1021/ja060662+ http://doi.org/10.1021/ja060662+ .

Zhang, X.; Jones, G. O.; Hedrick, J. L.; Waymouth, R. M . Fast and selective ring-opening polymerizations by alkoxides and thioureas . Nat. Chem. , 2016 . 8 1047 - 1053 . DOI: 10.1038/nchem.2574 http://doi.org/10.1038/nchem.2574 .

Lohmeijer, B. G. G.; Pratt, R. C.; Leibfarth, F.; Logan, J. W.; Long, D. A.; Dove, A. P.; Nederberg, F.; Choi, J.; Wade, C.; Waymouth, R. M.; Hedrick, J. L . Guanidine and amidine organocatalysts for ring-opening polymerization of cyclic esters . Macromolecules , 2006 . 39 8574 - 8583 . DOI: 10.1021/ma0619381 http://doi.org/10.1021/ma0619381 .

Li, H.; Wang, C.; Yue, J.; Zhao, X.; Bai, F . Living ring-opening polymerization of lactides catalyzed by guanidinium acetate . J. Polym. Sci., Part A: Polym. Chem. , 2004 . 42 3775 - 3781 . .

Makiguchi, K.; Kikuchi, S.; Yanai, K.; Ogasawara, Y.; Sato, S.; Satoh, T.; Kakuchi, T . Diphenyl phosphate/4-dimethylaminopyridine as an efficient binary organocatalyst system for controlled/living ring-opening polymerization of L-lactide leading to diblock and end-functionalized poly(L-lactide)s . J. Polym. Sci., Part A: Polym. Chem. , 2014 . 52 1047 - 1054 . .

Wang, X.; Cui, S.; Li, Z.; Kan, S.; Zhang, Q.; Zhao, C.; Wu, H.; Liu, J.; Wu, W.; Guo, K . A base-conjugate-acid pair for living/controlled ring-opening polymerization of trimethylene carbonate through hydrogen-bonding bifunctional synergistic catalysis . Polym. Chem. , 2014 . 5 6051 - 6059 . DOI: 10.1039/C4PY00773E http://doi.org/10.1039/C4PY00773E .

Miao, Y.; Stanley, N.; Favrelle, A.; Bousquet, T.; Bria, M.; Mortreux, A.; Zinck, P . New acid/base salts as co-catalysts for the organocatalyzed ring opening polymerization of lactide . J. Polym. Sci., Part A: Polym. Chem. , 2015 . 53 659 - 664 . DOI: 10.1002/pola.v53.5 http://doi.org/10.1002/pola.v53.5 .

Lin, B.; Waymouth, R. M . Urea anions: Simple, fast, and selective catalysts for ring-opening polymerizations . J. Am. Chem. Soc. , 2017 . 139 1645 - 1652 . DOI: 10.1021/jacs.6b11864 http://doi.org/10.1021/jacs.6b11864 .

Tan, C.; Xiong, S.; Chen, C . Fast and controlled ring-opening polymerization of cyclic esters by alkoxides and cyclic amides . Macromolecules , 2018 . 51 2048 - 2053 . DOI: 10.1021/acs.macromol.7b02697 http://doi.org/10.1021/acs.macromol.7b02697 .

Lin, L.; Han, D.; Qin, J.; Wang, S.; Xiao, M.; Sun, L.; Meng, Y . Nonstrained γ -butyrolactone to high-molecular-weight poly( γ -butyrolactone): Facile bulk polymerization using economical ureas/alkoxides . Macromolecules , 2018 . 51 9317 - 9322 . DOI: 10.1021/acs.macromol.8b01860 http://doi.org/10.1021/acs.macromol.8b01860 .

Xia, Y.; Chen, Y.; Song, Q.; Hu, S.; Zhao, J.; Zhang, G . Base-to-base organocatalytic approach for one-pot construction of poly(ethylene oxide)-based macromolecular structures . Macromolecules , 2016 . 49 6817 - 6825 . DOI: 10.1021/acs.macromol.6b01542 http://doi.org/10.1021/acs.macromol.6b01542 .

Pothupitiya, J. U.; Dharmaratne, N. U.; Jouaneh, T. M. M.; Fastnacht, K. V.; Coderre, D. N.; Kiesewetter, M. K . H-bonding organocatalysts for the living, solvent-free ring-opening polymerization of lactones: Toward an all-lactones, all-conditions approach . Macromolecules , 2017 . 50 8948 - 8954 . DOI: 10.1021/acs.macromol.7b01991 http://doi.org/10.1021/acs.macromol.7b01991 .

Zhang, C . Dual organocatalysts for highly active and selective synthesis of linear poly( γ -butyrolactone)s with high molecular weights . Macromolecules , 2018 . 51 8705 - 8711 . DOI: 10.1021/acs.macromol.8b01757 http://doi.org/10.1021/acs.macromol.8b01757 .

Blain, M.; Yau, H.; Jean-Gerard, L.; Auvergne, R.; Benazet, D.; Schreiner, P. R.; Caillol, S.; Andrioletti, B . Urea- and thiourea-catalyzed aminolysis of carbonates . ChemSusChem , 2016 . 9 2269 - 2272 . DOI: 10.1002/cssc.201600778 http://doi.org/10.1002/cssc.201600778 .

Jakab, G.; Tancon, C.; Zhang, Z.; Lippert, K. M.; Schreiner, P. R . (Thio)urea organocatalyst equilibrium acidities in DMSO . Org. Lett. , 2012 . 14 1724 - 1727 . DOI: 10.1021/ol300307c http://doi.org/10.1021/ol300307c .

Walvoord, R. R.; Huynh, P. N. H.; Kozlowski, M. C . Quantification of electrophilic activation by hydrogen-bonding organocatalysts . J. Am. Chem. Soc. , 2014 . 136 16055 - 16065 . DOI: 10.1021/ja5086244 http://doi.org/10.1021/ja5086244 .

Lin, B.; Waymouth, R. M . Organic ring-opening polymerization catalysts: Reactivity control by balancing acidity . Macromolecules , 2018 . 51 2932 - 2938 . DOI: 10.1021/acs.macromol.8b00540 http://doi.org/10.1021/acs.macromol.8b00540 .

Zhao, W.; Wang, Q.; Cui, Y.; He, J.; Zhang, Y . Living/controlled ring-opening (co)polymerization of lactones by Al-based catalysts with different sidearms . Dalton Trans. , DOI: 10.1039/C8DT03941K DOI: 10.1039/C8DT03941K http://doi.org/10.1039/C8DT03941K .

Wang, Q.; Zhao, W.; He, J.; Zhang, Y.; Chen, E. Y. X . Living ring-opening polymerization of lactones by N -heterocyclic olefin/Al(C 6 F 5 ) 3 Lewis pairs: Structures of intermediates, kinetics, and mechanism . Macromolecules , 2017 . 50 123 - 136 . DOI: 10.1021/acs.macromol.6b02398 http://doi.org/10.1021/acs.macromol.6b02398 .

Zhao, J.; Hadjichristidis, N . Polymerization of 5-alkyl δ -lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides . Polym. Chem. , 2015 . 6 2659 - 2668 . DOI: 10.1039/C5PY00019J http://doi.org/10.1039/C5PY00019J .

Pothupitiya, J. U.; Hewawasam, R. S.; Kiesewetter, M. K . Urea and thiourea H-bond donating catalysts for ring-opening polymerization: Mechanistic insights via (non)linear free energy relationships . Macromolecules , 2018 . 51 3203 - 3211 . DOI: 10.1021/acs.macromol.8b00321 http://doi.org/10.1021/acs.macromol.8b00321 .

Fuchise, K.; Igarashi, M.; Sato, K.; Shimada, S . Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts . Chem. Sci. , 2018 . 9 2879 - 2891 . DOI: 10.1039/C7SC04234E http://doi.org/10.1039/C7SC04234E .

Dove, A. P.; Pratt, R. C.; Lohmeijer, B. G. G.; Waymouth, R. M.; Hedrick, J. L . Thiourea-based bifunctional organocatalysis: Supramolecular recognition for living polymerization . J. Am. Chem. Soc. , 2005 . 127 13798 - 13799 . DOI: 10.1021/ja0543346 http://doi.org/10.1021/ja0543346 .

Kazakov, O. I.; Datta, P. P.; Isajani, M.; Kiesewetter, E. T.; Kiesewetter, M. K . Cooperative hydrogen-bond pairing in organocatalytic ring-opening polymerization . Macromolecules , 2014 . 47 7463 - 7468 . DOI: 10.1021/ma501847x http://doi.org/10.1021/ma501847x .

Kazakov, O. I.; Kiesewetter, M. K . Cocatalyst binding effects in organocatalytic ring-opening polymerization of L-lactide . Macromolecules , 2015 . 48 6121 - 6126 . DOI: 10.1021/acs.macromol.5b01140 http://doi.org/10.1021/acs.macromol.5b01140 .

Datta, P . Coupled equilibria in H-bond donating ring-opening polymerization: The effective catalyst-determined shift of a polymerization equilibrium . Eur. Polym. J. , 2017 . 95 671 - 677 . DOI: 10.1016/j.eurpolymj.2017.05.018 http://doi.org/10.1016/j.eurpolymj.2017.05.018 .

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