Isoselective Ring-opening Polymerization of Racemic Lactide Catalyzed by <italic style="font-style: italic">N</italic>-heterocyclic Olefin/(Thio)urea Organocatalysts

Zhen-Yu Wang; Guang-Qiang Xu; Li Zhou; Cheng-Dong Lv; Ru-Lin Yang; Bing-Zhe Dong; Qing-Gang Wang

doi:10.1007/s10118-021-2535-x

Your Location：

Home >

Browse articles >

Isoselective Ring-opening Polymerization of Racemic Lactide Catalyzed by N-heterocyclic Olefin/(Thio)urea Organocatalysts

ARTICLE | Updated：2021-01-05

- Isoselective Ring-opening Polymerization of Racemic Lactide Catalyzed by N-heterocyclic Olefin/(Thio)urea Organocatalysts
- Chinese Journal of Polymer Science Vol. 39, Issue 6, Pages: 709-715(2021)
- Affiliations：
  
  a.Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China
  b.Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
- Author bio：
  
  xu_gq@qibebt.ac.cn (G.Q.X.)
  zhouli@qibebt.ac.cn (L.Z.)
  wangqg@qibebt.ac.cn (Q.G.W.)
- Funds：
- DOI：10.1007/s10118-021-2535-x
  CLC：
- Received：29 October 2020，
  
  Revised：2020-11-25，
  
  Accepted：29 November 2020，
  
  Online First：05 January 2021，
  
  Published：15 April 2021
- Accepted：
Scan QR Code
Wang, Z. Y.; Xu, G. Q.; Zhou, L.; Lv, C. D.; Yang, R. L.; Dong, B. Z.; Wang, Q. G. Isoselective ring-opening polymerization of racemic lactide catalyzed by , N,-heterocyclic olefin/(thio)urea organocatalysts. Chinese J. Polym. Sci. 2021, 39, 709–715

Zhen-Yu Wang, Guang-Qiang Xu, Li Zhou, et al. Isoselective Ring-opening Polymerization of Racemic Lactide Catalyzed by N-heterocyclic Olefin/(Thio)urea Organocatalysts[J]. Chinese Journal of Polymer Science, 2021, 39(6): 709-715. DOI: 10.1007/s10118-021-2535-x.
Wang, Z. Y.; Xu, G. Q.; Zhou, L.; Lv, C. D.; Yang, R. L.; Dong, B. Z.; Wang, Q. G. Isoselective ring-opening polymerization of racemic lactide catalyzed by , N,-heterocyclic olefin/(thio)urea organocatalysts. Chinese J. Polym. Sci. 2021, 39, 709–715 DOI： 10.1007/s10118-021-2535-x.

Zhen-Yu Wang, Guang-Qiang Xu, Li Zhou, et al. Isoselective Ring-opening Polymerization of Racemic Lactide Catalyzed by N-heterocyclic Olefin/(Thio)urea Organocatalysts[J]. Chinese Journal of Polymer Science, 2021, 39(6): 709-715. DOI: 10.1007/s10118-021-2535-x. DOI：

摘要

Abstract

The isoselective ring-opening polymerization of racemic lactide was achieved by combining

-heterocyclic olefin (NHO) with mono(thio)ureas or bis(thio)ureas as catalytic systems. The polymerization process shows high stereoselectivity

controllability and reactivity

delivering multi-block isotactic polylactides with high chain-end fidelity and narrow molecular weight distributions. The enhancement of catalytic performance was observed in the following order: bisthiourea (DTU)

monothiourea (TU)

bisurea (DU)

urea (U). The highest

(probability of forming a

meso

dyad) = 0.91 was observed at −70 °C when using NHO/U1 catalytic system and the high stereoselectivity was attributed to chain-end control mechanism.

关键词

Keywords

references

Rangari, D.; Vasanthan, N. . Study of strain-induced crystallization and enzymatic degradation of drawn poly(L-lactic acid) (PLLA) films . Macromolecules , 2012 . 45 7397 - 7403 . DOI: 10.1021/ma301482j http://doi.org/10.1021/ma301482j .

Drumright, R. E.; Gruber, P. R.; Henton, D. E. . Polylactic acid technology . Adv. Mater. , 2000 . 12 1841 - 1846 . DOI: 10.1002/1521-4095(200012)12:23<1841::AID-ADMA1841>3.0.CO;2-E http://doi.org/10.1002/1521-4095(200012)12:23<1841::AID-ADMA1841>3.0.CO;2-E .

Wachsen, O.; Platkowski, K.; Reichert, K. H. . Thermal degradation of poly-L-lactide—studies on kinetics, modelling and melt stabilisation . Polym. Degrad. Stabil. , 1997 . 57 87 - 94 . DOI: 10.1016/S0141-3910(96)00226-1 http://doi.org/10.1016/S0141-3910(96)00226-1 .

Dechy-Cabaret, O.; Martin-Vaca, B.; Bourissou, D. . Controlled ring-opening polymerization of lactide and glycolide . Chem. Rev. , 2004 . 104 6147 - 6176 . DOI: 10.1021/cr040002s http://doi.org/10.1021/cr040002s .

Tang, X. Y.; Chen, E. Y. X. . Toward infinitely recyclable plastics derived from renewable cyclic esters . Chem , 2019 . 5 284 - 312 . DOI: 10.1016/j.chempr.2018.10.011 http://doi.org/10.1016/j.chempr.2018.10.011 .

Xu, G. Q.; Mahmood, Q.; Lv, C. D.; Yang, R. L.; Zhou, L.; Wang, Q. G. . Asymmetric kinetic resolution polymerization . Coordin. Chem. Rev. , 2020 . 414 213296 DOI: 10.1016/j.ccr.2020.213296 http://doi.org/10.1016/j.ccr.2020.213296 .

Nomura, N.; Hasegawa, J.; Ishii, R. . A direct function relationship between isotacticity and melting temperature of multiblock stereocopolymer poly( rac -lactide) . Macromolecules , 2009 . 42 4907 - 4909 . DOI: 10.1021/ma900760z http://doi.org/10.1021/ma900760z .

Orhan, B.; Tschan, M. J. L.; Wirotius, A. L.; Dove, A. P.; Coulembier, O.; Taton, D. . Isoselective ring-opening polymerization of rac -lactide from chiral Takemoto’s organocatalysts: elucidation of stereocontrol . ACS Macro Lett. , 2018 . 7 1413 - 1419 . DOI: 10.1021/acsmacrolett.8b00852 http://doi.org/10.1021/acsmacrolett.8b00852 .

Zhang, X. Y.; 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 .

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 .

Spassky, N.; Wisniewski, M.; Pluta, C.; LeBorgne, A. . Highly stereoelective polymerization of rac -(D,L)-lactide with a chiral Schiff's base/aluminium alkoxide initiator . Macromol. Chem. Phys. , 1996 . 197 2627 - 2637 . DOI: 10.1002/macp.1996.021970902 http://doi.org/10.1002/macp.1996.021970902 .

Zhong, Z. Y.; Dijkstra, P. J.; Feijen, J. . [(Salen)Al]-mediated, controlled and stereoselective ring-opening polymerization of lactide in solution and without solvent: synthesis of highly isotactic polylactide stereocopolymers from racemic D,L-lactide . Angew. Chem. Int. Ed. , 2002 . 41 4510 - 4513 . DOI: 10.1002/1521-3773(20021202)41:23<4510::AID-ANIE4510>3.0.CO;2-L http://doi.org/10.1002/1521-3773(20021202)41:23<4510::AID-ANIE4510>3.0.CO;2-L .

Nomura, N.; Ishii, R.; Yamamoto, Y.; Kondo, T. . Stereoselective ring-opening polymerization of a racemic lactide by using achiral salen- and homosalen-aluminum complexes . Chem. Eur. J. , 2007 . 13 4433 - 4451 . DOI: 10.1002/chem.200601308 http://doi.org/10.1002/chem.200601308 .

Maudoux, N.; Roisnel, T.; Dorcet, V.; Carpentier, J. F.; Sarazin, Y. . Chiral (1,2)-diphenylethylene-salen complexes of triel metals: coordination patterns and mechanistic considerations in the isoselective ROP of lactide . Chem. Eur. J. , 2014 . 20 6131 - 6147 . DOI: 10.1002/chem.201304788 http://doi.org/10.1002/chem.201304788 .

Abbina, S.; Du, G. D. . Zinc-catalyzed highly isoselective ring opening polymerization of rac -lactide . ACS Macro Lett. , 2014 . 3 689 - 692 . DOI: 10.1021/mz5002959 http://doi.org/10.1021/mz5002959 .

Kan, C.; Hu, J. W.; Huang, Y.; Wang, H. B.; Ma, H. Y. . Highly isoselective and active zinc catalysts for rac -lactide polymerization: effect of pendant groups of aminophenolate ligands . Macromolecules , 2017 . 50 7911 - 7919 . DOI: 10.1021/acs.macromol.7b01420 http://doi.org/10.1021/acs.macromol.7b01420 .

Marin, P.; Tschan, M. J. L.; Isnard, F.; Robert, C.; Haquette, P.; Trivelli, X.; Chamoreau, L. M.; Guerineau, V.; del Rosal, I.; Maron, L.; Venditto, V.; Thomas, C. M. . Polymerization of rac -lactide using achiral iron complexes: access to thermally stable stereocomplexes . Angew. Chem. Int. Ed. , 2019 . 58 12585 - 12589 . DOI: 10.1002/anie.201903224 http://doi.org/10.1002/anie.201903224 .

Zhang, J. J.; Xiong, J.; Sun, Y. Y.; Tang, N.; Wu, J. C. . Highly iso-selective and active catalysts of sodium and potassium monophenoxides capped by a crown ether for the ring-opening polymerization of rac -lactide . Macromolecules , 2014 . 47 7789 - 7796 . DOI: 10.1021/ma502000y http://doi.org/10.1021/ma502000y .

Chen, C. J.; Jiang, J. X.; Mao, X. Y.; Cong, Y.; Cui, Y. Q.; Pan, X. B.; Wu, J. C. . Isoselective polymerization of rac -lactide catalyzed by ion-paired potassium amidinate complexes . Inorg. Chem. , 2018 . 57 3158 - 3168 . DOI: 10.1021/acs.inorgchem.7b03184 http://doi.org/10.1021/acs.inorgchem.7b03184 .

Kan, Z.; Luo, W. L.; Shi, T.; Wei, C. Z.; Han, B. H.; Zheng, D. J.; Liu, S. F. . Facile preparation of stereoblock PLA from ring-opening polymerization of rac -lactide by a synergetic binary catalytic system containing ureas and alkoxides . Front. Chem. , 2018 . 6 547 DOI: 10.3389/fchem.2018.00547 http://doi.org/10.3389/fchem.2018.00547 .

Arnold, P. L.; Buffet, J. C.; Blaudeck, R. P.; Sujecki, S.; Blake, A. J.; Wilson, C. . C 3 -symmetric lanthanide tris(alkoxide) complexes formed by preferential complexation and their stereoselective polymerization of rac -lactide . Angew. Chem. Int. Ed. , 2008 . 47 6033 - 6036 . DOI: 10.1002/anie.200801279 http://doi.org/10.1002/anie.200801279 .

Myers, D.; White, A. J. P.; Forsyth, C. M.; Bown, M.; Williams, C. K. . Phosphasalen indium complexes showing high rates and isoselectivities in rac -lactide polymerizations . Angew. Chem. Int. Ed. , 2017 . 56 5277 - 5282 . DOI: 10.1002/anie.201701745 http://doi.org/10.1002/anie.201701745 .

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 http://doi.org/10.1021/acs.macromol.6b02439 .

Jones, M. D.; Hancock, S. L.; McKeown, P.; Schafer, P. M.; Buchard, A.; Thomas, L. H.; Mahon, M. F.; Lowe, J. P. . Zirconium complexes of bipyrrolidine derived salan ligands for the isoselective polymerisation of rac -lactide . Chem. Commun. , 2014 . 50 15967 - 15970 . DOI: 10.1039/C4CC07871C http://doi.org/10.1039/C4CC07871C .

Rosen, T.; Rajpurohit, J.; Lipstman, S.; Venditto, V.; Kol, M. . Isoselective polymerization of rac -lactide by highly active sequential {ONNN} magnesium complexes . Chem. Eur. J. , 2020 . DOI: 10.1002/chem.202003616 DOI: 10.1002/chem.202003616 http://doi.org/10.1002/chem.202003616 .

Dove, A. P.; Li, H. B.; Pratt, R. C.; Lohmeijer, B. G. G.; Culkin, D. A.; Waymouth, R. M.; Hedrick, J. L. . Stereoselective polymerization of rac - and meso -lactide catalyzed by sterically encumbered N -heterocyclic carbenes . Chem. Commun. , 2006 . 27 2881 - 2883 . .

Zhang, L.; Nederberg, F.; Messman, J. M.; Pratt, R. C.; Hedrick, J. L.; Wade, C. G. . Organocatalytic stereoselective ring-opening polymerization of lactide with dimeric phosphazene bases . J. Am. Chem. Soc. , 2007 . 129 12610 - 12611 . DOI: 10.1021/ja074131c http://doi.org/10.1021/ja074131c .

Liu, S. F.; Li, H. K.; Zhao, N.; Li, Z. B. . Stereoselective ring-opening polymerization of rac -lactide using organocatalytic cyclic trimeric phosphazene base . ACS Macro Lett. , 2018 . 7 624 - 628 . DOI: 10.1021/acsmacrolett.8b00353 http://doi.org/10.1021/acsmacrolett.8b00353 .

Sanchez-Sanchez, A.; Rivilla, I.; Agirre, M.; Basterretxea, A.; Etxeberria, A.; Veloso, A.; Sardon, H.; Mecerreyes, D.; Cossío, F. P. . Enantioselective ring-opening polymerization of rac -lactide dictated by densely substituted amino acids . J. Am. Chem. Soc. , 2017 . 139 4805 - 4814 . DOI: 10.1021/jacs.6b13080 http://doi.org/10.1021/jacs.6b13080 .

Zhou, L.; Xu, G. Q.; Mahmood, Q.; Lv, C. D.; Wang, X. W.; Sun, X. T.; Guo, K.; Wang, Q. G. . N -Heterocyclic olefins and thioureas as an efficient cooperative catalyst system for ring-opening polymerization of δ -valerolactone . Polym. Chem. , 2019 . 10 1832 - 1838 . DOI: 10.1039/C9PY00018F http://doi.org/10.1039/C9PY00018F .

Zhou, L.; Wang, Z. Y.; Xu, G. Q.; Yang, R. L.; Yan, H. T.; Hao, X. Q.; Wang, Q. G. . N -Heterocyclic olefins catalyzed ring-opening polymerization of N -tosyl aziridines . Eur. Polym. J. , 2020 . 140 110046 DOI: 10.1016/j.eurpolymj.2020.110046 http://doi.org/10.1016/j.eurpolymj.2020.110046 .

Kronig, S.; Jones, P. G.; Tamm, M. . Preparation of 2-alkylidene-substituted 1,3,4,5-tetramethylimidazolines and their reactivity towards Rh I complexes and B(C 6 F 5 ) 3 . Eur. J. Inorg. Chem. , 2013 . 13 2301 - 2314 . .

Naumann, S.; Thomas, A. W.; Dove, A. P. . N -heterocyclic olefins as organocatalysts for polymerization: preparation of well-defined poly(propylene oxide) . Angew. Chem. Int. Ed. , 2015 . 54 9550 - 9554 . DOI: 10.1002/anie.201504175 http://doi.org/10.1002/anie.201504175 .

Strukil, V.; Igrc, M. D.; Eckert-Maksic, M.; Friscic, T. . Click mechanochemistry: quantitative synthesis of "ready to use" chiral organocatalysts by efficient two-fold thiourea coupling to vicinal diamines . Chem. Eur. J. , 2012 . 18 8464 - 8473 . DOI: 10.1002/chem.201200632 http://doi.org/10.1002/chem.201200632 .

Lv, C. D.; Zhou, L.; Yuan, R. T.; Mahmood, Q.; Xu, G. Q.; Wang, Q. G. . Isoselective ring-opening polymerization and asymmetric kinetic resolution polymerization of rac -lactide catalyzed by bifunctional iminophosphorane-thiourea/urea catalysts . New J. Chem. , 2020 . 44 1648 - 1655 . DOI: 10.1039/C9NJ05074D http://doi.org/10.1039/C9NJ05074D .

Yuan, R. T.; Xu, G. Q.; Lv, C. D.; Zhou, L.; Yang, R. L.; Wang, Q. G. . Bifunctional phosphazene-thiourea/urea catalyzed ring-opening polymerization of cyclic esters . Mater. Today Commun. , 2020 . 22 100747 DOI: 10.1016/j.mtcomm.2019.100747 http://doi.org/10.1016/j.mtcomm.2019.100747 .

Lin, B. H.; 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 .

Lin, B. H.; 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 .

Fastnacht, K. V.; Spink, S. S.; Dharmaratne, N. U.; Pothupitiya, J. U.; Datta, P. P.; Kiesewetter, E. T.; Kiesewetter, M. K. . Bis- and tris-urea H-bond donors for ring-opening polymerization: unprecedented activity and control from an organocatalyst . ACS Macro Lett. , 2016 . 5 982 - 986 . DOI: 10.1021/acsmacrolett.6b00527 http://doi.org/10.1021/acsmacrolett.6b00527 .

Hewawasam, R. S.; Kalana, U. L. D. I.; Dharmaratne, N. U.; Wright, T. J.; Bannin, T. J.; Kiesewetter, E. T.; Kiesewetter, M. K. . Bisurea and bisthiourea H-bonding organocatalysts for ring-opening polymerization: cues for the catalyst design . Macromolecules , 2019 . 52 9232 - 9237 . DOI: 10.1021/acs.macromol.9b01875 http://doi.org/10.1021/acs.macromol.9b01875 .

Shen, Y.; Xiong, W.; Li, Y. Z.; Zhao, Z. C.; Lu, H.; Li, Z. B. . Chemoselective polymerization of fully biorenewable α -methylene- γ -butyrolactone using organophosphazene/urea binary catalysts toward sustainable polyesters . CCS Chem. , 2020 . 2 620 - 630 . .

Moins, S.; Hoyas, S.; Lemaur, V.; Orhan, B.; Delle Chiaie, K.; Lazzaroni, R.; Taton, D.; Dove, A. P.; Coulembier, O. . Stereoselective ROP of rac - and meso -lactides using achiral TBD as catalyst . Catalysts , 2020 . 10 620 DOI: 10.3390/catal10060620 http://doi.org/10.3390/catal10060620 .

Lv, C. D.; Xu, G. Q.; Yang, R. L.; Zhou, L.; Wang, Q. G. . Chiral phosphoric acid catalyzed asymmetric kinetic resolution polymerization of 6-aryl- ε -caprolactones . Polym. Chem. , 2020 . 11 4203 - 4207 . DOI: 10.1039/D0PY00514B http://doi.org/10.1039/D0PY00514B .

Li, H.; Ai, B. R.; Hong, M. . Stereoselective ring-opening polymerization of rac -lactide by bulky chiral and achiral N -heterocyclic carbenes . Chinese J. Polym. Sci. , 2018 . 36 231 - 236 . DOI: 10.1007/s10118-018-2071-5 http://doi.org/10.1007/s10118-018-2071-5 .

Mahmood, Q.; Xu, G. Q.; Zhou, L.; Guo, X. H.; Wang, Q. G . Chiral 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-catalyzed stereoselective ring-opening polymerization of rac -lactide: high reactivity for isotactic enriched polylactides (PLAs) . Polymers , 2020 . 12 2365 DOI: 10.3390/polym12102365 http://doi.org/10.3390/polym12102365 .

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+ .

Kou, X. H; Shen, Y.; Li, Z. B. . Stereoselective ring-opening polymerization of rac -lactide using chiral urea/strong organobase binary catalyst system . Acta Polymerica Sinica (in Chinese) , 2020 . 51 1121 - 1129 . .

Views

118

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Phenylimino-pyridine-phenolate Zinc Complexes for Polylactide Synthesis and Chemical Recycling to Monomers

Stereoselective Ring-opening Polymerization of rac-Lactide by Bulky Chiral and Achiral N-heterocyclic Carbenes

Synthesis of Ultraviolet Absorption Polylactide via Immortal Polymerization of rac-Lactide Initiated by a Salan-yttrium Catalyst

Silk Sericin-inspired Poly-β-homoserine for Protein Protection

Chemoselective Ring-opening Copolymerization of CO2-based Lactones towards Functional Polyesters

Related Author

Jia-Yue Li

Ming-Qian Wang

Zhi-Qiang Ding

He He

Xin-Cui Shi

Bin Wang

Bai-Ru Ai

Miao Hong

Related Institution

Tianjin Key Laboratory of Composite & Functional Materials, School of Materials Science and Engineering, Tianjin University

School of Chemistry and Environmental Engineering, Changchun University of Science and Technology

Key Laboratory of Marine Materials and Related Technologies, Key Laboratory of Marine Materials and Protective Technologies of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences

University of Chinese Academy of Sciences

⁰

Isoselective Ring-opening Polymerization of Racemic Lactide Catalyzed by N-heterocyclic Olefin/(Thio)urea Organocatalysts

DOI：10.1007/s10118-021-2535-x

摘要

Abstract

关键词

Keywords

references