Dynamic Ring-chain Equilibrium of Nucleophilic Thiol-yne “Click” Polyaddition for Recyclable Poly(dithioacetal)s

Jin-Xia Lei; Qi-Yuan Wang; Fu-Sheng Du; Zi-Chen Li

doi:10.1007/s10118-021-2587-y

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Dynamic Ring-chain Equilibrium of Nucleophilic Thiol-yne “Click” Polyaddition for Recyclable Poly(dithioacetal)s

ARTICLE | Updated：2021-05-27

- Dynamic Ring-chain Equilibrium of Nucleophilic Thiol-yne “Click” Polyaddition for Recyclable Poly(dithioacetal)s
- Dynamic Ring-chain Equilibrium of Nucleophilic Thiol-yne “Click” Polyaddition for Recyclable Poly(dithioacetal)s
- Chinese Journal of Polymer Science 2021年39卷第9期页码：1146-1154
- Affiliations：
  
  Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Polym. Chem. & Physics of Ministry of Education, Department of Polymer Science & Engineering, College of Chemistry and Molecular Engineering, Center for Soft Matter Science and Engineering, Peking University, Beijing 100871, China
- Author bio：
  
  fsdu@pku.edu.cn (F.S.D.)
  zcli@pku.edu.cn (Z.C.L.)
- Funds：
  
  This work was financially supported by the National Key Research and Development Program of China (No. 2016YFA0201400) and the National Natural Science Foundation of China (Nos. 21971005 and 21534001).
- DOI：10.1007/s10118-021-2587-y
  中图分类号：
- 收稿：2021-03-10，
  
  修回：2021-4-5，
  
  录用：2021-4-8，
  
  网络首发：2021-05-27，
  
  纸质出版：2021-07-18
- Accepted：
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Lei, J. X.; Wang, Q. Y.; Du, F. S.; Li, Z. C. Dynamic ring-chain equilibrium of nucleophilic thiol-yne “click” polyaddition for recyclable poly(dithioacetal)s. Chinese J. Polym. Sci. 2021, 39, 1146–1154

Jin-Xia Lei, Qi-Yuan Wang, Fu-Sheng Du, et al. Dynamic Ring-chain Equilibrium of Nucleophilic Thiol-yne “Click” Polyaddition for Recyclable Poly(dithioacetal)s[J]. Chinese Journal of Polymer Science, 2021, 39(9): 1146-1154.
Lei, J. X.; Wang, Q. Y.; Du, F. S.; Li, Z. C. Dynamic ring-chain equilibrium of nucleophilic thiol-yne “click” polyaddition for recyclable poly(dithioacetal)s. Chinese J. Polym. Sci. 2021, 39, 1146–1154 DOI： 10.1007/s10118-021-2587-y.

Jin-Xia Lei, Qi-Yuan Wang, Fu-Sheng Du, et al. Dynamic Ring-chain Equilibrium of Nucleophilic Thiol-yne “Click” Polyaddition for Recyclable Poly(dithioacetal)s[J]. Chinese Journal of Polymer Science, 2021, 39(9): 1146-1154. DOI： 10.1007/s10118-021-2587-y.

摘要

Abstract

We report a dynamic polymerization system based on the reversible nucleophilic Michael polyaddition of activated alkynes and dithiols. Four poly(dithioacetal)s (

−

) were prepared

via

the base-catalyzed thiol-yne “click” polyaddition of two dithiols (1

4-butanedithiol (

) and 1

5-pentanedithiol (

)) and two alkynones (3-butyn-2-one (

) and 1-phenyl-2-propyn-1-one (

)) at high concentrations. We systematically investigated the base-catalyzed polymerization of

and

(for polymer

) under different conditions

and found that this polymerization was a highly concentration-dependent dynamic system: polymer

was formed at high concentration

while seven-membered dithioacetal

1-(1

3-dithiepan-2-yl) propan-2-one (

)

was obtained at low concentration. The polymerization of

and

(for polymer

) displayed similar polymerization behavior

generating 2-(1

3-dithiepan-2-yl)-1-phenylethanone (

) at low concentration. On the contrary

polymer

(from

and

) was exclusively obtained with no formation of eight-membered dithioacetal. The polymerizations of

with 1

2-ethanedithiol (

) and 1

3-dimercaptopropane (

) only afforded corresponding five- and six-membered dithioacetals

1-(1

3-dithiolan-2-yl) propan-2-one (

) and 1-(1

3-dithian-2-yl) propan-2-one (

). This dynamic behavior of

and

was attributed to the concentration-dependent retro-Michael addition reaction between a thiol and a

-sulfido-

-unsaturated carbonyl compound catalyzed by bases. Furthermore

polymers

and

could be depolymerized into

and

in yields of 58% and 95%

respectively. The ring-opening polymerization of

at high concentration could successfully regenerate polymer

. Thus

a new type of closed-loop recyclable poly(dithioacetal)s was developed.

关键词

Keywords

references

Mutlu, H.; Ceper, E. B.; Li, X.; Yang, J.; Dong, W.; Ozmen, M. M.; Theato, P. . Sulfur chemistry in polymer and materials science . Macromol. Rapid Commun. , 2019 . 40 e1800650 DOI: 10.1002/marc.201800650 http://doi.org/10.1002/marc.201800650 .

Zhang, C. J.; Zhang, X. H. . Recent progress on COS-derived polymers . Chinese J. Polym. Sci. , 2019 . 37 951 - 958 . DOI: 10.1007/s10118-019-2288-y http://doi.org/10.1007/s10118-019-2288-y .

Wang, Y.; Yang, J. L.; Zhang, C. J.; Zhang, X. H. . Organocatalytic polymerization of sulfur-containing one-carbon monomer and epoxides . Acta Polymerica Sinica (in Chinese) , 2020 . 51 1092 - 1103 . .

Napoli, A.; Valentini, M.; Tirelli, N.; Müller, M.; Hubbell, J. A. . Oxidation-responsive polymeric vesicles . Nat. Mater. , 2004 . 3 183 - 189 . DOI: 10.1038/nmat1081 http://doi.org/10.1038/nmat1081 .

Kolb, H. C.; Finn, M. G.; Sharpless, K. B. . Click chemistry: diverse chemical function from a few good reactions . Angew. Chem. Int. Ed. , 2001 . 40 2004 - 2021 . DOI: 10.1002/1521-3773(20010601)40:11<2004::AID-ANIE2004>3.0.CO;2-5 http://doi.org/10.1002/1521-3773(20010601)40:11<2004::AID-ANIE2004>3.0.CO;2-5 .

Lowe, A. B. . Thiol-ene "click" reactions and recent applications in polymer and materials synthesis . Polym. Chem. , 2010 . 1 17 - 36 . DOI: 10.1039/B9PY00216B http://doi.org/10.1039/B9PY00216B .

Hoyle, C. E.; Lowe, A. B.; Bowman, C. N. . Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis . Chem. Soc. Rev. , 2010 . 39 1355 - 1387 . DOI: 10.1039/b901979k http://doi.org/10.1039/b901979k .

Lowe, A. B. . Thiol-yne ‘click’/coupling chemistry and recent applications in polymer and materials synthesis and modification . Polymer , 2014 . 55 5517 - 5549 . DOI: 10.1016/j.polymer.2014.08.015 http://doi.org/10.1016/j.polymer.2014.08.015 .

Lowe, A. B. . Thiol-ene "click" reactions and recent applications in polymer and materials synthesis: a first update . Polym. Chem. , 2014 . 5 4820 - 4870 . DOI: 10.1039/C4PY00339J http://doi.org/10.1039/C4PY00339J .

Nair, D. P.; Podgorski, M.; Chatani, S.; Gong, T.; Xi, W. X.; Fenoli, C. R.; Bowman, C. N. . The thiol-Michael addition click reaction: a powerful and widely used tool in materials chemistry . Chem. Mater. , 2014 . 26 727 - 744 . .

Schneiderman, D. K.; Hillmyer, M. A. . 50 th Anniversary perspective: there is a great future in sustainable polymers . Macromolecules , 2017 . 50 3733 - 3750 . DOI: 10.1021/acs.macromol.7b00293 http://doi.org/10.1021/acs.macromol.7b00293 .

Hong, M.; Chen, E. Y. X. . Chemically recyclable polymers: a circular economy approach to sustainability . Green Chem. , 2017 . 19 3692 - 3706 . DOI: 10.1039/C7GC01496A http://doi.org/10.1039/C7GC01496A .

Fortman, D. J.; Brutman, J. P.; De Hoe, G. X.; Snyder, R. L.; Dichtel, W. R.; Hillmyer, M. A. . Approaches to sustainable and continually recyclable cross-linked polymers . ACS Sustain. Chem. Eng. , 2018 . 6 11145 - 11159 . DOI: 10.1021/acssuschemeng.8b02355 http://doi.org/10.1021/acssuschemeng.8b02355 .

Zhang, X.; Fevre, M.; Jones, G. O.; Waymouth, R. M. . Catalysis as an enabling science for sustainable polymers . Chem. Rev. , 2018 . 118 839 - 885 . DOI: 10.1021/acs.chemrev.7b00329 http://doi.org/10.1021/acs.chemrev.7b00329 .

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 .

Coates, G. W.; Getzler, Y. . Chemical recycling to monomer for an ideal, circular polymer economy . Nat. Rev. Mater. , 2020 . 5 501 - 516 . DOI: 10.1038/s41578-020-0190-4 http://doi.org/10.1038/s41578-020-0190-4 .

Huang, D.; Liu, Y.; Qin, A.; Tang, B. Z. . Recent advances in alkyne-based click polymerizations . Polym. Chem. , 2018 . 9 2853 - 2867 . DOI: 10.1039/C7PY02047C http://doi.org/10.1039/C7PY02047C .

Huang, D.; Liu, Y.; Guo, S.; Li, B. X.; Wang, J.; Yao, B. C.; Qin, A. J.; Tang, B. Z. . Transition metal-free thiol-yne click polymerization toward Z-stereoregular poly(vinylene sulfide)s . Polym. Chem. , 2019 . 10 3088 - 3096 . DOI: 10.1039/C9PY00161A http://doi.org/10.1039/C9PY00161A .

Daglar, O.; Luleburgaz, S.; Baysak, E.; Gunay, U. S.; Hizal, G.; Tunca, U.; Durmaz, H. . Nucleophilic thiol-yne reaction in macromolecular engineering: from synthesis to applications . Eur. Polym. J. , 2020 . 137 109926 DOI: 10.1016/j.eurpolymj.2020.109926 http://doi.org/10.1016/j.eurpolymj.2020.109926 .

Han, J.; Zheng, Y.; Zhao, B.; Li, S.; Zhang, Y.; Gao, C. . Sequentially hetero-functional, topological polymers by step-growth thiol-yne approach . Scientif. Rep. , 2014 . 4 4387 .

Fairbanks, B. D.; Scott, T. F.; Kloxin, C. J.; Anseth, K. S.; Bowman, C. N. . Thiol-yne photopolymerizations: novel mechanism, kinetics, and step-growth formation of highly cross-linked networks . Macromolecules , 2009 . 42 211 - 217 . DOI: 10.1021/ma801903w http://doi.org/10.1021/ma801903w .

Chen, G.; Kumar, J.; Gregory, A.; Stenzel, M. H. . , Efficient synthesis of dendrimers via a thiol-yne and esterification process and their potential application in the delivery of platinum anti-cancer drugs . Chem. Commun. , 2009 . 6291 - 6293 . .

Konkolewicz, D.; Gray-Weale, A.; Perrier, S. . Hyperbranched polymers by thiol-yne chemistry: from small molecules to functional polymers . J. Am. Chem. Soc. , 2009 . 131 18075 - 18077 . DOI: 10.1021/ja908206a http://doi.org/10.1021/ja908206a .

Yao, B.; Hu, T.; Zhang, H.; Li, J.; Sun, J. Z.; Qin, A.; Tang, B. Z. . Multi-functional hyperbranched poly(vinylene sulfide)s constructed via spontaneous thiol-yne click polymerization . Macromolecules , 2015 . 48 7782 - 7791 . DOI: 10.1021/acs.macromol.5b01868 http://doi.org/10.1021/acs.macromol.5b01868 .

Kuroda, H.; Tomita, I.; Endo, T. . Facile synthetic method for the preparation of dithioacetals by the double conjugate addition of acetylenes bearing electron-withdrawing groups with thiols . Synthetic. Commun. , 1996 . 26 1539 - 1543 . DOI: 10.1080/00397919608003520 http://doi.org/10.1080/00397919608003520 .

Truong, V. X.; Dove, A. P. . Organocatalytic, regioselective nucleophilic "click" addition of thiols to propiolic acid esters for polymer-polymer coupling . Angew. Chem. Int. Ed. , 2013 . 52 4132 - 4136 . DOI: 10.1002/anie.201209239 http://doi.org/10.1002/anie.201209239 .

Jim, C. K. W.; Qin, A.; Lam, J. W. Y.; Mahtab, F.; Yu, Y.; Tang, B. Z. . Metal-free alkyne polyhydrothiolation: synthesis of functional poly(vinylenesulfide)s with high stereoregularity by regioselective thioclick polymerization . Adv. Funct. Mater. , 2010 . 20 1319 - 1328 . DOI: 10.1002/adfm.200901943 http://doi.org/10.1002/adfm.200901943 .

Du, J.; Huang, D.; Li, H.; Qin, A.; Tang, B. Z.; Li, Y. . Catalyst-free click polymerization of thiol and activated internal alkynes: a facile strategy toward functional poly( β -thioacrylate)s . Macromolecules , 2020 . 53 4932 - 4941 . DOI: 10.1021/acs.macromol.0c00311 http://doi.org/10.1021/acs.macromol.0c00311 .

Bell, C. A.; Yu, J.; Barker, I. A.; Truong, V. X.; Cao, Z.; Dobrinyin, A. V.; Becker, M. L.; Dove, A. P. . Independent control of elastomer properties through stereocontrolled synthesis . Angew. Chem. Int. Ed. , 2016 . 55 13076 - 13080 . DOI: 10.1002/anie.201606750 http://doi.org/10.1002/anie.201606750 .

Truong, V. X.; Ablett, M. P.; Richardson, S. M.; Hoyland, J. A.; Dove, A. P. . Simultaneous orthogonal dual-click approach to tough, in-situ-forming hydrogels for cell encapsulation . J. Am. Chem. Soc. , 2015 . 137 1618 - 1622 . DOI: 10.1021/ja511681s http://doi.org/10.1021/ja511681s .

Macdougall, L. J.; Truong, V. X.; Dove, A. P. . Efficient in situ nucleophilic thiol-yne click chemistry for the synthesis of strong hydrogel materials with tunable properties . ACS Macro Lett. , 2017 . 6 93 - 97 . DOI: 10.1021/acsmacrolett.6b00857 http://doi.org/10.1021/acsmacrolett.6b00857 .

Gunay, U. S.; Cetin, M.; Daglar, O.; Hizal, G.; Tunca, U.; Durmaz, H. . Ultrafast and efficient aza- and thiol-michael reactions on a polyester scaffold with internal electron deficient triple bonds . Polym. Chem. , 2018 . 9 3037 - 3054 . DOI: 10.1039/C8PY00485D http://doi.org/10.1039/C8PY00485D .

Perin, G.; Mello, L. G.; Radatz, C. S.; Savegnago, L.; Alves, D.; Jacob, R. G.; Lenardao, E. J. . Green, catalyst-free thioacetalization of carbonyl compounds using glycerol as recyclable solvent . Tetrahedron Lett. , 2010 . 51 4354 - 4356 . DOI: 10.1016/j.tetlet.2010.06.049 http://doi.org/10.1016/j.tetlet.2010.06.049 .

Fatona, A.; Moran-Mirabal, J.; Brook, M. A. . Controlling silicone networks using dithioacetal crosslinks . Polym. Chem. , 2019 . 10 219 - 227 . DOI: 10.1039/C8PY01352G http://doi.org/10.1039/C8PY01352G .

Xu, L.; Zhao, M.; Zhang, H.; Gao, W.; Guo, Z.; Zhang, X.; Zhang, J.; Cao, J.; Pu, Y.; He, B. . Cinnamaldehyde-based poly(ester-thioacetal) to generate reactive oxygen species for fabricating reactive oxygen species-responsive nanoparticles . Biomacromolecules , 2018 . 19 4658 - 4667 . DOI: 10.1021/acs.biomac.8b01423 http://doi.org/10.1021/acs.biomac.8b01423 .

Gaston Orrillo, A.; Escalante, A. M.; Furlan, R. L. E. . Dithioacetal exchange: a new reversible reaction for dynamic combinatorial chemistry . Chem. Eur. J. , 2016 . 22 6746 - 6749 . DOI: 10.1002/chem.201600208 http://doi.org/10.1002/chem.201600208 .

Orrillo, A. G.; Escalante, A. M.; Furlan, R. L. E. . Host amplification in a dithioacetal-based dynamic covalent library . Org. Lett. , 2017 . 19 1446 - 1449 . DOI: 10.1021/acs.orglett.7b00401 http://doi.org/10.1021/acs.orglett.7b00401 .

Joshi, G.; Anslyn, E. V. . Dynamic thiol exchange with β -sulfido- α , β -unsaturated carbonyl compounds and dithianes . Org. Lett. , 2012 . 14 4714 - 4717 . DOI: 10.1021/ol301781u http://doi.org/10.1021/ol301781u .

Fan, B.; Zhang, K.; Liu, Q.; Eelkema, R. . Self-healing injectable polymer hydrogel via dynamic thiol-alkynone double addition cross-links . ACS Macro Lett. , 2020 . 9 776 - 780 . DOI: 10.1021/acsmacrolett.0c00241 http://doi.org/10.1021/acsmacrolett.0c00241 .

van herck, N.; Maes, D.; Unal, K.; Guerre, M.; Winne, J. M.; Du Prez, F. E. . Covalent adaptable networks with tunable exchange rates based on reversible thiol-yne cross-linking . Angew. Chem. Int. Ed. , 2020 . 59 3609 - 3617 . DOI: 10.1002/anie.201912902 http://doi.org/10.1002/anie.201912902 .

Kuroda, H.; Tomita, I.; Endo, T. . A novel phosphine-catalysed polyaddition of terminal acetylenes bearing electron-withdrawing groups with dithiols. Synthesis of polymers having dithioacetal moieties in the main chain . Polymer , 1997 . 38 6049 - 6054 . DOI: 10.1016/S0032-3861(97)00152-3 http://doi.org/10.1016/S0032-3861(97)00152-3 .

Daglar, O.; Cakmakci, E.; Gunay, U. S.; Hizal, G.; Tunca, U.; Durmaz, H. . A straightforward method for fluorinated polythioether synthesis . Macromolecules , 2020 . 53 2965 - 2975 . DOI: 10.1021/acs.macromol.0c00548 http://doi.org/10.1021/acs.macromol.0c00548 .

Daglar, O.; Gunay, U. S.; Hizal, G.; Tunca, U.; Durmaz, H. . Extremely rapid polythioether synthesis in the presence of TBD . Macromolecules , 2019 . 52 3558 - 3572 . DOI: 10.1021/acs.macromol.9b00293 http://doi.org/10.1021/acs.macromol.9b00293 .

Andrzej, D.; Adam, K.; Jan, L.; Stanislaw, P. . Thermodynamic and kinetic polymerizability of cyclic esters . Macromol. Symp. , 2005 . 224 71 - 84 . DOI: 10.1002/masy.200550607 http://doi.org/10.1002/masy.200550607 .

Hong, M.; Tang, X.; Newell, B. S.; Chen, E. Y. X. . "Nonstrained" γ -butyrolactone-based copolyesters: copolymerization characteristics and composition-dependent (thermal, eutectic, cocrystallization, and degradation) properties . Macromolecules , 2017 . 50 8469 - 8479 . DOI: 10.1021/acs.macromol.7b02174 http://doi.org/10.1021/acs.macromol.7b02174 .

Shen, Y.; Li, Z. B. . Ring-opening polymerization of cyclic esters by utilizing organophosphazene bases toward biodegradable polyesters . Acta Polymerica Sinica (in Chinese) , 2020 . 51 777 - 790 . .

Musgrave, R. A.; Russell, A. D.; Hayward, D. W.; Whittell, G. R.; Lawrence, P. G.; Gates, P. J.; Green, J. C.; Manners, I. . Main-chain metallopolymers at the static-dynamic boundary based on nickelocene . Nat. Chem. , 2017 . 9 743 - 750 . DOI: 10.1038/nchem.2743 http://doi.org/10.1038/nchem.2743 .

Dewit, M. A.; Beaton, A.; Gillies, E. R. . A reduction sensitive cascade biodegradable linear polymer . J. Polym. Sci., Part A: Polym. Chem. , 2010 . 48 3977 - 3985 . DOI: 10.1002/pola.24180 http://doi.org/10.1002/pola.24180 .

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