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
- Chinese Journal of Polymer Science Vol. 39, Issue 9, Pages: 1146-1154(2021)
- 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：
- DOI：10.1007/s10118-021-2587-y
  CLC：
- Received：10 March 2021，
  
  Revised：2021-4-5，
  
  Accepted：08 April 2021，
  
  Online First：27 May 2021，
  
  Published：18 July 2021
- 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

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