Ring-closing-opening Copolymerization of Phthalaldehyde and Epoxide towards Acid-degradable Polyether and Polyurethane

Jie Pang; Yu-Bo Zhou; Li-Jun Liu; Hong-Xin Zhang; Jun-Peng Zhao

doi:10.1007/s10118-025-3297-7

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Ring-closing-opening Copolymerization of Phthalaldehyde and Epoxide towards Acid-degradable Polyether and Polyurethane

RESEARCH ARTICLE | Updated：2025-07-14

- Ring-closing-opening Copolymerization of Phthalaldehyde and Epoxide towards Acid-degradable Polyether and Polyurethane
- Chinese Journal of Polymer Science Vol. 43, Issue 6, Pages: 964-972(2025)
- Affiliations：
  
  a.Faculty of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China
  b.Faculty of Materials Science and Engineering, Qinghai University, Xining 810016, China
- Author bio：
  
  mszh.xin@qhu.edu.cn (H.X.Z.)
  msjpzhao@scut.edu.cn (J.P.Z.)
- Funds：
- DOI：10.1007/s10118-025-3297-7
  CLC：
- Received：18 December 2024，
  
  Revised：2025-01-15，
  
  Accepted：17 January 2025，
  
  Online First：04 March 2025，
  
  Published：20 May 2025
- Accepted：
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Pang, J.; Zhou, Y. B.; Liu, L. J.; Zhang, H. X.; Zhao, J. P. Ring-closing-opening copolymerization of phthalaldehyde and epoxide towards acid-degradable polyether and polyurethane. Chinese J. Polym. Sci. 2025, 43, 964–972

Jie Pang, Yu-Bo Zhou, Li-Jun Liu, et al. Ring-closing-opening Copolymerization of Phthalaldehyde and Epoxide towards Acid-degradable Polyether and Polyurethane[J]. Chinese Journal of Polymer Science, 2025, 43(6): 964-972.
Pang, J.; Zhou, Y. B.; Liu, L. J.; Zhang, H. X.; Zhao, J. P. Ring-closing-opening copolymerization of phthalaldehyde and epoxide towards acid-degradable polyether and polyurethane. Chinese J. Polym. Sci. 2025, 43, 964–972 DOI： 10.1007/s10118-025-3297-7.

Jie Pang, Yu-Bo Zhou, Li-Jun Liu, et al. Ring-closing-opening Copolymerization of Phthalaldehyde and Epoxide towards Acid-degradable Polyether and Polyurethane[J]. Chinese Journal of Polymer Science, 2025, 43(6): 964-972. DOI： 10.1007/s10118-025-3297-7.

摘要

Ring-closing-opening copolymerization of o-phthalaldehyde and epoxide occurs with organic Lewis pair catalysts

yielding polyacetals that are susceptible to acid degradation. Use of triethylborane reduces boronic ester formation

thus enhancing reaction control. Acetal-functionalized polyethers are produced when epoxide is used in large excess

and further transformed into acid-degradable polyurethane.

Abstract

Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions. We report here an in-depth study on the ring-closing-opening copolymerization of

-phthalaldehyde (OPA) and epoxide using Lewis pair type two-component org

anocatalysts for producing acetal-functionalized polyether and polyurethane. Notably

triethylborane as the Lewis acid

in comparison with tri(

-butyl)borane

more effectively enhances the polymerization activity by mitigating borane-induced reduction of the aldehyde group into extra initiating (borinic ester) species. Density functional theory (DFT) calculations present comparable energy barriers of OPA-epoxide cross-propagation and epoxide self-propagation

which is consistent with the experimental finding that an alternating-rich copolymer comprising mostly OPA-epoxide units but also epoxide-epoxide linkages is produced. In particular

when epoxide is added in a large excess

the product becomes a polyether containing acetal functionalities in the central part of the backbone and thus being convertible into polyurethane with refined acid degradability.

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references

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