Preparation and Hydrogenation of Dicyclopentadiene-based Cyclic Olefin Copolymers

Xiang-Han Zhang; Xiao-Hui Mao; Huan Gao; Shui-Yuan Luo; Zhe Ma; Li Pan; Yue-Sheng Li

doi:10.1007/s10118-025-3351-5

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Preparation and Hydrogenation of Dicyclopentadiene-based Cyclic Olefin Copolymers

RESEARCH ARTICLE | Updated：2025-08-25

- Preparation and Hydrogenation of Dicyclopentadiene-based Cyclic Olefin Copolymers
- Preparation and Hydrogenation of Dicyclopentadiene-based Cyclic Olefin Copolymers
- 高分子科学（英文） 2025年43卷第9期页码：1527-1536
- Affiliations：
  
  a.School of Materials Science and Engineering, State Key Laboratory of High Performance Roll Materials and Composite Forming, Tianjin University, Tianjin 300350, China
  b.Tianjin Key Laboratory of Composite and Functional Materials, Key Laboratory of Organic Integrated Circuits, Ministry of Education, Tianjin 300350, China
  c.College of Chemistry Engineering and Materials Science, Quanzhou Normal University, Quanzhou 362000, China
- Author bio：
  
  gaohuan926@tju.edu.cn (H.G.)
  ysli@tju.edu.cn (Y.S.L.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 52130307 and 5240031453).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3351-5.
- DOI：10.1007/s10118-025-3351-5
  中图分类号：
- 收稿：2025-03-13，
  
  修回：2025-04-17，
  
  录用：2025-04-18，
  
  网络首发：2025-06-04，
  
  纸质出版：2025-09-05
- Accepted：
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Zhang, X. H.; Mao, X. H.; Gao, H.; Luo, S. Y.; Ma, Z.; Pan, L.; Li, Y. S. Preparation and hydrogenation of dicyclopentadiene-based cyclic olefin copolymers. Chinese J. Polym. Sci. 2025, 43, 1527–1536

Xiang-Han Zhang, Xiao-Hui Mao, Huan Gao, et al. Preparation and Hydrogenation of Dicyclopentadiene-based Cyclic Olefin Copolymers[J]. Chinese Journal of Polymer Science, 2025, 43(9): 1527-1536.
Zhang, X. H.; Mao, X. H.; Gao, H.; Luo, S. Y.; Ma, Z.; Pan, L.; Li, Y. S. Preparation and hydrogenation of dicyclopentadiene-based cyclic olefin copolymers. Chinese J. Polym. Sci. 2025, 43, 1527–1536 DOI： 10.1007/s10118-025-3351-5.

Xiang-Han Zhang, Xiao-Hui Mao, Huan Gao, et al. Preparation and Hydrogenation of Dicyclopentadiene-based Cyclic Olefin Copolymers[J]. Chinese Journal of Polymer Science, 2025, 43(9): 1527-1536. DOI： 10.1007/s10118-025-3351-5.

摘要

The copolymerization of ethylene with DCPD is catalyzed using metallocene

followed by hydrogenation of the copolymer utilizing a Ni(acac)

Al. The COC synthesized exhibits optical and mechanical properties comparable to commercial COCs. DCPD is readily accessible with a significantly lower cost compared to NBE and TCD

enabling cost-effective polymerization.

Abstract

The design of low-cost and high-performance cyclic olefin copolymers remains challenging. Ethylene copolymers with dicyclopentadiene (DCPD) were prepared using Ph

C(Cp)(Flu)ZrCl

(

Cat. 1

)

rac

-Et(Ind)

ZrCl

(

Cat. 2

)

C(Cp)(Flu)ZrCl

(

Cat. 3

) and Me

Si(Ind)

ZrCl

(

Cat. 4

) combined with [Ph

]

[B(C

)

]

Al. Ni(acac)

Al was then used to catalyze the hydrogenation of the intracyclic double bonds of ethylene/DCPD copolymers. The results showed that compared to

symmetric catalysts (

Cat. 2

and

Cat. 4

)

symmetric catalysts (

Cat. 1

and

Cat. 3

) facilitated the incorporation of copolymers with higher DCPD.

H- and

C-NMR spectra indicated that ethylene/DCPD copolymerization occurred

via

enhancement of the norbornene ring. Additionally

measurement of the reactivity ratios provided further confirmation that the copolymers had random sequence distributions. All these samples demonstrated transmittance values above 90% in the visible wavelength range from 400 nm to 800 nm. By changing the fraction of monomers

the glass transition temperature

refractive index

Young's modulus

and tensile strength of the copolymer increased as the incorporation of DCPD increased

whereas the Abbe number and elongation at break decreased. Compared with ethylene/norbornene and ethylene/tetracyclicdodecene copolymers

ethylene/DCPD copolymers

with ex

cellent optical and mechanical properties

are promising materials.

关键词

Keywords

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