Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic <italic style="font-style: italic">α</italic>-Diimine Palladium Complexes

Feng-Bin Liu; Chun-Yu Zhang; Xue-Quan Zhang; Heng Liu; Xiao-Hua Wang

doi:10.1007/s10118-026-3594-9

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Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes

RESEARCH ARTICLE | Updated：2026-07-01

- Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes
- Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes
- Chinese Journal of Polymer Science 2026年44卷第7期页码：2177-2187
- Affiliations：
  
  State Key Laboratory of Advanced Optical Polymer and Manufacturing Technology, Key Laboratory of Rubber-Plastics, Ministry of Education, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
- Author bio：
  
  hengliu@qust.edu.cn (H.L.)
  BH146@qust.edu.cn (X.H.W.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 22201154, 22071236, and 21801236) and the Shandong Provincial Natural Science Foundation of China (No. ZR2022QB011). H.L. thanks the Taishan Scholars Program (No. tsqn202211165) for their financial support.;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3594-9.;All data included in this study are available from the corresponding author upon reasonable request. (E-mail BH146@qust.edu.cn)
- DOI：10.1007/s10118-026-3594-9
  中图分类号：
- 收稿：2026-01-19，
  
  录用：2026-01-27，
  
  网络首发：2026-05-12，
  
  纸质出版：2026-07-05
- Accepted：
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Liu, F. B.; Zhang, C. Y.; Zhang, X. Q.; Liu, H.; Wang, X. H. Modulating molecular weight of polyethylenes from oligomer to polymer using highly thermal stable cationic α-diimine palladium complexes. Chinese J. Polym. Sci. 2026, 44, 2177–2187

Feng-Bin Liu, Chun-Yu Zhang, Xue-Quan Zhang, et al. Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2177-2187. DOI: 10.1007/s10118-026-3594-9.
Liu, F. B.; Zhang, C. Y.; Zhang, X. Q.; Liu, H.; Wang, X. H. Modulating molecular weight of polyethylenes from oligomer to polymer using highly thermal stable cationic α-diimine palladium complexes. Chinese J. Polym. Sci. 2026, 44, 2177–2187 DOI： 10.1007/s10118-026-3594-9.

Feng-Bin Liu, Chun-Yu Zhang, Xue-Quan Zhang, et al. Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2177-2187. DOI: 10.1007/s10118-026-3594-9. DOI：

摘要

This work reports a new family of highly thermally stable unsymmetrical cationic

-diimine palladium complexes that combine both steric blockage and intra-ligand C―H···F non-covalent linkages affording polyethylenes with tunable molecular weights and adjustable branching densities.

Abstract

Developing highly thermostable catalytic systems remains a central objective in the field of late-transition-metal olefin polymerization. In this work

we report a new series of

-diimine Pd(II) catalysts that exhibit remarkable thermal resistance in ethylene polymerization (up to 100 °C). With the aid of concerted effects of both steric blockage and intra-ligand C―H···F hydrogen bonding linkage

conformational rotation of the

-aryl groups is substantially restricted

thereby imparting exceptional thermostability to these

-diimine Pd(II) precatalysts. By tuning the chain-walking degrees through the steric influence of

ortho

-substituent of

-phenyl substituents or by adjusting the polymerization temperature

the branching density of the resulting polyethylenes can be finely m

odulated from moderately branched to hyperbranched structures (72.7–142.1/1000C). More unexpectedly

these highly thermally robust unsymmetrical

-diimine Pd(II) complexes

stabilized by intra-ligand C―H···F hydrogen bonding

are capable of producing polyethylenes with widely adjustable molecular weights

ranging from oligomers to high-molecular-weight polymers (

=0.6×10

–87.2×10

g/mol). Furthermore

ethylene/methylacrylate (E/MA) copolymers were also successfully obtained using these catalysts

achieving MA incorporation levels of up to 4.7%.

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Keywords

references

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Modulating Molecular Weight of Polyethylenes from Oligomer to Polymer Using Highly Thermal Stable Cationic α-Diimine Palladium Complexes

DOI：10.1007/s10118-026-3594-9

摘要

Abstract

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Keywords

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