Ni-catalyzed Co-oligomerization of 1-Hexene with Vinyl Acetate: Synthesis of an N,O-type Complex and Structure of the Products

Eldar R. Palatov; Pavel V. Kovyazin; Tatyana V. Tyumkina; Denis N. Islamov; Evgeniy A. Paramonov; Lyudmila V. Parfenova

doi:10.1007/s10118-026-3857-5

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Ni-catalyzed Co-oligomerization of 1-Hexene with Vinyl Acetate: Synthesis of an N,O-type Complex and Structure of the Products

RESEARCH ARTICLE | 更新时间：2026-10-30

- Ni-catalyzed Co-oligomerization of 1-Hexene with Vinyl Acetate: Synthesis of an N,O-type Complex and Structure of the Products
- Ni-catalyzed Co-oligomerization of 1-Hexene with Vinyl Acetate: Synthesis of an N,O-type Complex and Structure of the Products
- Chinese Journal of Polymer Science 2026年44卷页码：1-14
- 作者机构：
  
  Institute of Petrochemistry and Catalysis, Ufa Federal Research Centre, Russian Academy of Sciences, Ufa 450075, Russian Federation
- 作者简介：
  
  luda_parfenova@mail.ru
- 基金信息：
  
  Structural studies of the compounds were carried out at the Center for Collective Use “Agidel” at the Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences. This study was carried out within the framework of state assignment to the Institute of Petrochemistry and Catalysis (No. FMRS-2025-0033).;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/s10118-026-3857-5.The data supporting the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3857-5
  中图分类号：
- 收稿：2026-06-11，
  
  录用：2026-08-23，
  
  网络首发：2026-10-30，
  
  纸质出版：2026-09
- 稿件说明：
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Palatov, E. R.; Kovyazin, P. V.; Tyumkina, T. V.; Islamov, D. N.; Paramonov, E. A.; Parfenova, L. V. Ni-catalyzed co-oligomerization of 1-hexene with vinyl acetate: synthesis of an N,O-type complex and structure of the products. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3857-5

Eldar R. Palatov, Pavel V. Kovyazin, Tatyana V. Tyumkina, et al. Ni-catalyzed Co-oligomerization of 1-Hexene with Vinyl Acetate: Synthesis of an N,O-type Complex and Structure of the Products[J/OL]. Chinese Journal of Polymer Science, 2026, 441-14.
Palatov, E. R.; Kovyazin, P. V.; Tyumkina, T. V.; Islamov, D. N.; Paramonov, E. A.; Parfenova, L. V. Ni-catalyzed co-oligomerization of 1-hexene with vinyl acetate: synthesis of an N,O-type complex and structure of the products. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3857-5 DOI：

Eldar R. Palatov, Pavel V. Kovyazin, Tatyana V. Tyumkina, et al. Ni-catalyzed Co-oligomerization of 1-Hexene with Vinyl Acetate: Synthesis of an N,O-type Complex and Structure of the Products[J/OL]. Chinese Journal of Polymer Science, 2026, 441-14. DOI： 10.1007/s10118-026-3857-5.

摘要

Abstract

This work reports the synthesis of a new N

O-type nickel complex and its application in a Ni–AlEt

–BF

·MeOH catalytic system for homo- and co-oligomerization of 1-hexene and vinyl acetate. The system shows variable activity depending on the AlEt

content and monomer ratio: 3.5 kg·(mol

·h)

–1

for 1-hexene

10.4 kg·(mol

·h)

–1

for vinyl acetate

and up to 12.5 kg·(mol

·h)

–1

in co-oligomerization (40 °C

toluene). Vinyl acetate is more reactive

and varying the monomer ratio allows control over the molecular weight and copolymer composition. Atmospheric pressure chemical ionization (APCI

/APCI

–

) mass spectrometry revealed chains with different initiating groups (H―

Et―

Bu―

and―CH

―)

indicating the involvement of Ni–alkyl

Ni–hydride

and Ni–ethylene species.

C-NMR and quantum chemical c

alculations show predominant 1

2-insertion of alkenes

as well as mainly syndiotactic fragments

and isomerization of 1-hexene to 3-hexene at the nickel center. An ionic mechanism is proposed in which the balance of active Ni species and competitive monomer coordination governs the catalytic activity and product structure. Differential scanning calorimetry showed that the thermal behavior of the co-oligomers was strongly dependent on the AlEt

content and comonomer ratio

underscoring their potential as tunable functionalized additives.

关键词

Keywords

references

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