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

Your Location：

Home >

Browse articles >

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

RESEARCH ARTICLE | Updated：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
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-14(2026)
- Affiliations：
  
  Institute of Petrochemistry and Catalysis, Ufa Federal Research Centre, Russian Academy of Sciences, Ufa 450075, Russian Federation
- Author bio：
  
  luda_parfenova@mail.ru
- Funds：
- DOI：10.1007/s10118-026-3857-5
  CLC：
- Received：11 June 2026，
  
  Accepted：23 August 2026，
  
  Online First：30 October 2026，
  
  Published：2026-09
- Accepted：
Scan QR Code
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

[Guan, Z., in Metal Catalysts in Olefin Polymerization . Springer, Berlin, Heidelberg, 2009 , pp. 159–178..

Keyes, A.; Basbug Alhan, H. E.; Ordonez, E.; Ha, U.; Beezer, D. B.; Dau, H.; Liu, Y. S.; Tsogtgerel, E.; Jones, G. R.; Harth, E. Olefins and vinyl polar monomers: bridging the gap for next generation materials. Angew. Chem. Int. Ed. 2019 , 58 , 12370−12391..

Chen, J.; Gao, Y.; Marks, T. J. Early transition metal catalysis for olefin–polar monomercopolymerization. Angew. Chem. Int. Ed. 2020 , 59 , 14726−14735..

[Nesvadba, P. Radical polymerization in industry, in Encyclopedia of Radicals in Chemistry, Biology and Materials , Wiley, 2012 ..

Mu, H.; Zhou, G.; Hu, X.; Jian, Z. Recent advances in nickel mediated copolymerization of olefin with polar monomers. Coord. Chem. Rev. 2021 , 435 , 213802..

Luckham, S. L. J.; Nozaki, K. Toward the copolymerization of propylene with polar comonomers. Acc. Chem. Res. 2021 , 54 , 344−355..

Tan, C.; Chen, C. Emerging palladium and nickel catalysts for copolymerization of olefins with polar monomers. Angew. Chem. Int. Ed. 2019 , 58 , 7192−7200..

Chen, Z.; Brookhart, M. Exploring ethylene/polar vinyl monomer copolymerizations using Ni and Pd α -diimine catalysts. Acc. Chem. Res. 2018 , 51 , 1831−1839..

Houk, K. N.; Sims, J.; Duke, R. E.; Strozier, R. W.; George, J. K. Frontier molecular orbitals of 1,3 dipoles and dipolarophiles. J. Am. Chem. Soc. 1973 , 95 , 7287−7301..

Song, Z.; Wang, S.; Gao, R.; Wang, Y.; Gou, Q.; Zheng, G.; Feng, H.; Fan, G.; Lai, J. Recent advancements in mechanistic studies of palladium- and nickel-catalyzed ethylene copolymerization with polar monomers. Polymers 2023 , 15 , 4343..

Mecking, S. Olefin polymerization by late transition metal complexes-a root of Ziegler catalysts gains new ground. Angew. Chem. Int. Ed. 2001 , 40 , 534−540..

Poljanšek, I.; Fabjan, E.; Burja, K.; Kukanja, D. Emulsion copolymerization of vinyl acetate-ethylene in high pressure reactor-characterization by inline FTIR spectroscopy. Prog. Org. Coat. 2013 , 76 , 1798−1804..

Zarrouki, A.; Espinosa, E.; Boisson, C.; Monteil, V. Free radical copolymerization of ethylene with vinyl acetate under mild conditions. Macromolecules 2017 , 50 , 3516−3523..

[Drent, E.; Pello, D. H.; Jager, W. W, 1994 , Eur. Pat. Appl ., EP0589527B1..

Drent, E.; van Dijk, R.; van Ginkel, R.; van Oort, B.; Pugh, R. I. The First example of palladium catalysed non-perfectly alternating copolymerisation of ethene and carbon monoxide. Chem. Commun. 2002 , 9 , 964−965..

Nakamura, A.; Ito, S.; Nozaki, K. Coordination-insertion copolymerization of fundamental polar monomers. Chem. Rev. 2009 , 109 , 5215−5244..

Ito, S.; Munakata, K.; Nakamura, A.; Nozaki, K. Copolymerization of vinyl acetate with ethylene by palladium/alkylphosphine–sulfon ate catalysts. J. Am. Chem. Soc. 2009 , 131 , 14606−14607..

Zhang, R.; Gao, R.; Gou, Q.; Lai, J.; Li, X. Recent advances in the copolymerization of ethylene with polar comonomers by nickel catalysts. Polymers 2022 , 14 , 3809..

Cao, L.; Cai, Z.; Li, M. Phosphinobenzenamine nickel catalyzed efficient copolymerization of methyl acrylate with ethylene and norbornene. Macromolecules 2022 , 55 , 3513−3521..

Parfenova, L. V.; Bikmeeva, A. K.; Kovyazin, P. V.; Khalilov, L. M. The dimerization and oligomerization of alkenes catalyzed with transition metal complexes: catalytic systems and reaction mechanisms. Molecules 2024 , 29 , 502..

Qasim, M.; Ahmad, N.; Wang, F.; Tan, C.; Chen, M. A constrained structural symmetry strategy for nickel-catalyzed olefin polymerization and copolymerization with polar monomers. J. Am. Chem. Soc. 2025 , 147 , 45486−45494..

Wang, F.; Chen, C. A continuing legend: the Brookhart-type α -diimine nickel and palladium catalysts. Polym. Chem. 2019 , 10 , 2354−2369..

Zhang, D.; Zhang, R.; Xue, H.; Li, C.; Wang, F.; Chen, M. Indole-based nickel catalysts for ethylene polymerization and copolymerization with norbornene derivatives. Macromolecules 2025 , 58 , 9083−9090..

Yu, F.; Gong, Y.; Liu, N.; Xu, G.; Li, P.; Liu, B.; Li, C.; Wang, F. Positional heterogenization effect in salicylaldimine nickel catalyzed ethylene polymerization. J. Appl. Polym. Sci. 2024 , 141 , e55643..

Ji, H. Y.; Mu, H. L.; Tang, C. F.; Zhang, Y. X.; Chi, Y.; Jian, Z. B. Concerted steric and electronic strategy in thermostable salicylaldiminato nickel catalysts for ethylene (co)polymerization. Chinese J. Polym. Sci. 2024 , 42 , 1085−1092..

Laikov, D. N.; Ustynyuk, Y. A. PRIRODA-04: a quantum-chemical program suite. New possibilities in the study of molecular systems with the application of parallel computing. Russ. Chem. Bull. 2005 , 54 , 820−826..

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996 , 77 , 3865−3868..

[Laikov, D. N. Ph.D. Thesis, Moscow State University, Moscow, Russia, 2000 .

Laikov, D. N. Fast evaluation of density functional exchange-correlation terms using the expansion of the electron density in auxiliary basis sets. Chem. Phys. Lett. 1997 , 281 , 151−156..

Ditchfield, R. On molecular orbital theories of NMR chemical shifts. Chem. Phys. Lett. 1972 , 15 , 203−206..

Pankratyev, E. Y.; Tulyabaev, A. R.; Khalilov, L. M. How reliable are GIAO calculations of 1 H and 13 C NMR chemical shifts? A statistical analysis and empirical corrections at DFT (PBE/3z) level. J. Comput. Chem. 2011 , 32 , 1993−1997..

Pandey, S.; Srivastava, R. S. Synthesis and characterization of some heterocyclic Schiff bases: potential anticonvulsant agents. Med. Chem. Res. 2011 , 20 , 1091−1101..

Azizi, K.; Madsen, R. Molybdenum-catalyzed dehydrogenative synthesis of imines from alcohols and amines. ChemCatChem 2018 , 10 , 3703−3708..

Tverdova, N. V.; Giricheva, N. I.; Girichev, G. V.; Kuz’mina, N. P.; Kotova, O. V.; Zakharov, A. V. IR spectra of N,N ’-ethylene-bis(salicylaldiminates) and N,N ’-ethylene-bis(acetylacetoniminates) of Ni(II), Cu(II), and Zn(II). Russ. J. Phys. Chem. 2009 , 83 , 2255−2265..

[Rieger, B.; Baugh, L. S.; Kacker, S.; Striegler, S, in Late Transition Metal Polymerization Catalysis . Wiley-VCH, Weinheim, 2003, pp 125–137..

Tkach, V. S.; Suslov, D. S.; Gomboogiin, M.; Ratovskii, G. V.; Shmidt, F. K. Isomerization of alkenes in the presence of Pd(acac) 2 -BF 3 OEt2 catalytic system. Russ. J. Appl. Chem. 2006 , 79 , 85−88..

Keim, W. Nickel hydrides: catalysis in oligomerization and polymerization reactions of olefins. Ann. N Y Acad. Sci. 1983 , 415 , 191−200..

[Petrovskii, S. K. Mechanism of activation and functioning of catalytic systems based on bis(1,5-cyclooctadiene)nickel(0) in the transformations of olefinic hydrocarbons, Thesis, G. K. Boreskov Institute of Catalysis, Novosibirsk, 2017 .

Bekmukhamedov, G. E.; Sukhov, A. V.; Kuchkaev, A. M.; Yakhvarov, D. G. Ni-based complexes in selective ethylene oligomerization processes. Catalysts 2020 , 10 , 498..

Mecking, S. Cationic nickel and palladium complexes with bidentate ligands for the C–C linkage of olefins. Coord. Chem. Rev. 2000 , 203 , 325−351..

Berkefeld, A.; Drexler, M.; Möller, H. M.; Mecking, S. Mechanistic insights on the copolymerization of polar vinyl monomers with neutral Ni(II) catalysts. J. Am. Chem. Soc. 2009 , 131 , 12613−12622..

Chen, Y.; Dong, H. Recent advancements in the synthesis of functional polyolefins by non-bridged half-titanocenes. Molecules 2025 , 30 , 39..

Na, Y.; Zhang, D.; Chen, C. Modu lating polyolefin properties through the incorporation of nitrogen-containing polar monomers. Polym. Chem. 2017 , 8 , 2405−2409..

Franssen, N. M. G.; Reek, J. N. H.; de Bruin, B. Synthesis of functional 'polyolefins': state of the art and remaining challenges. Chem. Soc. Rev. 2013 , 42 , 5809−5832..

Bazhanov, D. A.; Nikulova, U. V.; Khasbiullin, R. R.; Budylin, N. Y.; Ermakova, E. V.; Shapagin, A. V. Ethylene-vinyl acetate copolymer as a polyfunctional modifier for low-viscosity photosensitive compositions. Polymers 2025 , 17 , 2787..

Geretschläger, K. J.; Wallner, G. M.; Fischer, J. Structure and basic properties of photovoltaic module backsheet films. Sol. Energy Mater. Sol. Cells 2016 , 144 , 451−456..

Henderson, A. M. Ethylene-vinyl acetate (EVA) copolymers: a general review. IEEE Electr. Insul. Mag. 1993 , 9 , 30−38..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

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

Preparation and Hydrogenation of Dicyclopentadiene-based Cyclic Olefin Copolymers

Highly Cis-1,4 Selective Polymerization of Conjugated Dienes Catalyzed by N-heterocyclic Carbene-ligated Neodymium Complexes

End-group and Side-chain Dual-engineering of Selenium-fused Acceptors for 20.08% Efficiency Polymer Solar Cells with Low Energy Loss

Experimental Investigation of Graphene and TiO2 Reinforced Poly(vinyl alcohol)-based Fiber Metal Laminates

Related Author

Xiao-Hua Wang

Heng Liu

Xue-Quan Zhang

Chun-Yu Zhang

Feng-Bin Liu

Yue-Sheng Li

Xiang-Han Zhang

Xiao-Hui Mao

Related Institution

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

School of Materials Science and Engineering, State Key Laboratory of High Performance Roll Materials and Composite Forming, Tianjin University

Tianjin Key Laboratory of Composite and Functional Materials, Key Laboratory of Organic Integrated Circuits, Ministry of Education

College of Chemistry Engineering and Materials Science, Quanzhou Normal University

State Key Laboratory of Chemical Resource Engineering, Beijing Advanced innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology

⁰