Polyolefins Journal

With the collaboration of Iran Polymer Society

Current Issue

By Issue

By Author

By Subject

Author Index

Keyword Index

About Journal

Aims and Scope

Indexing and Abstracting

Related Links

Peer Review Process

FAQ

News

Reviewers

Guide for Reviewers

Kinetic and microstructural studies of Cp2ZrCl2 and Cp2HfCl2-catalyzed oligomerization of higher α-olefins in mPAO oil base stocks production

Document Type : Original research

Authors

1 Polymerization Engineering Department, Iran Polymer and Petrochemical Institute (IPPI), P.O. Box 14975/112, Tehran, Iran

2 Miandoab Petrochemical Company, Bakhtar holding, Miandoab, Iran

Abstract

Herein a quenched-flow kinetic technique was applied to calculate the rate constants of 1-hexene and 1-octene oligomerization catalyzed by the Cp2ZrCl2 and Cp2HfCl2/MAO catalyst systems, and subsequently a mechanism for the higher α-olefin oligomerization reaction was proposed. The oligomerization results showed that Zr-based catalyst in the oligomerization of 1-octene had the highest activity of 17 in comparison to Hfbased one with an activity value of 15 g oligomer/(mmolCat.h)). According to the obtained results, increasing monomer length led to a shift in molecular weight and polydispersity index value (Mw/Mn) to lower values. Furthermore, the microstructure-viscosity relationship was followed by the calculation of branching ratio and short-chain branching percentage. The obtained results revealed that, the oligomers synthesized by the Cp2HfCl2 catalyst had lower short chain branching ratio value and short-chain branching percentages. According to the kinetic results, the initiation rate constant (ki) of Zr-based catalyst was higher than that of Hf-based catalyst, and the order of calculated propagation rate constants was Zr>Hf for both the 1-hexene and 1-octene-based oligomerizations.

Keywords

Main Subjects

References
  1. Hanifpour A, Bahri-Laleh N, NekoomaneshHaghighi M, Karimi M (2016) Study on unsaturated structure and tacticity of poly1- hexene and new copolymer of 1-hexene/5- hexene-1-ol prepared by metallocene catalyst. J Organomet Chem 819: 103-108
  2. Dehghani S, Hanifpour A, NekoomaneshHaghighi M, Sadjadi S, Mirmohammadi S A, Farhadi A, Bahri-Laleh N (2020) Highly efficient supported AlCl3 -based cationic catalysts to produce poly α-olefin oil base stocks. J Appl Polym Sci 137: 49018
  3. Jalali A, Nekoomanesh-Haghighi M, Dehghani S, Bahri-Laleh N (2019) Effect of metal type on the metallocene-catalyzed oligomerization of 1-hexene and 1-octene to produce polyα-olefinbased synthetic lubricants. Appl Organometal Chem 34: e5338
  4. Hanifpour A, Bahri-Laleh N, NekoomaneshHaghighi M, Poater A (2020) Coordinative chain transfer polymerization of 1-decene in the presence of a Ti-based diamine bis (phenolate) catalyst: A sustainable approach to produce low viscosity PAOs. Green Chem 22: 4617-4626
  5. Mynott R, Fink G, Fenzl W (1987) Ethylene insertion with soluble Ziegler catalysts. III. The system cp2TiMeCl/AlMe2Cl/13C2H4 studied by 13C-NMR spectroscopy. The time-development of chain propagation and oligomer distribution. Angew Makromol Chem 154: 1-21
  6. Busico V, Cipullo R, Esposito V (1999) Stoppedflow polymerizations of ethene and propene in the presence of the catalyst system racMe2Si(2-methyl-4-phenyl-1-indenyl)2ZrCl2 / methylaluminoxane. Macromol Rapid Commun 20: 116-121
  7. Manz TA, Phomphrai K, Medvedev G, Krishnamurthy BB, Sharma S, Haq J, Novstrup KA, Thomson KT, Delgass WN, Caruthers JM, Abu-Omar MM (2007) Structure-activity correlation in titanium single-Site olefin polymerization catalysts containing mixed cyclopentadienyl/aryloxide Ligation. J Am Chem Soc 129: 3776-3777
  8. Mehrkhodavandi P, Schrock RR, Pryor LL (2003) Living polymerization of 1-hexene by cationic zirconium and hafnium complexes that contain a diamido/donor ligand of the type [H3CC(2- C5 H4 N)(CH2 NMesityl)2 ]2 -. A comparison of methyl and isobutyl initiators. Organometallics 22: 4569-4583
  9. Liu ZX, Somsook E, White CB, Rosaaen KA, Landis C, Mulhaupt R, Duschek T, Rieger B (2001) Kinetics of initiation, propagation, and termination for the [rac-(C2H4 (1-indenyl)2 ) ZrMe][MeB(C6 F5)3 ]-catalyzed polymerization of 1-hexene. J Am Chem Soc 123: 11193-11207
  10. Christianson MD, Tan EHP, Landis CR (2010) Stopped-flow NMR: Determining the kinetics of [rac-(C2H4 (1-indenyl)2 )ZrMe][MeB(C6F5)3 ]- Catalyzed polymerization of 1-hexene by direct observation. J Am Chem Soc 132: 11461-11463
  11. Chen MC, Roberts JAS, Marks TJ (2004) Marked counteranion effects on single-site olefin polymerization processes. Correlations of ion pair structure and dynamics with polymerization activity, chain transfer, and syndioselectivity. J Am Chem Soc 126: 4605-4625
  12. Naga N, Mizunuma K (1998) Chain transfer reaction by trialkylaluminum (AIR3 ) in the stereospecific polymerization of propylene with metallocene-AIR3 /Ph3CB(C6F5)4 . Polymer 39: 5059-5067
  13. Kotzabasakis V, Kostakis K, PitsikalisI M, Hadjichristidis N, Lohse D J, Mavromoustakos T, Potamitis C (2009) Polymerization of higher α-olefins using a Cs-symmetry hafnium metallocene catalyst. Kinetics of the polymerization and microstructural analysis. J Polym Sci Pol Chem 47: 4314-4325
  14. Kissin YV (2019) Oligomerization reactions of 1-hexene with metallocene catalysts: Detailed data on reaction chemistry and kinetics. Mol Catal 463: 87-93
  15. Kissin YV (2009) Detailed kinetics of 1-hexene oligomerization reaction with (n-Bu-Cp)2 ZrCl2 - MAO catalyst. Macromol Chem Phys 210: 1241- 1246
  16. Chen C-H, Shih W-C, Hilty C (2015) In Situ determination of tacticity, deactivation, and kinetics in [rac-(C2H4 (1-Indenyl)2 ) ZrMe][B(C6F5)4 ] and [Cp2ZrMe][B(C6F5 )4 ]- catalyzed polymerization of 1-hexene using 13C hyperpolarized NMR. J Am Chem Soc 137: 6965-6971
  17. Liu Z, Somsook E, White CB, Rosaaen KA, Landis CR (2001) Kinetics of initiation, propagation, and termination for the [rac-(C2H4 (1-indenyl)2 ) ZrMe][MeB(C6 F5 )3 ]-catalyzed polymerization of 1-hexene. J Am Chem Soc 123: 11193-11207
  18. Basset J-M, Coperet C, Soulivong D, Taoufik M, Cazat J T(2010) Metathesis of alkanes and related reactions. Acc Chem Res 43: 323-334
  19. Hanifpour A, Bahri-Laleh N, NekoomaneshHaghighi M, Poater A (2020) Group IV diamine bis (phenolate) catalysts for 1-decene oligomerization. Mol Catal 493: 111047
  20. Rahmatiyan S, Bahri-Laleh N, Hanifpour A, Nekoomanesh-Haghighi M (2018) Different behaviors of metallocene and Ziegler– Natta catalysts in ethylene/1, 5-hexadiene copolymerization. Polym Int 68: 94-101
  21. Suzuki N, MasubuchiY, Yamaguchi Y, Kase T, Mayamoto T. K, Horiuchi A, Mise T (2000) Olefin polymerization using highly congested ansametallocenes under high pressure: Formation of superhigh molecular weight polyolefins. macromolecules 33: 754-759
  22. Galland GB, Forgiarini Da Silva L, Nicolini A (2005) Tacticity of poly-α-olefins from poly-1- hexene to poly-1-octadecene. J Polym Sci Polym Chem 43: 4744-4753
  23. Thiam Z, Abou-Hamad E, Dereli B, Liu L, Emwas A-H, Ahmad R, Jiang H, Adamu Isah A, Ndiaye P B, Taoufik M, Han Y, Cavallo L, Basset J-M, Eddaoudi M (2020) Extension of surface organometallic chemistry to metalorganic frameworks: Development of a welldefined single site [(≡Zr-O-)W(═O)(CH2tBu)3 ] olefin metathesis catalyst. J Am Chem Soc 142: 16690-16703
  24. Hanifpour A, Bahri-Laleh N, NekoomaneshHaghighi M (2020) Single-phase photo-crosslinkable adhesive synthesized from methacrylic acid-grafted 1-decene/9-decene-1-ol cooligomer. J Appl Polym Sci138: 49654
  25. Park JH, Jang YE, Jeon JY, Go MJ, Lee J, Kim SK, Lee V, Lee BY (2014) Preparation of ansametallocenes for production of poly (α-olefin) lubricants. Dalton Trans 43: 10132-10138
  26. Hanifpour A, Bahri-Laleh N, NekoomaneshHaghighi M (2020) Methacrylate-functionalized POSS as an efficient adhesion promoter in olefinbased adhesives. Polym Eng Sci 1-10
  27. Hanifpour A, Bahri-Laleh N, NekoomaneshHaghighi M, Karimi M (2017) Synthesis and characterization of poly1-hexene/silica nanocomposites. Polym Test 61: 27-34
  28. Dong SQ, Mi PK, Xu S, Zhang J, Zhao RD (2019) Preparation and characterization of single-component poly-α-olefin oil base stocks. Energy & Fuels 33: 9796-9804
  29. Kissounko DA, Zhang Y, Harney MB, Sita LR (2005) Evaluation of (η5-C5Me5)Hf(R)2[N(Et) C(Me)N(t-Bu)] (R=Me and i-Bu) for the stereospecific living and degenerative transfer living Ziegler-Natta polymerization of α-olefins. Adv Synth Catal 347: 426-432
  30. Bahri-Laleh N, Hanifpour A, Mirmohammadi S A, Poater A, Nekoomanesh-Haghighi M, Talarico G, Cavallo L (2018) Computational modeling of heterogeneous Ziegler-Natta catalysts for olefins polymerization. Prog Polym Sci 84: 89-114
  31. Hanifpour A, Bahri-Laleh N, NekoomaneshHaghighi M (2020) Preparation of novel, liquid, solvent-free, polyolefin-based adhesives. Polym Adv Technol 31: 922-931
  32. Hanifpour A, Bahri-Laleh N, Mirmohammadi SA (2019) Silica-grafted poly1-hexene: A new approach to prepare polyethylene/silica nanocomposites. Polym Comp 40: 1053-1060
  33. Pino P, Cioni P, Wei J (1987) Asymmetric hydrooligomerization of propylene. J Am Chem Soc 109: 6189- 6191
Polyolefins Journal
Volume 8, Issue 1 - Serial Number 15
January 2021
Pages 31-40
Files
Cited by
History
  • Receive Date: 04 November 2020
  • Revise Date: 25 November 2020
  • Accept Date: 29 November 2020
  • First Publish Date: 29 November 2020
Share
How to cite
Statistics