Homo- and co-polymerization of polar and non-polar olefinic monomers using bicenter cobalt-diimine catalysts

Document Type : Original research

Authors

1 Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, P.O. Box 91775, Mashhad, Iran

2 Department of Engineering, Iran Polymer and Petrochemical Institute (IPPI), P.O. Box 14965/115, Tehran, Iran

Abstract

Bicenter (BCn) cobalt-bis(imine) catalysts were synthesized, used to polymerize methyl methacrylate (MMA), and 1-hexene. The effect of catalyst structure, bridging ligand, and polymerization reaction conditions were investigated. Synthesis of primary ligand of (2,6-dibenzhydryl-4-ethoxyphenyl)-N=(CH3)-C(CH3)=O is prepared. Following to that, the final ligands of BC1 and BC2 bicenter catalysts were prepared via reacting the primary ligand with 2,3,5,6-tetramethylbenzene-1,4-diamine and 4,4-methylenedianiline bridges, respectively. The BC1 catalyst demonstrated higher activity than the BC2 catalyst. The highest activity for the BC1 catalyst was obtained when the co-catalyst to catalyst molar ratio was [Al]/[Co]=1500:1, and the polymerization temperature was 40 °C. In comparison the BC2 catalyst demonstrated the highest activity in [Al]/[Co]=500:1 ratio, polymerization temperature of 70 °Cand showed higher thermal stability. 1HNMR analysis revealed that the highest branching density for poly(methyl methacrylates) (PMMA) produced by BC1 and BC2 catalysts was 222 and 249 branches per 1000 carbon atoms, respectively. PMMA synthesized with BC2 catalysts had the highest syndiotacticity (59%). The polymer produced with bicenter catalyst (BC1) had a relatively broad molecular weight distribution (2.9), according to GPC analysis. The synthesized catalysts demonstrated appropriate activity for the polymerization of MMA, but only moderate activity for 1-hexene monomer

Graphical Abstract

Homo- and co-polymerization of polar and non-polar olefinic monomers using bicenter cobalt-diimine catalysts

Highlights

  • Catalysts for homo- and Co polymerization of polymerization of methyl methacrylate.
  • Homopolymer with high amount of syndiotacticity was obtained.
  • The homopolymers with banching ranged from 201-249 per 1000 carbons synthesized.
  • The branching density of copolymer increased by increasing the polar monomer

Keywords

Main Subjects

References

  1. Li F, Liu W (2023) Progress in the catalyst for ethylene/α‐olefin copolymerization at high temperature. Canadian J Chem Eng 101: 4992-5019 [CrossRef]
  2. Alzamly A, Bakiro M, Ahmed SH, Siddig LA, Nguyen HL (2022) Linear α-olefin oligomerization and polymerization catalyzed by metal-organic frameworks. Coord Chem Rev 462: 214522  [CrossRef]
  3. Skupinska J (1991) Oligomerization of. alpha.-olefins to higher oligomers. Chem Rev 91: 613-648 [CrossRef]
  4. Corma A, Iborra S (2006) Oligomerization of alkenes. In: Catalysts for Fine Chemical Synthesis: Microporous and Mesoporous Solid Catalysts, Vol 4, ed: Eric G. Derouane, pp.125-140 [CrossRef]
  5. Antunes BM, Rodrigues AE, Lin Z, Portugal I, Silva CM (2015) Alkenes oligomerization with resin catalysts. Fuel Process Technol 138: 86-99 [CrossRef]
  6. Bekmukhamedov GE, Sukhov AV, Kuchkaev AM, Yakhvarov DG (2020) Ni-based complexes in selective ethylene oligomerization processes. Catalysts 10: 498 [CrossRef]
  7. Chen C, Alalouni MR, Dong X, Cao Z, Cheng Q, Zheng L, Meng L, Guan C, Liu L, Abou-Hamad E, Wang J, , Shi Z, Huang K-W, Cavallo L, Han Y (2021) Highly active heterogeneous catalyst for ethylene dimerization prepared by selectively doping Ni on the surface of a zeolitic imidazolate framework. J Am Chem Soc 143: 7144-7153 [CrossRef]
  8. Egger KW, Cocks AT (1971) Reactions of group III metalalkyls in the gas phase. Part 4.—Kinetics of the homogeneous dimerization of ethylene to 1-butene, catalyzed by gaseous triethylaluminium. Trans Faraday Soc 67: 2638-2644 [CrossRef]
  9. Mahdaviani SH, Parvari M, Soudbar D (2012) Ethylene dimerization by a homogeneous Ti-based three-component catalyst system: process evaluation and optimization of parametric performance. Procedia Eng 42: 616-622 [CrossRef]
  10. Albright LF, Smith CS (1968) Reactions of ethylene with triethyl aluminum: Effect of operating variables and kinetics of reaction. AIChE J 14: 325-320 [CrossRef]
  11. Sivalingam G, Natarajan V, Sarma KR, Parasuveera U (2008) Solubility of ethylene in the presence of hydrogen in process solvents under polymerization conditions. Ind Eng Chem Res 47: 8940-8946 [CrossRef]
  12. Reyhan SB, Alavi SM, Soudbar D (2023) Investigation of catalytic reaction of ethylene dimerization to butene-1 by use of DCPDS as a modifier based on response surface methodology. Heliyon 9: e20481 [CrossRef]
  13. Bigdeli P, Abdouss M, Abedi S (2018) Ti alkoxide-based catalyst system in selective ethylene dimerization: High performance through modifying by alkylsilanes. Chem Eng Commun 205: 102-109 [CrossRef]
  14. Xu Z, Chada JP, Xu L, Zhao D, Rosenfeld DC, Rogers JL, Hermans I, Mavrikakis M, Huber GW (2018) Ethylene dimerization and oligomerization to 1-butene and higher olefins with chromium-promoted cobalt on carbon catalyst. Acs Catal 8: 2488-2497 [CrossRef]
  15. Ren F, Ji P (2020) Recent advances in the application of metal–organic frameworks for polymerization and oligomerization reactions. Catalysts 10: 1441 [CrossRef]
  16. Cordier, A (2019) Oligomerization and polymerization of ethylene by phenoxy-imine titanium catalysts, PhD diss., Université de Lyon [CrossRef]
  17. Masoori M, Nekoomanesh M, Posada-Pérez S, Rashedi R, Bahri-Laleh N (2022) A systematic study on the effect of co-catalysts composition on the performance of Ziegler-Natta catalyst in ethylene/1-butene co-polymerizations. Polymer 261: 125423 [CrossRef]
  18. Mahdaviani SH, Soudbar D, Parvari M (2010) Selective ethylene dimerization toward 1-butene by a new highly efficient catalyst system and determination of its optimum operating conditions in a buchi reactor. Int J Chem Eng Appl 1: 276-281 [CrossRef]
  19. Mahdaviani SH, Parvari M, Soudbar D (2012) Production of 1-butene via selective ethylene dimerization by addition of bromoethane as a new promoter to titanium-based catalyst in the presence of tetrahydropyran modifier and triethylaluminum co-catalyst. Iran J Chem Eng 9: 3-13 [CrossRef]
  20. Henrici‐Olive G, Olivé S (1967) The Active Species in Homogeneous Ziegler‐Natta Catalysts for the Polymerization of Ethylene. Angew Chem, Int Ed Engl 6: 790-798 [CrossRef]
  21. Davis-Gilbert ZW, Wen X, Goodpaster JD, Tonks IA (2018) Mechanism of Ti-catalyzed oxidative nitrene transfer in [2+ 2+ 1] pyrrole synthesis from alkynes and azobenzene. J Am Chem Soc 140: 7267-7281 [CrossRef]
  22. Al-Sa'doun AW (1993) Dimerization of ethylene to butene-1 catalyzed by Ti (OR') 4-AlR3. Appl Catal A-Gen105: 1-40 [CrossRef]
  23. Pillai SM, Tembe GL, Ravindranathan M, Sivaram S (1988) Dimerization of ethylene to 1-butene catalyzed by the titanium alkoxide-trialkylaluminum system. Ind Eng Chem Res 27: 1971-1977 [CrossRef]
  24. Trischler H, Schöfberger W, Paulik C (2013) Influence of Alkylaluminum Co‐catalysts on TiCl4 Transalkylation and Formation of Active Centers C* in Ziegler–Natta Catalysts. Macromolecular React Eng 7: 146-154 [CrossRef]
  25. Belov GP, Matkovsky PE (2010) Processes for the production of higher linear α-olefins. Petrol Chem 50: 296-302 [CrossRef]
  26. Bigdeli P, Abdouss M, Abedi S (2017) Alkoxysilane modification of a T i‐based catalyst system for ethylene dimerization: A step forward in enhancing productivity and selectivity. J Appl Polym Sci 134: 44615 [CrossRef]
  27. Mahdaviani SH, Parvari M, Soudbar D (2011) Effect of two halohydrocarbons as new promoters suitable for titanium-catalyzed ethylene dimerization toward 1-butene. In: Proceedings of the World Congress on Engineering and Computer Science, Vol. 2 [CrossRef]
  28. Stangret J, Gampe T (2005) Hydration of tetrahydrofuran derived from FTIR spectroscopy. J Mol Struct 734: 183-190 [CrossRef]
  29. Albanese JA, Staley DL, Rheingold AL, Burmeister JL (1990) Phosphorus ylides as hard donor ligands: synthesis and characterization of MCl4 (ylide-O)(THF) (M= Ti, Zr, Hf; ylide=(acetylmethylene) triphenylphosphorane, (benzoylmethylene) triphenylphosphorane). Molecular structure of trans-((acetylmethylene) triphenylphosphorane-O) (tetrahydrofuran) tetrachlorotitanium-(IV)-tetrahydrofuran. Inorg Chem 29: 2209-2213 [CrossRef]
  30. Koohestani H, Mansouri H, Pirmoradian A, Hassanabadi M (2020) Investigation of Photocatalytic Efficiency of Supported CuO Nanoparticles on Natural Zeolite Particles in Photodegradation of Methyl Orange. J Nanosci Nanotechnol 20: 5964-5969 [CrossRef]
  31. Koohestani H, Hasanabadi M (2023) Production and Investigation of Natural Zeolite-TiO2/CuO Nanoparticles Composite. Mech Adv Compos Struct 10: 205-210 [CrossRef]
  32. Velasco MJ, Rubio F, Rubio J, Oteo JL (1999) Hydrolysis of titanium tetrabutoxide. Study by FT-IR spectroscopy. Spectroscopy Letters 32: 289-304 [CrossRef]
  33. Esmaile F, Koohestani H, Abdollah-Pour H (2020) Characterization and antibacterial activity of silver nanoparticles green synthesized using Ziziphora clinopodioides extract. Environ. Nanotechnol. Monit 14: 100303 [CrossRef]
  34. Jiang T, Ning Y, Zhang B, Li J, Wang G, Yi J, Huang Q (2006) Preparation of 1-octene by the selective tetramerization of ethylene. J Mol Catal A-Chem 259: 161-165 [CrossRef]
  35. Kashiwa N (1983) Transition Metal Catalyzed Polymerization: Alkenes and Dienes, Harwood, New York, p. 379
  36. Ye J, Jiang B, Wang J, Yang Y, Pu Q (2014) Siloxane‐mediated ethylene oligomerization with iron‐based catalysts: Retarding the polymer formation. J Polym Sci Pol Chem 52: 2748-2759 [CrossRef]

 

Files

History

  • Receive Date: 16 March 2024
  • Revise Date: 20 April 2024
  • Accept Date: 30 April 2024

Share

How to cite

Statistics