Skip to main content
SpringerLink
Log in

New olefin block copolymers of ethylene/1-hexene synthesized by iron and zirconocene catalysts in the presence of ZnEt2

Insights from thermal properties

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

Development of olefin block copolymers (OBCs) based on new catalytic systems is challenging. We evaluate the performance of rac-ethylenebis(1-η 5-indenyl)zirconium dichloride (Zr) and bis(imino)pyridine iron (Fe) catalysts, with different comonomer affinities, in copolymerization of ethylene/1-hexene. In-depth investigation of thermal properties reveals that chain shuttling agent (CSA) has diverse effects on the microstructure formed by the individual catalysts. Specifically, as confirmed by CNMR measurements, the comonomer affinity of the Zr catalyst is noticeably reduced while it remains unchanged for the Fe catalyst. Copolymers produced by the binary catalytic system in the presence of CSA do not show indications for formation of blocky structure at higher Zr fractions, while at lower fractions, a significantly different behavior is exposed, e.g., high melting temperature peak is replaced by broad low-temperature endotherm and lower molar mass with narrow distribution is obtained. It could be concluded that this catalyst composition can be a good candidate for operative production of OBCs.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Domski GJ, Rose JM, Coates GW, Bolig AD, Brookhart M. Living alkene polymerization: new methods for the precision synthesis of polyolefins. Prog Polym Sci. 2007;32(1):30–92.

    Article  CAS  Google Scholar 

  2. Makio H, Terao H, Iwashita A, Fujita T. FI catalysts for olefin polymerization, a comprehensive treatment. Chem Rev. 2011;111(3):2363–449.

    Article  CAS  Google Scholar 

  3. Gates DP, Svejda SA, Oñate E, Killian CM, Johnson LK, White PS, et al. Synthesis of branched polyethylene using (α-diimine) nickel (II) catalysts: influence of temperature, ethylene pressure, and ligand structure on polymer properties. Macromolecules. 2000;33(7):2320–34.

    Article  CAS  Google Scholar 

  4. Valente A, Mortreux A, Visseaux M, Zinck P. Coordinative chain transfer polymerization. Chem Rev. 2013;113(5):3836–57.

    Article  CAS  Google Scholar 

  5. Rouholahnejad F, Mathis D, Chen P. Narrowly distributed polyethylene via reversible chain transfer to aluminum by a sterically hindered zirconocene/MAO. Organometallics. 2009;29(2):294–302.

    Article  Google Scholar 

  6. Hustad PD, Kuhlman RL, Carnahan EM, Wenzel TT, Arriola DJ. An exploration of the effects of reversibility in chain transfer to metal in olefin polymerization. Macromolecules. 2008;41(12):4081–9.

    Article  CAS  Google Scholar 

  7. Mazzolini J, Espinosa E, D’Agosto F, Boisson C. Catalyzed chain growth (CCG) on a main group metal: an efficient tool to functionalize polyethylene. Polym Chem. 2010;1(6):793–800.

    Article  CAS  Google Scholar 

  8. Briquel R, Mazzolini J, Le Bris T, Boyron O, Boisson F, Delolme F, et al. Polyethylene building blocks by catalyzed chain growth and efficient end functionalization strategies, including click chemistry. Angew Chem Int Ed. 2008;47(48):9311–3.

    Article  CAS  Google Scholar 

  9. German I, Kelhifi W, Norsic S, Boisson C, D’Agosto F. Telechelic polyethylene from catalyzed chain-growth polymerization. Angew Chem Int Ed. 2013;52(12):3438–41.

    Article  CAS  Google Scholar 

  10. Arriola DJ, Carnahan EM, Hustad PD, Kuhlman RL, Wenzel TT. Catalytic production of olefin block copolymers via chain shuttling polymerization. Science. 2006;312(5774):714–9.

    Article  CAS  Google Scholar 

  11. Mohammadi Y, Ahmadi M, Saeb MR, Khorasani MM, Yang P, Stadler FJ. A detailed model on kinetics and microstructure evolution during copolymerization of ethylene and 1-octene: from coordinative chain transfer to chain shuttling polymerization. Macromolecules. 2014;47(14):4778–89.

    Article  CAS  Google Scholar 

  12. Ahmadi M, Nasresfahani A. Realistic representation of kinetics and microstructure development during chain shuttling polymerization of Olefin block copolymers. Macromol Theory Simul. 2015;24(4):311–21.

    Article  CAS  Google Scholar 

  13. Ahmadi M, Saeb MR, Mohammadi Y, Khorasani MM, Stadler FJ. A perspective on modeling and characterization of transformations in the blocky nature of olefin block copolymers. Ind Eng Chem Res. 2015;54(36):8867–73.

    Article  CAS  Google Scholar 

  14. Saeb MR, Khorasani MM, Ahmadi M, Mohammadi Y, Stadler FJ. A unified picture of hard-soft segmental development along olefin chain shuttling copolymerization. Polymer. 2015;76:245–53.

    Article  CAS  Google Scholar 

  15. Xiao A, Wang L, Liu Q, Yu H, Wang J, Huo J, et al. A novel linear-hyperbranched multiblock polyethylene produced from ethylene monomer alone via chain walking and chain shuttling polymerization. Macromolecules. 2009;42(6):1834–7.

    Article  CAS  Google Scholar 

  16. Ahmadjo S. Preparation of ultra high molecular weight amorphous poly(1-hexene) by a Ziegler-Natta catalyst. Polym Adv Technol. 2016;27:1523–9.

    Article  CAS  Google Scholar 

  17. Britovsek GJ, Cohen SA, Gibson VC, Maddox PJ, van Meurs M. Iron-catalyzed polyethylene chain growth on zinc: linear α-olefins with a poisson distribution. Angew Chem Int Ed. 2002;41(3):489–91.

    Article  CAS  Google Scholar 

  18. Britovsek GJ, Cohen SA, Gibson VC, van Meurs M. Iron catalyzed polyethylene chain growth on zinc: a study of the factors delineating chain transfer versus catalyzed chain growth in zinc and related metal alkyl systems. J Am Chem Soc. 2004;126(34):10701–12.

    Article  CAS  Google Scholar 

  19. Zinck P. Unexpected reactivities in chain shuttling copolymerizations. Polym Int. 2016;65(1):11–5.

    Article  CAS  Google Scholar 

  20. Zhang M, Karjala TW, Jain P. Modeling of α-olefin copolymerization with chain-shuttling chemistry using dual catalysts in stirred-tank reactors: molecular weight distributions and copolymer composition. Ind Eng Chem Res. 2010;49(17):8135–46.

    Article  CAS  Google Scholar 

  21. Mahdavi H, Badiei A, Zohuri GH, Rezaee A, Jamjah R, Ahmadjo S. Homogeneous polymerization of ethylene using an iron-based metal catalyst system. J Appl Polym Sci. 2007;103(3):1517–22.

    Article  CAS  Google Scholar 

  22. Park HE, Dealy JM, Marchand GR, Wang J, Li S, Register RA. Rheology and Structure of molten, olefin multiblock copolymers. Macromolecules. 2010;43:6789–99.

    Article  CAS  Google Scholar 

  23. Shan CLP, Hazlitt LG. Block index for characterizing olefin block copolymers. Macromol Symp. 2007;257(1):80–93.

    Article  CAS  Google Scholar 

  24. Tong Z-Z, Zhou B, Huang J, Xu J-T, Fan Z-Q. Regulation of crystallization kinetics, morphology, and mechanical properties of olefinic blocky copolymers. Macromolecules. 2014;47(1):333–46.

    Article  CAS  Google Scholar 

  25. Wang H, Khariwala D, Cheung W, Chum S, Hiltner A, Baer E. Characterization of some new olefinic block copolymers. Macromolecules. 2007;40(8):2852–62.

    Article  CAS  Google Scholar 

  26. Kuhlman RL, Wenzel TT. Investigations of chain shuttling olefin polymerization using deuterium labeling. Macromolecules. 2008;41(12):4090–4.

    Article  CAS  Google Scholar 

  27. Wang W. Effect of diethylzinc on the activity of ethylene polymerization by metallocene catalyst. Macromol React Eng. 2015;9(4):333–8.

    Article  CAS  Google Scholar 

  28. Wei J, Zhang W, Sita LR. Aufbaureaktion redux: scalable production of precision hydrocarbons from AlR3 (R = Et or iBu) by dialkyl zinc mediated ternary living coordinative chain-transfer polymerization. Angew Chem Int Ed. 2010;49:1768–72.

    Article  CAS  Google Scholar 

  29. van Meurs M, Britovsek GJ, Gibson VC, Cohen SA. Polyethylene chain growth on zinc catalyzed by olefin polymerization catalysts: a comparative investigation of highly active catalyst systems across the transition series. J Am Chem Soc. 2005;127(27):9913–23.

    Article  Google Scholar 

  30. Mehdiabadi S, Soares JB. Quantifying the copolymerization kinetics of ethylene and 1-octene catalyzed with rac-Et (Ind) 2ZrCl2 in a solution reactor. Macromolecules. 2016;49(7):2448–57.

    Article  CAS  Google Scholar 

  31. Bianchini C, Giambastiani G, Rios IG, Mantovani G, Meli A, Segarra AM. Ethylene oligomerization, homopolymerization and copolymerization by iron and cobalt catalysts with 2, 6-(bis-organylimino) pyridyl ligands. Coord Chem Rev. 2006;250(11):1391–418.

    Article  CAS  Google Scholar 

  32. Gibson VC, Redshaw C, Solan GA. Bis (imino) pyridines: surprisingly reactive ligands and a gateway to new families of catalysts. Chem Rev. 2007;107(5):1745–76.

    Article  CAS  Google Scholar 

  33. Zhang M, Carnahan EM, Karjala TW, Jain P. Theoretical analysis of the copolymer composition equation in chain shuttling copolymerization. Macromolecules. 2009;42(21):8013–6.

    Article  CAS  Google Scholar 

  34. Ahmadi M, Mortazavi SMM, Ahmadjo S, Zahmati M, Valieghbal K, Jafarifar D. Evaluation of continuous and discrete melting endotherms in determination of structural heterogeneities in Ziegler-Natta catalyzed linear low density polyethylene. Polyolefins J. 2016;3(2):135–46.

    Google Scholar 

  35. Ahmadi M, Rezaei F, Mortazavi SMM, Entezam M, Stadler FJ. Complex interplay of short-and long-chain branching on thermal and rheological properties of ethylene/α-olefin copolymers made by metallocene catalysts with oscillating ligand structure. Polymer. 2017;112:43–52.

    Article  CAS  Google Scholar 

  36. Hosoda S. Structural distribution of linear low-density polyethylenes. Polym J. 1988;20(5):383–97.

    Article  CAS  Google Scholar 

  37. Bhriain NN, Brintzinger H-H, Ruchatz D, Fink G. Polymeryl exchange between a nsa-zirconocene catalysts for norbornene-ethene copolymerization and aluminum or zinc alkyls. Macromolecules. 2005;38(6):2056–63.

    Article  CAS  Google Scholar 

  38. Georges S, Touré AO, Visseaux M, Zinck P. Coordinative chain transfer copolymerization and terpolymerization of conjugated dienes. Macromolecules. 2014;47(14):4538–47.

    Article  CAS  Google Scholar 

  39. Loughmari S, Hafid A, Bouazza A, El Bouadili A, Zinck P, Visseaux M. Highly stereoselective coordination polymerization of β-myrcene from a lanthanide-based catalyst: access to bio-sourced elastomers. J Polym Sci A Polym Chem. 2012;50(14):2898–905.

    Article  CAS  Google Scholar 

  40. Ventura A, Chenal T, Bria M, Bonnet F, Zinck P, Ngono-Ravache Y, et al. Trans-stereospecific polymerization of butadiene and random copolymerization with styrene using borohydrido neodymium/magnesium dialkyl catalysts. Eur Polym J. 2013;49(12):4130–40.

    Article  CAS  Google Scholar 

  41. Britovsek GJ, Gibson VC, McTavish SJ, Solan GA, White AJ, Williams DJ, et al. Novel olefin polymerization catalysts based on iron and cobalt. Chem Commun. 1998;7:849–50.

    Article  Google Scholar 

  42. Kissin YV, Qian C, Xie G, Chen Y. Multi-center nature of ethylene polymerization catalysts based on 2, 6-bis (imino) pyridyl complexes of iron and cobalt. J Polym Sci A Polym Chem. 2006;44(21):6159–70.

    Article  CAS  Google Scholar 

  43. Mortazavi SMM, Jafarian H, Ahmadi M, Ahmadjo S. Characteristics of linear/branched polyethylene reactor blends synthesized by metallocene/late transitional metal hybrid catalysts. J Therm Anal Calorim. 2016;123(2):1469–78.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

MA would like to thank Iran National Science Foundation (INSF) for their financial support.

Author information

Authors and Affiliations

  1. Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran, Iran

    Mostafa Ahmadi

  2. Research and Development, Jam Petrochemical Co, Tehran, Iran

    Reza Rashedi & Majid Zahmaty

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

    Saeid Ahmadjo, Mahsa Karimi & Seyed Mohammad Mahdi Mortazavi

Authors
  1. Mostafa Ahmadi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Reza Rashedi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Saeid Ahmadjo
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mahsa Karimi
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Majid Zahmaty
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Seyed Mohammad Mahdi Mortazavi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Seyed Mohammad Mahdi Mortazavi.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ahmadi, M., Rashedi, R., Ahmadjo, S. et al. New olefin block copolymers of ethylene/1-hexene synthesized by iron and zirconocene catalysts in the presence of ZnEt2 . J Therm Anal Calorim 131, 2523–2533 (2018). https://doi.org/10.1007/s10973-017-6824-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-017-6824-0

Keywords

Search

Navigation