Polymerization of 1,3-butadiene using neodymium versatate: optimization of NdV3/TEAL/EASC molar ratios via response surface methodology (RSM)


Response surface methodology (RSM) with central composite design was used to optimize and analyze the molar ratio of catalyst components for polymerization of 1,3-butadiene (Bd) using Ziegler–Natta catalyst. In this research work, the catalyst component includes neodymium versatate (NdV3) as catalyst, triethylaluminum as cocatalyst or activator and ethylaluminum sesquichloride as chloride donor. The symbols [Nd], [Al], [Cl] and [Bd] were used for catalyst, cocatalyst, donor and monomer concentration, respectively. The interaction between three important and critical variables was studied and modeled. For this purpose, independent variables are [Bd]/[Nd], [Al]/[Nd] and [Cl]/[Nd] molar ratios at three levels to optimize the dependent or response ones which are monomer conversion, molecular weight and cis content of resulting polymer. Quadratic models were achieved and developed to correlate the catalyst components’ molar ratio with dependent variables. The optimum conditions predicted via RSM were in good agreement with experimental data obtained from the experimental runs. The statistical analysis of the results showed that [Cl]/[Nd] molar ratio had a significant effect on monomer conversion and cis content. Furthermore, the catalyst components’ molar ratio to reach the desirable response parameters is forecasted and experimentally verified. The optimum catalyst components’ molar ratio derived via RSM is as follows: [Bd]/[Nd] = 5363.0, [Al]/[Nd] = 27.2 and [Cl]/[Nd] = 2.2.

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Data availability

The raw/processed data required to reproduce these findings cannot be shared at this time as the data also form a part of an ongoing study.


  1. 1.

    Singh A, Chavda A, Subrahmanyam N, Jasra RV, Maiti M (2012) Kinetic study on stereospecific polymerization of 1,3-butadiene using a nickel-based catalyst system in environmentally friendly solvent. Ind Eng Chem Res 51:11066–11071

    CAS  Article  Google Scholar 

  2. 2.

    Friebe L, Nuyken O, Obrecht W (2006) Neodymium-based Ziegler/Natta catalyst and their application in diene polymerization. Adv Polym Sci 204:1–154

    CAS  Article  Google Scholar 

  3. 3.

    Friebe L, Nuyken O, Obrecht W (2006) Neodymium-based Ziegler catalysts-fundamental chemistry. Springer, Munich, pp 287–295

    Google Scholar 

  4. 4.

    Dong W, Endo K, Masuda T (2003) Effect of tert-butyl chloride on the isoprene polymerization with neodymium isopropox/diisobutylaluminum hydride and neodymium isopropoxide/methylaluminoxane catalysts. Macromol Chem Phys 204:104–110

    CAS  Article  Google Scholar 

  5. 5.

    Summer A, Marwede G, Kelbech AS (1997) Rubber and plastics news. In: Proceeding of ITEC’96, pp 158–165

  6. 6.

    Lundstedt T, Seifert E, Abramo L, Thelin B, Nystrӧm A, Pettersen J, Bergman R (1998) Experimental design and optimization. Chemo Intell Labor Syst 42:3–40

    CAS  Article  Google Scholar 

  7. 7.

    Yabalak E, Gormez O, Giriz AM (2018) Subcritical water oxidation of propham by H2O2 using response surface methodology (RSM). J Environm Sci Heal Part B 53:334–339

    CAS  Article  Google Scholar 

  8. 8.

    Mehat NM, Kamaruddin S (2011) Multi-response optimization of injection moulding processing parameters using the taguchi method. Polym Plast Technol Eng 50:1519–1526

    CAS  Article  Google Scholar 

  9. 9.

    Lee KS, Jeon B, Cha SW, Jeong KY, Han IS, Lee YS, Lee K, Cho SM (2011) A study on optimizing the mechanical properties of glass fiber-reinforced polypropylene for automotive parts. Polym Plast Technol Eng 50:95–101

    CAS  Article  Google Scholar 

  10. 10.

    Bas D, Boyaci IH (2007) Modeling and optimization I: usability of response surface methodology. J Food Eng 78:836–845

    CAS  Article  Google Scholar 

  11. 11.

    Hivechi A, Bahrami H, Gholami Akerdi A (2018) Cellulose fabric with enhanced water absorbance and permeability using microwave radiation: modeling and optimization by RSM. J Text Inst 110:117–123

    Article  Google Scholar 

  12. 12.

    Ghasemi I, Karrabi M, Mohammadi M, Azizi H (2010) Evaluating the effect of processing conditions and organoclay content on the properties of styrene-butadiene rubber/organoclay nanocomposites by response surface methodology. Express Polym Lett 4:62–70

    CAS  Article  Google Scholar 

  13. 13.

    Chow WS, Yap YP (2008) Optimization of process variables on flexural properties of epoxy/organo-montmorillonite nanocomposites by response surface methodology. Express Polym Lett 2:2–11

    CAS  Article  Google Scholar 

  14. 14.

    William RM (2013) Response surface methodology: encyclopedia of biopharmaceutical statictics, 2nd edn. Taylor & Francis, Philadelphia, pp 860–870

    Google Scholar 

  15. 15.

    De Camargo MM, Vieira FO, Zimnoch JH, Zacca JJ (2003) Ethylene and 1-butene copolymerization catalyzed by a Ziegler–Natta/metallocene hybrid catalyst through a 23 factorial experimental design. Polymer 44:1377–1384

    Article  Google Scholar 

  16. 16.

    Nassiri H, Arabi H, Hakim S, Bolandi S (2011) Polymerization of propylene with Ziegler–Natta catalyst: optimization of operating conditions by response surface methodology (RSM). Polym Bull 67:1393–1411

    CAS  Article  Google Scholar 

  17. 17.

    Carrero A, Van-Grieken R, Paredes B (2011) Ethylene polymerization with methylaluminoxane/(nBuCp)2ZrCl2 catalyst supported on silica and silica-alumina at different AlMAO/Zr molar ratios. J Appl Polym Sci 120:599–606

    CAS  Article  Google Scholar 

  18. 18.

    Ahmadi M, Jamjah R, Nekoomanesh M, Zohuri G, Arabi H (2007) Investigation of ethylene polymerization using soluble Cp2ZrCl2/MAO catalytic system via response surface methodology. Iran Polym J 16:133–140

    CAS  Google Scholar 

  19. 19.

    Najafi M, Haddadi-Asl V (2007) Effects of reaction and processing parameters on ethylene polymerization using different Ziegler–Natta catalysts: employment of taguchi experimental design and response surface method. Chin J Polym Sci 25:153–162

    CAS  Article  Google Scholar 

  20. 20.

    Mosaddeghi MR, Pajoum Shariati F, Vaziri Yazdi SA, Nabi Bidhendi Gh (2018) Application of response surface methodology (RSM) for optimizing coagulation process of paper recycling wastewater using ocimum basilicum. Environ Technol 39:1–9

    Article  Google Scholar 

  21. 21.

    Bezerra MA, Santelli RE, Oliveira EP, Villar LS, Escaleira LA (2008) Response surface methodology (RSM) as a tool for optimization in analytical chemistry. Talanta 76:965–977

    CAS  Article  Google Scholar 

  22. 22.

    Arabi H, Beheshti MS, Yousefi M, Ghasemi Hamedani N, Ghafelebashi M (2013) Study of triisobutylaluminum as cocatalyst and processing parameters on ethylene polymerization performance of α-diimine nickel (II) complex by response surface method. Polym Bull 70:2765–2781

    CAS  Article  Google Scholar 

  23. 23.

    Brzozowski B, Lewandowska M (2014) Prolyl endopeptidase-optimization of medium and culture conditions for enhanced production by lactobacillus acidophilus. Electron J Biotechnol 17:204–210

    CAS  Article  Google Scholar 

  24. 24.

    Wang F, Liu H, Zheng W, Guo J, Zhang Ch, Zhao L, Zhang H, Hu Y, Bai Ch, Zhang X (2013) Fully-reversible and semi-reversible coordinative chain transfer polymerizations of 1,3-butadiene with neodymium-based catalytic systems. Polymer 54:6716–6724

    CAS  Article  Google Scholar 

  25. 25.

    Friebe L, Nuyken O, Windisch H, Obrecht W (2002) Polymerization of 1,3-butadiene initiated by neodymium versatate/diisobutylaluminium hydride/ethylaluminum sesquichloride: kinetics and conclusions about the reaction mechanism. Macromol Chem Phys 203:1055–1064

    CAS  Article  Google Scholar 

  26. 26.

    Friebe L, Windisch H, Nuyken O, Obrecht W (2004) Polymerization of 1,3-butadiene initiated by neodymium versatate/triisobutylaluminum/ethylaluminum sesquichloride: impact of the alkylaluminum cocatalyst component. J Macromol Sci Part A Pure Appl Chem 41:245–256

    Article  Google Scholar 

  27. 27.

    Witte J (1981) Polymerisation diene butadiene for high 1,4-cis. Angew Makromol Chem 94:119–120

    CAS  Article  Google Scholar 

  28. 28.

    Pross A, Marquardt P, Reichert KH, Nentwig W, Knauf T (1993) Modeling the polymerization of 1,3-butadiene in solution with a neodymium catalyst. Angew Makromol Chem 211:89–101

    CAS  Article  Google Scholar 

  29. 29.

    Jamjah R, Zohuri G (2008) Synthesizing UHMWPE using Ziegler–Natta catalyst system of MgCl2 (ethoxide type)/TiCl4/tri-isobutylaluminum. Macromol Symp 274:148–153

    CAS  Article  Google Scholar 

  30. 30.

    Evans WJ, Giarikos DG, Ziller JW (2001) Lanthanide carboxylate precursors for diene polymerization catalysis: syntheses, structures and reactivity with Et2AlCl. Organometallics 20:5751–5758

    CAS  Article  Google Scholar 

  31. 31.

    Neusa MTP, Fernanda MBC, Marcos ASC (2004) Synthesis and characterization of high cis-polybutadiene: influence of monomer concentration and reaction temperature. Eur Polym J 40:2599–2603

    Article  Google Scholar 

  32. 32.

    Safizadeh HM, Thornton BM (1984) Optimization in simulation experiments using response surface methodology. Comput Ind Eng 8:11–27

    Article  Google Scholar 

  33. 33.

    Najafi B, Faizollahzadeh Ardabili S, Shamshirband Sh, Chau KW, Rabczuk T (2018) Application of ANNs, ANFIS and RSM to estimating and optimizing the parameters that affect the yield and cost of biodiesel production. Eng Appl Comput Fluid Mach 12:611–624

    Google Scholar 

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Correspondence to Saeid Talebi or Mehdi Salami-Kalajahi.

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Shokri, Aa., Talebi, S. & Salami-Kalajahi, M. Polymerization of 1,3-butadiene using neodymium versatate: optimization of NdV3/TEAL/EASC molar ratios via response surface methodology (RSM). Polym. Bull. 77, 5245–5260 (2020). https://doi.org/10.1007/s00289-019-03012-6

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  • Polymerization
  • Ziegler–Natta
  • Polybutadiene
  • Neodymium versatate
  • Response surface methodology