1-Hexene Polymerization Using Ziegler-Natta Catalytic System with Response Surface Methodology

Document Type : Research Paper

Authors

1 Chemical Engineering Department, Faculty of Engineering, Ferdowsi University of Mashhad, P.O. Box: 91775-1111, Mashhad, Iran

2 Department of Catalyst, Iran Polymer and Petrochemical Institute, P.O. Box: 14965-115, Tehran, Iran

Abstract

The effects of process conditions and their interactions on the catalyst activity in 1-hexene polymerization were studied with design of experiments by response surface methodology (RSM) using a commercial Ziegler-Natta (ZN) catalyst in the form of TiCl4/MgCl2/Di-n-butyl phthalate. The effect of different operational variables on the catalyst activity was examined by performing the primary experiments of 1-hexene polymerization.  Among different operational variables, three variables including monomer concentration, polymerization temperature and cocatalyst/catalyst molar ratio (Al/Ti) were considered as the main parameters which affected the catalyst activity in the 1-hexene polymerization. The Box-Behnken model with three main parameters in three level responses for each factor was applied to analyze the parameter relationships. After demonstrating the reproducibility of the experimental results, the statistical analysis of experimental data showed that the monomer concentration and Al/Ti molar ratio affected the catalyst activity significantly. It was found that, at room temperature, by increasing the monomer concentration from 80.0 mmol to 239.9 mmol, the activity of the studied ZN catalyst increased from 75.2 to 265.1 gpoly(1-hexene)/gcat. In addition, by changing the Al/Ti ratio from 45.9 to 136.8, the catalyst activity increased from 145.2 to 265.1 gpoly(1-hexene)/gcat. The maximum activity of catalyst was obtained at the polymerization temperature around 25°C, and by increasing the temperature the activity of studied catalyst decreased. Based on the RSM, the best polymerization condition was obtained at a polymerization temperature of about 35°C, Al/Ti ratio of 136.8, and monomer concentration of 239.9 mmol, which resulted in maximum productivity of the catalyst.

Keywords


AlMa’adeed M.A.A. and Krupa I., Polyolefin Compounds and Materials: Fundamentals and Industrial Applications, Springer, Switzerland, 1-10, 2016.
Ahmadjo S., Arabi H., Zohuri G.H., Nekoomanesh-Haghighi M., Nejabat G., and Mortazavi S.M.M., Preparation of Ethylene/α-OlefinsCopolymers Using (2-RInd)2ZrCl2/MCM-41(R:Ph,H) Catalyst Microstructural Study, J. Therm. Anal. Calorim.,116, 417-426, 2014.
Arabi H., Ghafari M., Zohuri G.H., Damavandi S., and Ahmadjo S., Polymerization of Ethylene Using α-Diimine Nickel Catalyst, Iran. J. Polym. Sci. Technol. (Persian), 26, 327-335, 2013.
Mortazavi S.M.M., Ahmadjo S., Nekoomanesh-Haghighi M., Arabi H., and Zohuri G.H., Synthesis of Metallocene Catalyst for Terpolymerization of Ethylene, Propylene and Diene. Iran. J. Polym. Sci. Technol. (Persian), 27, 25-35, 2014.
Ahmadjo S., Preparation of Ultra High Molecular Weight Amorphous Poly(1-hexene) by a Ziegler–Natta Catalyst, Polym. Adv. Technol., 27, 1523-1529, 2016.
Martín-Alfonso J.E., Valencia C., Sánchez M.C., Franco J.M., and Gallegos C., Evaluation of Different Polyolefins as Rheology Modifier Additives in Lubricating Grease Formulations, Mater. Chem. Phys., 128, 530-538, 2011.
Mortazavi S.M.M., Correlation of Polymerization Conditions with Drag Reduction Efficiency of Poly(1-hexene) in Oil Pipelines, Iran. Polym. J., 25, 731-737, 2016.
Piloz A., Pham Q.T., Decroix J.Y., and Guillot J., Copolymerization of Olefins by Ziegler-Natta Catalyst. The Copolymerization of 1-Hexene and Propylene. Kinetic Study, J. Macromol. Sci., Chem., 9, 517-537, 1975.
Kothandaraman H. and Devi M.S., Kinetics of Polymerization of 1-Octene with MgCl2-Supported TiCl4 Catalysts, J. Polym. Sci., Part A: Polym. Chem., 32, 1283-1294, 1994.
Saxena P.K., Polymerization of 1-Hexene Using Supported Magnesium/Titanium Catalyst: Effect of Cocatalyst, Eur. Polym. J., 35, 1313-1317, 1999.
Vasilenko I.V. and Kostjuk S.V., The Influence of Cocatalysts on 1-Hexene Polymerization with Various Supported Magnesium–Titanium Catalysts, Polym. Bull., 57, 129-138, 2006.
Dashti A., Ramazani S.A.A., Hiraoka Y., Kim S.Y., Taniike T., and Terano M., Kinetic and Morphological Study of a Magnesium Ethoxide-based Ziegler–Natta Catalyst for Propylene Polymerization, Polym. Int., 58, 40-45, 2009.
Fan Z., Zhang L., Xia S., and Fu Z., Effects of Ethylene as Comonomer on the Active Center Distribution of 1-Hexene Polymerization with MgCl2-Supported Ziegler–Natta Catalysts, J. Mol. Catal. A: Chem., 351, 93-99, 2011.
Echevskaya L., Matsko M., Nikolaeva M., Sergeev S., and Zakharov V., Kinetic Features of Hexene-1 Polymerization Over Supported Titanium–Magnesium Catalyst, Macromol. React. Eng., 8, 666-672, 2014.
Yang H., Zhang L., Zang D., Fu Z., and Fan Z., Effects of Alkylaluminum as Cocatalyst on the Active Center Distribution of 1-Hexene Polymerization with MgCl2-Supported Ziegler–Natta Catalysts, Catal. Commun., 62, 104-106, 2015.
Myers R.H., Montgomery D.C., and Anderson-Cook C.M., Response Surface Methodology: Process and Product Optimization Using Designed Experiments, John Wiley and Sons, USA, 3rd ed., Chapt.1, 2009.
Ahmadi M., Jamjah R., Nekoomanesh M., Zohuri G.H., and Arabi H., Investigation of Ethylene Polymerization Using Soluble Cp2ZrCl2/MAO Catalytic System via Response Surface Methodology, Iran. Polym. J.,16, 133-140, 2007.
Arabi H., Mobarakeh H.S., Balzadeh Z., and Nejabat G.R., Copolymerization of Ethylene/5-Ethylidene-2-Norbornene with Bis(2-phenylindenyl) Zirconium Dichloride Catalyst: I. Optimization of the Operating Conditions by Response Surface Methodology, J. Appl. Polym. Sci., 129, 3047-3053, 2013.
Shiva M., Hadadi A., Nakhaei A., and Varasteh H., Study of Abrasion of Rubber Materials by Experimental Design, Response Surface and Artificial Neural Network Modeling, Iran. J. Polym. Sci. Technol. (Persian), 28, 197-209, 2015.
Shafiee M., Ramazani S.A.A., Bahrami H., and Kheradmand A., Preparation of Ultra High Molecular Weight Polyethylene Using Ziegler-Natta Catalyst System: Optimization of Parameters by Response Surface Methodology, Iran. J. Chem. Eng., 11, 55-62, 2014.
Mazaheriyan M., 1-Hexene polymerization Using Zeigler-Natta Catalyst, MSc Thesis, Ferdowsi University of Mashhad, 2015.
Khuri A.I. and Mukhopadhyay S., Response Surface Methodology, Wiley Interdiscip. Rev. Comput. Stat., 2, 128-149, 2010.
Nassiri H., Arabi H., Hakim S., and Bolandi S., Polymerization of Propylene with Ziegler–Natta Catalyst: Optimization of Operating Conditions by Response Surface Methodology (RSM), Polym. Bull., 67, 1393-1411, 2011.
Brüll R., Pasch H., Raubenheimer H.G., Sanderson R., and Wahner U.M., Polymerization of Higher Linear α-olefins with (CH3)2Si(2-methylbenzeindenyl)2ZrCl2, J. Polym. Sci., Part A: Polym. Chem., 38, 2333-2339, 2000.
Fregonese D., Mortara S., and Bresadola S., Ziegler–Natta MgCl2-Supported Catalysts: Relationship Between Titanium Oxidation States Distribution and Activity in Olefin Polymerization, J. Mol. Catal. A: Chem., 172, 89-95, 2001.
Kissin Y.V., Mink R.I., Nowlin T.E., and Brandolini A.J., Kinetics and Mechanism of Ethylene Homopolymerization and Copolymerization Reactions with Heterogeneous Ti-based Ziegler–Natta Catalysts, Top. Catal., 7, 69-88, 1999.
Zohuri G.H., Azimfar F., Jamjah R., and Ahmadjo, S., Polymerization of Propylene Using the HighActivity Ziegler–Natta Catalyst System SiO2/MgCl2 (Ethoxide type)/TiCl4/Di-n-butyl phthalate/Triethylaluminum/Dimethoxy Methyl Cyclohexyl Silane, J. Appl. Polym. Sci., 89, 1177-1181, 2003.
Kaur S., Naik D.G., Singh G., Patil H.R., Kothari A.V., and Gupta, V. K., Poly(1-octene) Synthesis Using High Performance Supported Titanium Catalysts, J. Appl. Polym. Sci., 115, 229-236, 2010.
Rahbar A., Nekoomanesh-Haghighi M., Bahri-Laleh N., and Abedini, H. Effect of Water on the Supported Ziegler–Natta Catalysts: Optimization of the Operating Conditions by Response Surface Methodology, Catal. Lett., 145, 1186-1195, 2015.
Khan M.J.H., Hussain M.A., and Mujtaba, I.M., Developed Hybrid Model for Propylene Polymerisation at Optimum Reaction Conditions, Polymers, 8, 47, 2016.