Comparison of the Effects of Ethers Compounds as the New Internal Donors on Ziegler-Natta Catalysts for Polymerization of Propylene

Document Type : Research Article


1 Department of Chemistry, Amirkabir University of Technology, Tehran, I.R. IRAN

2 Department of Polymer Engineering, Amirkabir University of Technology, Tehran, I.R. IRAN

3 Iran Polymer and Petrochemical Institute (IPPI), Tehran, I.R. IRAN


In this study, 1,3-dimethoxy-2,2-bis(methoxymethyl)propane (Yield: 85%), 5,5-bis(methoxymethyl)-1,3-dioxane (Yield: 89%), 1-methoxy-2,2-bis(methoxymethyl)butane (Yield: 98%), 1,3-dimethoxy-2-((3-methoxy-2,2- bis(methoxymethyl)propoxy)methyl)-2-(methoxymethyl)propane (Yield: 78%) and 1-(2,2-bis(methoxymethyl)butoxy)-2,2-bis(methoxymethyl)butane (Yield: 93%) as the new internal electron donors were synthesized using the Williamson reaction. The synthesized ethers were characterized by FTIR, NMR, and GC techniques. The MgCl2-supported Ziegler-Natta catalysts were prepared with optimum ID/Mg molar ratio of synthesized internal electron donors, and also without the internal electron donor. Then, polymerization of propylene was carried out with the prepared catalysts and also with industrial Ziegler-Natta catalyst, with and without the external donor, in the presence of triethylaluminum as a co-catalyst and hydrogen as a chain transfer agent. Effects of ethers compounds as the new internal donors on the catalytic activity, Hydrogen response of the prepared catalysts, xylene solubility, weight-average molecular weight, molecular weight distribution, crystallinity degree, and thermal properties of the produced polypropylenes were examined. Then the performance of the prepared MgCl2-supported Ziegler-Natta catalysts with new internal electron donors on the properties of produced polypropylenes were compared with each other and also, with industrial Ziegler-Natta catalyst containing diisobutyl phthalate internal donor and catalyst without the internal electron donor.


Main Subjects

[1] Potapov A.G., Politanskaya L.V., The Study of the Adsorption of 1,3-Diethers on the MgCl2 Surface, J. Mol. Catal. A: Chem., 368–369: 159-162 (2013).
[2] Tangjituabun K., Jongsomjit B., Praserthdam P., The Role of CaO in the Ziegler-Natta Catalyst for Propylene Polymerization, Catal. Lett., 109(3): 147-152 (2006).
[3] Credendino R., Minenkov Y., Liguori D., Piemontesi F., Melchior A., Morini G., Tolazzi M., Cavallo, L., Accurate Experimental and Theoretical Enthalpies of Association of TiCl4 with Typical Lewis Bases Used in Heterogeneous Ziegler–Natta CatalysisPhys. Chem. Chem. Phys.19(39): 26996-27006 (2017).
[4] Thushara K., Gnanakumar E.S., Mathew R., Jha R.K., Ajithkumar T., Rajamohanan P., Sarma K., Padmanabhan S., Bhaduri S., Gopinath C.S., Toward an Understanding of the Molecular Level Properties of Ziegler-Natta Catalyst Support with and without the Internal Electron Donor, J. Phys. Chem. C, 115(5): 1952-1960 (2010).
[5] Mori H., Hasebe K., Terano M., XPS Study of the Interaction of Titanium Species with Internal Electron Donors on MgCl2-Supported Ziegler Catalysts, J. Mol. Catal. A: Chem.,140(2): 165-172 (1999).
[6] Matsuoka H., Liu B., Nakatani H., Nishiyama I., Terano M., Active Sites Deterioration of MgCl2‐Supported Catalyst Induced by the Electron Donor Extraction by Alkylaluminium, Polym. Int., 51(9): 781-784 (2002).
[7] Makwana U.C., Singala K.J., Patankar R.B., Singh S.C., Gupta V.K., Propylene Polymerization Using Supported Ziegler-Natta Catalyst Systems with Mixed Donors, J. Appl. Polym. Sci., 125(2): 896-901 (2012).
[8] Groppo E., Seenivasan K., Barzan C., The Potential of Spectroscopic Methods Applied to Heterogeneous Catalysts for Olefin Polymerization, Catal. Sci. Tech., 3(4): 858-878 (2013).
[9] Bazhenov A.S., Denifl P., Leinonen T., Pakkanen A., Linnolahti M., Pakkanen T.A., Modeling Coadsorption of Titanium Tetrachloride and Bidentate Electron Donors on Magnesium Dichloride Support Surfaces, J. Phys. Chem. C, 118(48): 27878-27883 (2014).
[10] Ratanasak M., Rungrotmongkol T., Saengsawang O., Hannongbua S., Parasuk V., Towards the Design of New Electron Donors for Ziegler-Natta Catalyzed Propylene Polymerization Using QSPR Modeling, Polym., 56: 340-345 (2015).
[11] Thushara K., Gnanakumar E.S., Mathew R., Ajithkumar T., Rajamohanan P., Bhaduri S., Gopinath C.S., MgCl2·4((CH3)2CHCH2OH): A New Molecular Adduct for the Preparation of TiClx/MgCl2 Catalyst for Olefin Polymerization, Dalton Trans., 41(37): 11311-11318 (2012).
[12] Gnanakumar E.S., Gowda R.R., Kunjir S., Ajithkumar T., Rajamohanan P., Chakraborty D., Gopinath C.S., MgCl2.6CH3OH: A Simple Molecular Adduct and its Influence As a Porous Support for Olefin Polymerization, ACS Catal., 3(3): 303-311 (2013).
[14] Kumawat J., Gupta V.K., Vanka K., Donor Decomposition by Lewis Acids in Ziegler-Natta Catalyst Systems: A Computational Investigation, Organomet., 33(17): 4357-4367 (2014).
[15] Paukkeri R., Iiskola E., Lehtinen A., Salminen H., Microstructural Analysis of Polypropylenes Polymerized with Ziegler-Natta Catalysts Without External Donors, Polym., 35(12): 2636-2643 (1994).
[16] Zhang H.-X., Lee Y.-J., Park J.-R., Lee D.-H., Yoon K.-B., Control of Molecular Weight Distribution for Polypropylene Obtained by Commercial Ziegler-Natta Catalyst: Effect of Electron Donor, Macromol. Res., 19(6): 622-628 (2011).
[17] Andoni A., Chadwick J.C., Milani S., Niemantsverdriet H.J., Thüne P.C., Introducing a New Surface Science Model for Ziegler-Natta Catalysts: Preparation, Basic Characterization and Testing, J. Catal., 247(2): 129-136 (2007).
[18] Capone F., Rongo L., D’Amore M., Budzelaar P.H., Busico V., Periodic Hybrid DFT Approach (Including Dispersion) to MgCl2-Supported Ziegler-Natta Catalysts. 2. Model Electron Donor Adsorption on MgCl2 Crystal Surfaces, J. Phys. Chem. C, 117(46): 24345-24353 (2013).
[21] Heikkinen H., Liitiä T., Virkkunen V., Leinonen T., Helaja T., Denifl P., Solid State 13C NMR Characterisation Study on Fourth Generation Ziegler-Natta Catalysts, Solid State Nucl. Magn. Reson., 43-44: 36-41 (2012).
[22] Wen X., Ji M., Yi Q., Niu H., Dong J.Y., Magnesium Chloride Supported Ziegler‐Natta Catalysts Containing Succinate Internal Electron Donors for the Polymerization of Propylene, J. Appl. Polym. Sci., 118(3): 1853-1858 (2010).
[23] Gnanakumar E.S., Thushara K., Bhange D.S., Mathew R., Ajithkumar T., Rajamohanan P., Bhaduri S., Gopinath C.S., MgCl2.6PhCH2OH - A New Molecular Adduct as Support Material for Ziegler–Natta Catalyst: Synthesis, Characterization and Catalytic Activity, Dalton Trans., 40(41): 10936-10944 (2011).
[24] Bazhenov A., Linnolahti M., Pakkanen T.A., Denifl P., Leinonen T., Modeling the Stabilization of Surface Defects by Donors in Ziegler-Natta Catalyst Support, J. Phys. Chem. C, 118(9): 4791-4796 (2014).
[25] Chadwick J.C., Morini G., Balbontin G., Camurati I., Heere J.J., Mingozzi I., Testoni F., Effects of Internal and External Donors on the Regio‐and Stereoselectivity of Active Species in MgCl2‐Supported Catalysts for Propene Polymerization, Macromol. Chem. Phys., 202(10): 1995-2002 (2001).
[26] Andoni A., Chadwick J.C., Niemantsverdriet H.J., Thüne P.C., A Preparation Method for Well‐Defined Crystallites of MgCl2‐Supported Ziegler‐Natta Catalysts and their Observation by AFM and SEM, Macromol. Rapid Commun., 28(14): 1466-1471 (2007).
[27] Andoni A., Chadwick J.C., Niemantsverdriet H.J., Thüne P.C., The Role of Electron Donors on Lateral Surfaces of MgCl2-Supported Ziegler-Natta Catalysts: Observation by AFM and SEM, J. Catal., 257(1): 81-86 (2008).
[30] Qiao J., Guo M., Wang L., Liu D., Zhang X., Yu L., Song W., Liu Y., Recent Advances in Polyolefin Technology, Polym. Chem., 2(8): 1611-1623 (2011).
[31] Pirinen S., Pakkanen T.T., Polyethers as Potential Electron Donors for Ziegler-Natta Ethylene Polymerization Catalysts, J. Mol. Catal. A: Chem., 398: 177-183 (2015).
[32] Marques M.D.F.V., Cardoso R.D.S., Da Silva M.G., Preparation of MgCl2-Supported Ziegler-Natta Catalyst Systems with New Electron Donors, Appl. Catal. A: Gen., 374(1–2): 65-70 (2010).
[33] Guo J., Hu G., Chen Z., Synthesis of Novel Electron Donors and Their Application to Propylene Polymerization, Trans. Tianjin Univ., 18: 8-14 (2012).
[34] Cavallo L., Del Piero S., Ducéré J.-M., Fedele R., Melchior A., Morini G., Piemontesi F., Tolazzi M., Key Interactions in Heterogeneous Ziegler-Natta Catalytic Systems: Structure and Energetics of TiCl4-Lewis Base Complexes, J. Phys. Chem. C, 111(11): 4412-4419 (2007).
[35] Jenny C., Maddox P., Supported Polyolefin Catalysts, Curr. Opin. Solid State Mater. Sci., 3(1): 94-103 (1998).
[36] Zohuri G.H., Kasaeian A.B., Torabi Angagi M., Jamjah R., Mousavian M.A., Emami M., Ahmadjo S., Polymerization of Propylene Using MgCl2 (Ethoxide Type)/TiCl4/Diether Heterogeneous Ziegler–Natta Catalyst, Polym. Int., 54(6): 882-885 (2005).
[38] Junting X., Linxian F., Senhui W., Shilin Y., Supported Catalyst Without External Electron Donor for Propylene Polymerization Ⅱ. Tacticity Distribution and Microstructure of Polypropylene, Chin. J. Polym. Sci., 16(1): 56-61 (1998).
[39] Wang N., Qin Y., Huang Y., Niu H., Dong J.-Y., Wang Y., Functionalized Multi-Walled Carbon Nanotubes with Stereospecific Ziegler-Natta Catalyst Species: Towards Facile in Situ Preparation of Polypropylene Nanocomposites, Appl. Catal. A: Gen., 435-436: 107-114 (2012).
[40] Chadwick J.C., Van Der Burgt F.P., Rastogi S., Busico V., Cipullo R., Talarico G., Heere J.J., Influence of Ziegler-Natta Catalyst Regioselectivity on Polypropylene Molecular Weight Distribution and Rheological and Crystallization Behavior, Macromol., 37(26): 9722-9727 (2004).
[41] Phiwkliang W., Jongsomjit B., Praserthdam P., Synergistic Effects of the ZnCl2-SiCl4 Modified TiCl4/MgCl2/THF Catalytic System on Ethylene/1-Hexene and Ethylene/1-Octene Copolymerizations, Chin. J. Polym. Sci., 32(1): 84-91 (2014).
[42]  Zahedi R., Afshar Taromi F., Mirjahanmardi S. H., Nekoomanesh Haghighi M., Jadidi K., Jamjah R. Propylene Polymerization over MgCl2‐Supported Ziegler–Natta Catalysts Containing Tri‐Ether as the Internal DonorAdv. Poly. Tech.37(1): 144-153 (2018).
[43] Mirjahanmardi S. H., Taromi F. A., Zahedi R., Haghighi M. N., Effects of Various Amounts of New Hepta-Ether as the Internal Donor on the Polymerization of Propylene with and without the External Donor. Polym. Sci., Ser. B., 59(6): 639-649 (2017).
[44] Zahedi R., Taromi F. A., Mirjahanmardi S. H., Haghighi M. N., Jadidi K., Jamjah R. New Penta-Ether as the Internal Donor in the MgCl2-supported Ziegler-Natta Catalysts for Propylene PolymerizationChin. J. Polym. Sci.34(3): 268-279 (2016).
[46] Wang J., Cheng R., He X., Liu Z., Tian Z., Liu B., A Novel (SiO2/MgO/MgCl2).TiClx Ziegler-Natta Catalyst for Ethylene and Ethylene/1‐Hexene Polymerization, Macromol. Chem. Phys., 216(13): 1472-1482 (2015).
[47] Bichinho K.M., Pires G.P., Dos Santos J.H.Z., De Camargo Forte M.M., Wolf C.R., Determination of Mg, Ti and Cl in Ziegler-Natta Catalysts by WDXRF, Anal. Chim. Acta, 512(2): 359-367 (2004).
[49] Lima A., Azeredo A.P., Nele M., Liberman S., Pinto J.C., Synthesis and Characterization of Diolefin/Propylene Copolymers by Ziegler-Natta Polymerization, Macromol. Symp., 344(1): 86-93 (2014).
[50] Salakhov I., Batyrshin A., Sergeev S., Bukatov G., Barabanov A., Sakhabutdinov A., Zakharov V., Gilmanov K.K., Polymerization of propylene in liquid Monomer Using State-of-the-Art High-Performance Titanium-Magnesium Catalysts, Catal. Ind., 6(3): 198-201 (2014).
[52] Chang H., Li H., Zheng T., Zhou Q., Zhang L., Hu Y., The Effects of New Aminosilane Compounds as External Donors on Propylene Polymerization, J. Polym. Res., 21(9): 1-11 (2014).
[54] Zhou Q., Zheng T., Li H., Li Q., Zhang Y., Zhang L., Hu Y., Effects of Some New Alkoxysilane External Donors on Propylene Polymerization in MgCl2-Supported Ziegler-Natta Catalysis, Ind. Eng. Chem. Res., 53(46): 17929-17936 (2014).
[55] Shin Y.-J., Zhang H.-X., Yoon K.-B., Lee D.-H., Preparation of Ultra-High Molecular Weight Polyethylene with MgCl2/TiCl4 Catalysts: Effect of Temperature and Pressure, Macromol. Res., 18(10): 951-955 (2010).