مروری بر نسل های گوناگون کاتالیست های زیگلر ـ ناتا و اجزای تشکیل دهنده آن ها برای پلیمریزاسیون پروپیلن

نوع مقاله: مروری

نویسندگان

1 گروه شیمی، دانشگاه صنعتی امیرکبیر (پلی‌تکنیک تهران)، کدپستی: 4413-15875، تهران، ایران

2 دانشکده مهندسی پلیمر، دانشگاه صنعتی امیرکبیر (پلی‌تکنیک تهران)، کدپستی: 4413-15875، تهران، ایران

3 پژوهشگاه پلیمر و پتروشیمی ایران، کدپستی: 13115-14977، تهران، ایران

چکیده

کشف پلیمریزاسیون اولفین ­ها با کاتالیست ­های فلزهای واسطه در اوایل دهه­ ی1950میلادی توسط زیگلر و ناتا از اهمیت به­ سزایی برخوردار بود و آغازی برای تولید پلی ­اولفین ­های صنعتی بود.این کاتالیست ­ها طی بیش از 60 سال گذشته رشد چشمگیری داشته ­اند و امروزه به ­عنوان کاتالیست­ هایی مؤثر برای انواع پلیمریزاسیون اولفین ­ها استفاده می­ شوند. برای تولید پلی ­پروپیلن­ ایزوتاکتیک از کاتالیست ­های تیتانیوم کلرید بر پایه­ی منیزیم کلرید همراه با الکترون ­دهنده­ درونی، الکترون­ دهنده بیرونی و کمک ­کاتالیست آلومینیوم آلکیل استفاده می­ شود. کشف پایه­ منیزیم کلرید در سال 1968 میلادی و سپس الکترون ­دهنده ­ها در سال 1970 میلادی منجر به بهبود فضاویژگی و فعالیت کاتالیست­ های زیگلر - ناتا شد. به­ دلیل اهمیت کاتالیست­ های زیگلر - ناتا در پلیمریزاسیون پروپیلن، تاریخچه­ کشف نسل­ های گوناگون کاتالیست­ های زیگلر - ناتا، معرفی پایه­ ی کاتالیست، سطوح موجود در پایه­ منیزیم کلرید، نوع­های گوناگون الکترون­دهنده­های درونی و بیرونی و نقش آن­ها در کارایی کاتالیست­های پلیمریزاسیون پروپیلن، روش­ های جذب الکترون ­دهنده­ ها روی پایه و تعادل­ های پیشنهادی بین اجزای کاتالیست در فرایند پلیمریزاسیون بررسی شده است.

کلیدواژه‌ها

موضوعات


[1] Talaei A., Afshar-Taromi F., Arefazar A., Ahmadjo S., Jazani O. M., Teh Influence of Bridge Type on teh Activity of Supported Metallocene Catalysts in Ethylene Polymerization, Chin. J. Polym. Sci., 32(2): 137-142 (2014).

[2] Albizzati E., Galimberti M., Catalysts for Olefins Polymerization, Catal. Today, 41(1): 159-168 (1998).

[3] Pater J., Weickert G., van Swaaij W. P., Polymerization of Liquid Propylene wif a 4th Generation Ziegler-Natta Catalyst-Influence of Temperature, Hydrogen and Monomer Concentration and Prepolymerization Method on Polymerization Kinetics, Chem. Eng. Sci., 57(16): 3461-3477 (2002).

[4] Redzic E., Garoff T., Mardare C. C., List M., Hesser G., Mayrhofer L., Hassel A. W., Paulik C., Heterogeneous Ziegler–Natta Catalysts wif Various sizes of MgCl2 Crystallites: Synthesis and Characterization, Iranian Polymer J., 25(4): 321-337 (2016).

[5] Kissin Y., “Alkene Polymerization Reactions wif Transition Metal Catalysts”, Elsevier Science, Amsterdam, Netherlands (2008).

[6] Correa A., Credendino R., Pater J. T., Morini G., Cavallo L., Theoretical Investigation of Active Sites at teh Corners of MgCl2 Crystallites in Supported Ziegler-Natta Catalysts, Macromol., 45(9): 3695-3701 (2012).

[7] Monji M., Abedi S., Pourmahdian S., Afshar-Taromi F., Effect of Prepolymerization on Propylene Polymerization, J. Appl. Polym. Sci., 112(4):1863-1867 (2009).

[8] Alshaiban A., Soares J. B., Effect of Hydrogen, Electron Donor, and Polymerization Temperature on Poly(propylene) Microstructure, Macromol. Symp., Wiley Online Library, 312: 72-80 (2012).

[9] Gnanakumar E. S., Thushara K., Gowda R. R., Raman S. K., Ajithkumar T., Rajamohanan P., Chakraborty D., Gopinath C. S., MgCl2·6C6H11OH: A High Mileage Porous Support for Ziegler-Natta Catalyst, J. Phys. Chem. C, 116(45): 24115-24122 (2012).

[10] Kumawat J., Kumar Gupta V., Vanka K., Teh Nature of teh Active Site in Ziegler-Natta Olefin Polymerization Catalysis Systems - A Computational Investigation, Eur. J. Inorg. Chem., 2014(29): 5063-5076 (2014).

[11] Ray H. L., “Stereoselective Propylene Polymerization wif Supported Titanium Catalysts”, Wesleyan University, Middletown, Connecticut (2007).

[12] Mitani M., Saito J., Ishii S. me., Nakayama Y., Makio H., Matsukawa N., Matsui S., Mohri J.me., Furuyama R., Terao H., FI Catalysts: New Olefin polymerization Catalysts for teh Creation of Value‐Added Polymers, Chem. Record, 4(3): 137-158 (2004).

[13] Bukatov G. D., Zakharov V. A., Barabanov A. A., Mechanism of Olefin Polymerization on Supported Ziegler-Natta Catalysts Based on Data on teh Number of Active Centers and Propagation Rate Constants, Kinet. Catal., 46 (2): 166-176 (2005).

[14] Mirjahanmardi S. H., Taromi F. A., Zahedi R., Haghighi M. N., Jamjah R., Asl G. J., Effect of Multi-Ethers and Conventional Alkoxysilanes as External Donors on teh 4th Generation Ziegler-Natta Catalysts for Propylene Polymerization. Polymer Science Series B, 58(6): 619-628 (2016).

[15] Zahedi R., Taromi F. A., Mirjahanmardi S. H., Haghighi M. N., Jamjah R., Jadidi K., Comparison of teh Role of New Ethers and Conventional Alkoxysilanes as External Donors in teh Polymerization of Propylene Using teh Industrial Ziegler-Natta Catalyst, Polym. Sci. Series B, 58(2): 143-151 (2016).

[16] Groppo E., Seenivasan K., Barzan C., Teh Potential of Spectroscopic Methods Applied to Heterogeneous Catalysts for Olefin Polymerization, Catal. Sci. Tech., 3(4): 858-878 (2013).

[17] Kashiwa N., Teh Discovery and Progress of MgCl2‐Supported TiCl4 Catalysts, J. Polym. Sci., Part A: Polym. Chem., 42(1):1-8 (2004).

[18] Terao H., Iwashita A., Ishii S., Tanaka H., Yoshida Y., Mitani M., Fujita T., Ethylene/Norbornene Copolymerization Behavior of Bis(phenoxy-imine) Ti Complexes Combined wif MAO, Macromol., 42(13): 4359-4361 (2009).

[19] Nayeri H.H., Afshar-Taromi F., Hemmati M., Rekabdar F., Preparation method of Superactive Ziegler–Natta Catalysts to Produce Ultra-High Molecular Weight Amorphous Poly(1-octene), Poly(1-decene), and Their Copolymers, J. Coord. Chem., 67(19): 3270-3278 (2014).

[20] Marques M.d.F.V., Cardoso R.d.S., da Silva M.G., Preparation of MgCl2-Supported Ziegler-Natta Catalyst Systems wif New Electron Donors, Appl. Catal. A: Gen., 374(1–2): 65-70 (2010).

[21] Soares J. B., Mathematical Modelling of teh Microstructure of Polyolefins Made by Coordination Polymerization: A Review, Chem. Eng. Sci., 56(13): 4131-4153 (2001).

[22] Moballegh L., Hakim S., Morshedian J., Nekoomanesh M., Investigating Effects of Using Mixtures of Two External Electron Donors on Microstructure and Properties of Polypropylene/poly (ethylene‐co‐propylene) In‐Reactor Blends Based on Ziegler–Natta Catalyst, Macromol. React. Eng., 9: 350-359 (2015).

[23] Taniike T., Terano M., Teh Use of Donors to Increase teh Isotacticity of Polypropylene, In: Kaminsky W., (Ed.) “Polyolefins: 50 Years after Ziegler and Natta me”, Springer Berlin Heidelberg, 257: 81-97 (2013).

[24] Suhm J., Heinemann J., Wörner C., Müller P., Stricker F., Kressler J., Okuda J., Mülhaupt R., Novel Polyolefin Materials via Catalysis and Reactive Processing, Macromol. Symp., 129(1): 1-28 (1998).

[25] Chang H., Li H., Zheng T., Zhang L., Yuan W., Li L., Huang H., Hu Y., Characterization of teh Effects of teh C/N Mixed External Donors on teh Stereo-Defects Distribution of Polypropylene by Successive Self-Nucleating and Annealing and 13C-NMR Techniques, J. Polym. Res., 20(8): 1-8 (2013).

[26] Alshaiban A., Soares J. B., Effect of Hydrogen and External Donor on Propylene Polymerization Kinetics wif a 4th‐Generation Ziegler‐Natta Catalyst, Macromol. React. Eng., 6(6‐7): 265-274 (2012).

[27] 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).

[28] Busico V., Cipullo R., Microstructure of Polypropylene, Prog. Polym. Sci., 26(3): 443-533 (2001).

[29] Yu E. Y., Choi B. R., Teh Effects of Prepolymerization on Propylene Polymerization wif Mg(OC2H5)2 Supported Catalyst, J. Ind. Eng. Chem., 2(1): 7-17 (1996).

[30] Andoni A., Chadwick J. C., Niemantsverdriet J. H., Thüne P. C., Investigation of Planar Ziegler-Natta Model Catalysts Using Attenuated Total Reflection Infrared Spectroscopy, Catal. Lett., 130(3-4): 278-285 (2009).

[31] 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 Temperature, Polym. Bull., 67(8): 1519-1527 (2011).

[32] 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).

[33] Jenny C., Maddox P., Supported Polyolefin Catalysts, Curr. Opin. Solid State Mater. Sci., 3(1): 94-103 (1998).

[34] Alshaiban A., “Propylene Polymerization Using 4th Generation Ziegler-Natta Catalysts: Polymerization Kinetics and Polymer Microstructural Investigation”, University of Waterloo, Ontario, Canada (2011).

[35] Ratanasak M., Parasuk V., Understanding teh Roles of Novel Electron Donors in Ziegler–Natta Catalyzed Propylene Polymerization, RSC Advances, 6(114): 112776-112783 (2016).

[36] Furuyama R., Saito J., Ishii S., Makio H., Mitani M., Tanaka H., Fujita T., Fluorinated Bis (phenoxy–imine) Ti Complexes wif MAO: Remarkable Catalysts for Living Ethylene and Syndioselective Living Propylene Polymerization, J. Organomet. Chem., 690(20): 4398-4413 (2005).

[37] 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).

[38] Corradini P., Guerra G., Cavallo L., Do New Century Catalysts Unravel teh Mechanism of Stereocontrol of Old Ziegler-Natta Catalysts?, Acc. Chem. Res., 37(4): 231-241 (2004).

[39] Ribour D., Spitz R., Monteil V., Modifications of teh Active Sites Distribution in teh Ziegler‐Natta Polymerization of Propylene Using Lewis Acids, J. Polym. Sci., Part A: Polym. Chem., 48(12): 2631-2635 (2010).

[40] Wang Y., Zuo M., Li Y., Theoretical Investigation of teh Mechanism of Ethylene Polymerization wif Salicylaldiminato Vanadium (III) Complexes, Chin. J. Catal., 36(4): 657-666 (2015).

[41] 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).

[42] Claverie J. P., Schaper F., Ziegler-Natta Catalysis: 50 Years After teh Nobel Prize, MRS Bull., 38(03): 213-218 (2013).

[43] Fujisawa K., Nabika M., Development of New Polymerization Catalysts wif Manganese (II) Complexes, Coord. Chem. Rev., 257(1): 119-129 (2013).

[44] Collins R. A., Russell A. F., Mountford P., Group 4 Metal Complexes for Homogeneous Olefin Polymerisation: A Short Tutorial Review, Appl. Petrochem. Res., 1-19 (2015).

[45] Gupta V., Ravindranathan M., Studies on Magnesium Dichloride-2,2-Dimethoxypropane-Titanium Tetrachloride Catalyst System for Propylene Polymerization, Polym., 37(8): 1399-1403 (1996).

[46] 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 wif Typical Lewis Bases Used in Heterogeneous Ziegler–Natta Catalysis, Phys. Chem. Chem. Phys., 19(39): 26996-27006 (2017).

[47] Dil E. J., Pourmahdian S., Vatankhah M., Afshar-Taromi, F., Effect of Dealcoholation of Support in MgCl2-Supported Ziegler–Natta Catalysts on Catalyst Activity and Polypropylene Powder Morphology, Polym. Bull., 64 (5): 445-457 (2010).

[48] Korányi T. me., Magni E., Somorjai G. A., Surface Science Approach to teh Preparation and Characterization of Model Ziegler–Natta Heterogeneous Polymerization Catalysts, Top. Catal., 7(1-4): 179-185 (1999).

[49] 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 teh Molecular Level Properties of Ziegler-Natta Catalyst Support wif and Wifout teh Internal Electron Donor, J. Phys. Chem. C, 115(5): 1952-1960 (2010).

[50] 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 teh Preparation of TiClx/MgCl2 Catalyst for Olefin Polymerization, Dalton Trans., 41(37): 11311-11318 (2012).

[51] Zhang L., Fu Z., Fan Z., A New Method of Active Center Determination for Olefin Polymerization wif Supported Ziegler-Natta Catalysts, Macromol. Res., 18(7): 695-700 (2010).

[52] Song B. G., Ihm S. -K., Teh Role of Two Different Internal Donors (phthalate and 1,3-diether) on teh Formation of Surface Structure in MgCl2-Supported Ziegler-Natta Catalysts and Their Catalytic Performance of Propylene Polymerization, J. Appl. Polym. Sci., 131(15): 40536-40542 (2014).

[53] Li H., Wang J., He L., Nan F., Wang F., Yang W., Zhang M., Sun T., Huang Q., Yi J., Study on Hydrogen Sensitivity of Ziegler–Natta Catalysts wif Novel Cycloalkoxy Silane Compounds as External Electron Donor, Polymers, 8(12): 433 (2016).

[54] Albizzat E., Polyolefins In: Beccari M., Romano, U., (Eds.) “Encyclopaediaof Hydrocarbons: RefiningandPetrochemicals”, Istituto della Enciclopedia Italiana, 2, 759-788 (2006).

[55] Lutz, M., “Structure/property Relationships of Commercial Propylene/1-pentene Random Copolymers”, University of Stellenbosch, South Africa (2006).

[56] Sita L. R., From Heterogeneous Ziegler-Natta to Homogeneous Single-Center Group 4 Organometallic Catalysts: A Primer on teh Coordination Polymerization of Olefins, In: Schluter A. D., Hawker C. J., Sakamoto J., (Eds.), “Synthesis of Polymers: New Structures and Methods”, 1th Edition, Wiley-VCH Verlag GmbH & Co. KGaA, 25-66 (2012).

[57] Cerruti L., Historical and Philosophical Remarks on Ziegler-Natta Catalysts, Int. J. Philos. Chem., 5(1): 3-41 (1999).

[58] Alshaiban A., “Active Site Identification and Mathematical Modeling of Polypropylene Made wif Ziegler Natta Catalyst”, University of Waterloo, Ontario, Canada (2008).

[59] Mülhaupt R., Catalytic Polymerization and Post Polymerization Catalysis Fifty Years After teh Discovery of Ziegler's Catalysts, Macromol. Chem. Phys., 204(2): 289-327 (2003).

[60]  Malpass D. B., Band E. me., Propylene Polymerization Catalysts, In” Introduction to Industrial Polypropylene: Properties, Catalysts Processes”,1th Edition, Wiley-Scrivener, 75-109 (2012).

[61] Soga K., Shiono T., Ziegler-Natta Catalysts for Olefin Polymerizations, Prog. Polym. Sci., 22(7): 1503-1546 (1997).

[62] Jiang T., Chen W., Zhao F., Liu Y., Wang R., Du H., Zhang T., Preparation of Porous Spherical MgCl2/SiO2 Complex Support as Precursor for Catalytic Propylene Polymerization, J. Appl. Polym. Sci., 98(3): 1296-1299 (2005).

[63] Bukatov G., Sergeev S., Zakharov V., Potapov A., Supported Titanium-Magnesium Catalysts for Propylene Polymerization, Kinet. Catal., 49(6): 782-790 (2008).

[64] Zakirov M., Kleiner V., Adrov O., Nifant’ev me., Shklyaruk B., Stroganov V., Nedorezova P., Klyamkina A., Effect of Electron Donors on Polymerization of Propylene in teh Presence of Titanium-Magnesium Catalysts, Polym. Sci. Ser. B, 52(9-10): 584-588 (2010).

[65] Tangjituabun K., Kim S. Y., Hiraoka Y., Taniike T., Terano M., Jongsomjit B., Praserthdam P., Poisoning of Active Sites on Ziegler-Natta Catalyst for Propylene Polymerization, Chin. J. Polym. Sci., 26(5): 547-552 (2008).

[66] Panchenko V. N., Vorontsova L. V., Zakharov V. A., Ziegler-Natta Catalysts for Propylene Polymerization–Interaction of an External Donor wif teh Catalyst, Polyolefins J., 4(1): 87-97 (2016).

[67] Chadwick J. C., Morini G., Balbontin G., Mingozzi me., Albizzati E., Sudmeijer O., Propene Polymerization wif MgCl2‐Supported Catalysts: Effects of Using a Diether as External Donor, Macromol. Chem. Phys., 198(4): 1181-1188 (1997).

[68] Park H. M., Lee W. Y., Teh Effect of Triethylaluminium Treatment on a Ziegler-Natta Catalyst Supported on Magnesium Chloride Prepared by a Recrystallization Method, for Propylene Polymerization, Eur. Polym. J., 28 (11): 1417-1422 (1992).

[69] Andoni A., Chadwick J. C., Niemantsverdriet H., Thune P. C., A Flat Model Approach to Ziegler-Natta Catalysts for Propylene Polymerization and a Preparation Method of Well-defined Crystallites of MgCl2-supported Catalysts, Macromol. Symp., 260(1): 140-146 (2007).

[70] Tao L., Weili L., Xianzhi X., Bingquan M., Study of a Novel Fourth-Generation Supported Ziegler-Natta Catalyst for Propylene Polymerization: Relationship between Catalyst Structure and Polymerization Properties, China Petroleum Processing & Petrochem. Tech., 17(1): 39-47 (2015).

[71] Galli P., Vecellio G., Polyolefins: Teh Most promising Large‐Volume Materials for teh 21st Century, J. Polym. Sci., Part A: Polym. Chem., 42(3): 396-415 (2004).

[72] Chang H., Li H., Zheng T., Zhou Q., Zhang L., Hu Y., Teh Effects of New Aminosilane Compounds as External donors on Propylene Polymerization, J. Polym. Res., 21(9): 1-11 (2014).

[73] Guo J., Hu G., Chen Z., Synthesis of Novel Electron Donors and Their Application to Propylene Polymerization, Trans. Tianjin Univ., 18: 8-14 (2012).

[74] Junting X., Linxian F., Senhui W., Shilin Y., Supported Catalyst Wifout External Electron Donor for Propylene Polymerization II. Tacticity Distribution and Microstructure of Polypropylene, Chin. J. Polym. Sci., 16(1): 56-61 (1998).

[75] Potapov A. G., Politanskaya L. V., Teh Study of teh Adsorption of 1,3-diethers on teh MgCl2 Surface, J. Mol. Catal. A: Chem., 368–369: 159-162 (2013).

[76] Cavallo L., Del PieroS., 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).

[77] Wang N., Qin Y., Huang Y., Niu H., Dong J. -Y., Wang Y., Functionalized Multi-Walled Carbon Nanotubes wif Stereospecific Ziegler-Natta Catalyst Species: Towards Facile in Situ Preparation of Polypropylene Nanocomposites, App. Catal. A: Gen., 435: 107-114 (2012).

[78] 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).

[79] John C. C., Ziegler-Natta Catalysis, In: Lee S., (Ed.), “Encyclopedia of Chemical Processing”, Taylor & Francis, Vol. 5, 3247-3259 (2006).

[80] Barino L., Scordamaglia R., Modeling of isospecific Ti sites in MgCl2 supported heterogeneous Ziegler‐Natta Catalysts, Macromol. Theory Simul., 7(4): 407-419 (1998).

[81] Chadwick J. C., Morini G., Balbontin G., Camurati me., Heere J. J., Mingozzi me., Testoni F., Effects of Internal and External Donors on teh Regio‐and Stereoselectivity of Active Species in MgCl2‐Supported Catalysts for Propene Polymerization, Macromol. Chem. Phys., 202(10): 1995-2002 (2001).

[82] Bi F., He A., Li H., Hu Y., He Z., Han C. C., Copolymerization of Propylene wif 1‐octene Catalyzed by MgCl2/TiCl4/Diether Catalyst, Poly. Int., 60(8): 1167-1172 (2011).

[83] Albizzati E., Cecchin G., Chadwick J. C., Collina G., Giannini U., Morini G., Noristi L., Catalysts for Polymerization, In: Pasquini N., (Ed.), “Polypropylene Handbook”, 2nd Edition, Hanser Gardner (2005).

[84] Andoni A., “A Flat Model Approach to Ziegler-Natta Olefin Polymerization Catalysts”, Eindhoven University of Technology, Netherlands (2009).

[85] 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).

[86] Hu J., Han B., Shen X. -R., Fu Z. -S., Probing teh Roles of Diethylaluminum Chloride in Propylene Polymerization wif MgCl2-Supported Ziegler-Natta Catalysts, Chin. J. Polym. Sci., 31(4): 583-590 (2013).

[87] Taniike T., Wada T., Kouzai me., Takahashi S., Terano M., Role of Dispersion State of Ti Species in Deactivation of MgCl2-Supported Ziegler-Natta Catalysts, Macromol. Res., 18(9): 839-844 (2010).

[88] Yang H., Zhang L., Zang D., Fu Z., Fan Z., Effects of Alkylaluminum as Cocatalyst on teh Active Center Distribution of 1-Hexene Polymerization wif MgCl2-Supported Ziegler–Natta Catalysts, Catal. Commun., 62: 104-106 (2015).

[89] Mukhopadhyay S., Kulkarni S. A., Bhaduri S., Density Functional Study on teh Role of Electron Donors in Propylene Polymerization Using Ziegler-Natta Catalyst, J. Organomet. Chem., 690(5): 1356-1365 (2005).

[90] Ye Z.Y., Wang L., Feng L.F., Gu X.P., Chen H.H., Zhang P.Y., Pan J., Jiang S., Feng L.X., Novel Spherical Ziegler–Natta Catalyst for Polymerization and Copolymerization. me. Spherical MgCl2 Support, J. Polym. Sci., Part A: Polym. Chem., 40(18): 3112-3119 (2002).

[91] Stukalov D. V., Zakharov V. A., Active Site Formation in MgCl2-Supported Ziegler-Natta Catalysts. A Density Functional Theory Study, J. Phys. Chem. C, 113(51): 21376-21382 (2009).

[92] Bahri‐Laleh N., Arabi H., Mehdipor‐Ataei S., Nekoomanesh‐Haghighi M., Zohuri G., Seifali M., Akbari Z., Activation of Ziegler‐Natta Catalysts by Organohalide Promoters: A Combined Experimental and Density Functional Theory Study, J. Appl. Polym. Sci. 123(4): 2526-2533 (2012).

[93] Pokasermsong P., Praserthdam P., Comparison of Activity of Ziegler-Natta Catalysts Prepared by Recrystallization and Chemical Reaction Methods Towards Polymerization of Ethylene, Eng. J., 13(1): 57-64 (2009).

[94] 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).

[95] Suba P., Árva P., Németh S., Teh Effect of a Ziegler-Natta Catalyst and teh Polymerization Parameters on teh Basic Properties of Polyethylene, Hung. J. Ind. Chem., 35(1): 31-37 (2007).

[96] Hoff R. E., Mathers R. T., “Handbook of Transition Metal Polymerization Catalysts”, Wiley, Hoboken, New Jersey, United States (2010).

[97] Credendino R, Liguori D., Morini G., Cavallo L., Investigating Phthalate and 1,3-Diether Coverage and Dynamics on teh (104) and (110) Surfaces of MgCl2-Supported Ziegler–Natta Catalysts, J. Phys. Chem. C, 118 (15): 8050-8058 (2014).

[98] Vanka K., Singh G., Iyer D., Gupta V. K., DFT Study of Lewis Base Interactions wif teh MgCl2 Surface in teh Ziegler-Natta Catalytic System: Expanding teh Role of teh Donors, J. Phys. Chem. C, 114(37): 15771-15781 (2010).

[99] Monaco G., Toto M., Guerra G., Corradini P., Cavallo L., Geometry and Stability of Titanium Chloride Species Adsorbed on teh (100) and (110) Cuts of teh MgCl2 Support of teh Heterogeneous Ziegler-Natta Catalysts, Macromol., 33(24): 8953-8962 (2000).

[100] Singh G., Kaur S., Makwana U., Patankar R. B., Gupta V. K., Influence of Internal Donors on teh Performance and Structure of MgCl2 Supported Titanium Catalysts for Propylene Polymerization, Macromol. Chem. Phys., 210 (1): 69-76 (2009).

[101] 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).

[102] 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).

[103] 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).

[104] Bazhenov A., Linnolahti M., Karttunen A. J., Pakkanen T. A., Denifl P., Leinonen T., Modeling of Substitutional Defects in Magnesium Dichloride Polymerization Catalyst Support, J. Phys. Chem. C, 116(14): 7957-7961 (2012).

[105] Bazhenov A., Linnolahti M., Pakkanen T. A., Denifl P., Leinonen T., Modeling teh Stabilization of Surface Defects by Donors in Ziegler-Natta Catalyst Support, J. Phys. Chem. C, 118(9): 4791-4796 (2014).

[106] Batt-Coutrot D., Wolf V., Malinge J., Saudemont T., Grison C., Coutrot P., Study of Dimethoxysilacycloalkanes as External Donors in Ziegler-Natta Stereospecific Propylene Polymerisation, Polym. Bull., 54(6): 377-385 (2005).

[107] Busico V., Causà M., Cipullo R., Credendino R., Cutillo F., Friederichs N., Lamanna R., Segre A., Van Axel Castelli V., Periodic DFT and High-Resolution Magic-Angle-Spinning (HR-MAS) 1H NMR Investigation of teh Active Surfaces of MgCl2-Supported Ziegler-Natta Catalysts. Teh MgCl2 Matrix, J. Phys. Chem. C, 112(4): 1081-1089 (2008).

[108] D’Amore M., Credendino R., Budzelaar P. H., Causá M., Busico V., A periodic hybrid DFT approach (including dispersion) to MgCl2-supported Ziegler-Natta catalysts-1: TiCl4 adsorption on MgCl2 crystal surfaces, J. Catal., 286: 103-110 (2012).

[109] Boero M., Parrinello M., Weiss H., Hüffer S., A First Principles Exploration of a Variety of Active Surfaces and Catalytic Sites in Ziegler-Natta Heterogeneous Catalysis, J. Phys. Chem. A, 105(21): 5096-5105 (2001).

[110] Stukalov D. V., Zakharov V. A., Zilberberg me. L., Adsorption Species of Ethyl Benzoate in MgCl2-Supported Ziegler-Natta Catalysts. A Density Functional Theory Study, J. Phys. Chem. C, 114(1): 429-435 (2009).

[111] Stukalov D. V., Zilberberg me. L., Zakharov V. A., Surface Species of Titanium (IV) and Titanium (III) in MgCl2-Supported Ziegler-Natta Catalysts. A Periodic Density Functional Theory Study, Macromol., 42(21): 8165-8171 (2009).

[112] Credendino R., Pater J. T., Liguori D., Morini G., Cavallo L., Investigating Alkoxysilane Coverage and Dynamics on teh (104) and (110) Surfaces of MgCl2-Supported Ziegler–Natta Catalysts, J. Phys. Chem. C, 116 (43): 22980-22986 (2012).

[113] Ratanasak M., Rungrotmongkol T., Saengsawang O., Hannongbua S., Parasuk V., Towards teh Design of New Electron Donors for Ziegler-Natta Catalyzed Propylene Polymerization Using QSPR Modeling, Polym., 56: 340-345 (2015).

[114] Correa A., Piemontesi F., Morini G., Cavallo L., Key Elements in teh Structure and Function Relationship of teh MgCl2/TiCl4/Lewis Base Ziegler-Natta Catalytic System, Macromol., 40(25): 9181-9189 (2007).

[115] Karol F. J., Studies wif High Activity Catalysts for Olefin Polymerization, Catal. Rev. Sci. Eng., 26(3-4): 557-595 (1984).

[116] Puhakka E., Pakkanen T. T., Pakkanen T. A., Theoretical Investigations on Heterogeneous Ziegler-Natta Catalyst Supports: Stability of teh Electron Donors at Different Coordination Sites of MgCl2, J. Phys. Chem. A, 101(34): 6063-6068 (1997).

[117] Taniike T., Terano M., Coadsorption Model for First-Principle Description of Roles of Donors in Heterogeneous Ziegler-Natta Propylene Polymerization, J. Catal., 293: 39-50 (2012).

[118] 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).

[119] Gale J. D., Catlow C. R. A., Gillan M. J., A Density Functional Study of Ti/MgCl2-Supported Ziegler-Natta Catalysts, Top. Catal., 9(3-4): 235-250 (1999).

[120] Makwana U. C., Singala K. J., Patankar R. B., Singh S. C., Gupta V. K., Propylene Polymerization Using Supported Ziegler-Natta Catalyst Systems wif Mixed Donors, J. Appl. Polym. Sci., 125(2): 896-901 (2012).

[121] Singh G., Kumar N., Kaur S., Bantu B., Kapur G. S., Ziegler-Natta Catalyst Synthesis and Process theirof: Google Patents, EP 3 162 819 A1 (2016).

[122] 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).

[123] Stukalov D.V., Zakharov V.A., Potapov A.G., Bukatov G.D., Supported Ziegler-Natta Catalysts for Propylene Polymerization. Study of Surface Species Formed at Interaction of Electron Donors and TiCl4 wif Activated MgCl2, J. Catal., 266(1): 39-49 (2009).

[124] Kumawat J., Gupta V. K., Vanka K., Donor Decomposition by Lewis Acids in Ziegler-Natta Catalyst Systems: A Computational Investigation, Organome., 33(17): 4357-4367 (2014).

[125] Lyubimtsev A., Nifant’ev me., Stereo-and Enantioselective Polymerization of Hexa-1,5-diene on Heterogeneous Ziegler-Natta Catalysts Obtained wif teh use of Optically Active Internal Donors, Russ. Chem. Bull., 58(8): 1672-1680 (2009).

[126] 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).

[127] Lee J. W., Jo W. H., Chemical Structure-Stereospecificity Relationship of Internal Ddonor in Heterogeneous Ziegler-Natta Catalyst for Propylene Polymerization by DFT and MM Calculations, J. Organomet. Chem., 694(19): 3076-3083 (2009).

[128] Balogh me., Examination of teh Effects of Different Internal Electron Donors of Ziegler-Natta Catalysts on Propylene Polymerization, Development, 98-104 (2011).

[129] Paukkeri R., Iiskola E., Lehtinen A., Salminen H., Microstructural analysis of polypropylenes polymerized wif Ziegler-Natta Catalysts wifout External Donors, Polym., 35(12): 2636-2643 (1994).

[130] Coutinho F., Santa Maria L., Influence of Internal and External Electron-Donors on teh Activity and Stereospecificity of Ziegler-Natta Catalysts, Eur. Polym. J., 27(9): 987-989 (1991).

[131]Tanase S., Katayama K., Yabunouchi N., Sadashima T., Tomotsu N., Ishihara N., Design of Novel Malonates as Internal Donors for MgCl2-Supported TiCl4 Type Polypropylene Catalysts and Their Mechanistic Aspects, Part 1, J. Mol. Catal., A: Chem., 273(1): 211-217 (2007).

[132] Basson N., “Teh Effect of Molecular Architecture on teh Properties of Propylene Impact Copolymers”, University of Stellenbosch, South Africa (2010).

[133] Zakharov V., Bukatov G., Barabanov A., Recent Data on teh Number of Active Centers and Propagation Rate Constants in Olefin Polymerization wif Supported ZN Catalysts, Macromol. Symp., Wiley Online Library, 213: 19-28 (2004).

[134] Song B. G., Choi Y. H., Ihm S. -K., Characteristics of Diether- and Phthalate-Based Ziegler-Natta Catalysts for Copolymerization of Propylene and Ethylene and Terpolymerization of Propylene, Ethylene, and 1-Butene, J. Appl. Polym. Sci., 130(2): 851-859 (2013).

[135] Andoni A., Chadwick J. C., Niemantsverdriet H. J., Thüne P. C., Teh 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).

[136] Wen X., Ji M., Yi Q., Niu H., Dong J. Y., Magnesium Chloride Supported Ziegler‐Natta Catalysts Containing Succinate Internal Electron Donors for teh Polymerization of Propylene, J. Appl. Polym. Sci., 118(3): 1853-1858 (2010).

[137] Gao M., Liu H., Wang J., Li C., Ma J., Wei G., Novel MgCl2-Supported Catalyst Containing Diol Dibenzoate Donor for Propylene Polymerization, Polym., 45(7): 2175-2180 (2004).

[138] Kudinova O., Kron T., Ladygina T., Kozhevnikov A., Petrov E., Novokshonova L., Polydentate Phosphine Oxides as External Electron Donors for Titanium-Magnesium Catalysts for Propylene Polymerization, Kinet. Catal., 51(2): 229-234 (2010).

[139] Zhou Q., Wang A., Li H., Luo Z., Zheng T., Zhang L., Hu Y., Microstructure of Polypropylene and Active Center in Ziegler–Natta Catalyst: Effect of Novel Salicylate Internal donor, RSC Advances, 6(79): 75023-75031 (2016).

[140] Dang X., Li Q., Li H., Yang Y., Zhang L., Hu Y., Ziegler-Natta Catalysts wif Novel Internal Electron Donors for Propylene Polymerization, J. Polym. Res., 21(12): 1-8 (2014).

[141] Wondimagegn T., Ziegler T., Teh Role of External Alkoxysilane Donors on Stereoselectivity and Molecular Weight in MgCl2-Supported Ziegler-Natta Propylene Polymerization: A Density Functional Theory Study, J. Phys. Chem. C, 116(1): 1027-1033 (2011).

[142] 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).

[143] 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).

[144] Toto M., Morini G., Guerra G., Corradini P., Cavallo L., Influence of 1,3-Diethers on teh Stereospecificity of Propene Polymerization by Supported Ziegler-Natta Catalysts. A Theoretical Investigation on their Adsorption on (110) and (100) Lateral Cuts of MgCl2 Platelets, Macromol., 33(4): 1134-1140 (2000).

[145] Zhang H. -X., Shin Y. -J., Lee D. -H., Yoon K. -B., Preparation of Ultra High Molecular Weight Polyethylene wif MgCl2/TiCl4 Catalyst: Effect of Internal and External Donor on Molecular Weight and Molecular Weight Distribution, Polym. Bull., 66(5): 627-635 (2011).

[146] 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).

[147] Wang Q., Murayama N., Liu B., Terano M., Effects of Electron Donors on Active Sites Distribution of MgCl2‐Supported Ziegler‐Natta Catalysts Investigated by Multiple Active Sites Model, Macromol. Chem. Phys., 206(9): 961-966 (2005).

[148] Frolov me., Kleiner V., Krentsel B., Mardanov R., Munshi K., Bukatov G., Zakharov V., Sergeev S., Effect of teh External Donors on teh Polymerization of 4‐methyl‐1‐pentene wif High Activity MgCl2/TiCl4 Catalytic System, Die Makromol. Chem., 194(8): 2309-2321 (1993).

[149] Da Silva Filho A. A., Alves M., do Carmo M., dos Santos J. H. Z., XPS and EXAFS Characterization of Ziegler-Natta Catalyst Systems, J. Appl. Polym. Sci., 109(3): 1675-1683 (2008).

[150] Ma Z., Wang L., Wang W., Feng L., Gu X., Study of Propylene Polymerization Catalyzed by a Spherical MgCl2‐Supported Ziegler-Natta Catalyst System: Teh Effects of External Donors, J. Appl. Polym. Sci., 95(3): 738-742 (2005).

[151] Vestberg T., Denifl P., Parkinson M., WilÉN C. E., Effects of External Donors and Hydrogen Concentration on Oligomer Formation and Chain end Distribution in Propylene Polymerization wif Ziegler‐Natta Catalysts, J. Polym. Sci., Part A: Polym. Chem., 48(2): 351-358 (2010).

[152] Kang K. K., Shiono T., Jeong Y. T., Lee D. H., Polymerization of Propylene by Using Mg(OEt)2-DNBP-TiCl4 Catalyst wif Alkoxy Disilanes as External Donor, J. Appl. Polym. Sci., 71(2): 293-301 (1999).

[153] Sacchi M. C., Fan Z. Q., Forlini F., Tritto me., Locatelli P., Use of Different Alkoxysilanes as External Donors in MgCl2‐Supported Ziegler‐Natta Catalysts to Obtain Propene/1‐Butene Copolymers wif Different Microstructure, Macromol. Chem. Phys., 195(8): 2805-2816 (1994).

[154] Soga K., Shiono T., Influence of Internal and External Donors on Activity and Stereospecificity of Ziegler‐Natta Catalysts, Die Makromol. Chem., 189(7): 1531-1541 (1988).

[155] Shen X. -R., Fu Z. -S., Hu J., Wang Q., Fan Z. -Q., Mechanism of Propylene Polymerization wif MgCl2-Supported Ziegler-Natta Catalysts Based on Counting of Active Centers: Teh Role of External Electron Donor, J. Phys. Chem. C, 117(29): 15174-15182 (2013).

[156] Härkönen M., Seppälä J. V., External Silane Donors in Ziegler‐Natta Catalysis. An Approach to teh Optimum Structure of teh Donor, Die Makromol. Chem., 192(12): 2857-2863 (1991).

[157] Kemp R. A., Brown D. S., Lattman M., Li J., Calixarenes as a New class of External Electron Donors in Ziegler-Natta Polypropylene Catalysts, J. Mol. Catal. A: Chem., 149(1): 125-133 (1999).

[158] زاهدی، ر.؛ افشار طارمی، ف.؛ جم جاه، ر.؛ تأثیر الکترون دهنده­ های بیرونی نوین اتری و سیلانی رایج بر کاتالیست ­های نسل چهارم زیگلر ـ ناتا برای پلیمریزاسیون پروپیلن، نشریه شیمی و مهندسی شیمی ایران، (3)36: 21 تا 39 (1396).

[159] Chen B., Zhang Q. -F., Zhao L. -P., Zhang X. -Q., Zhang H. -X., Preparation and Properties of Isotactic Polypropylene Obtained From MgCl2-Supported TiCl4 Catalyst Bearing Bifunctional Internal Donor, Polym. Bull., 70(10): 2793-2800 (2013).

[160] Turunen A., Linnolahti M., Karttunen V. A., Pakkanen T. A., Denifl P., Leinonen T., Microstructure Control of Magnesium Dichloride Crystallites by Electron Donors: Teh Effect of Methanol, J. Mol. Catal. A: Chem., 334(1): 103-107 (2011).

[161] Hasan A. K., Liu B., Terano M., Effects of Various Preparation and Polymerization Procedures on teh Isospecific Nature of TiCl3-Based Polypropylene Catalysts, Polym. Bull., 54(4-5): 225-236 (2005).

[162] Taniike T., Terano M., A Density Functional Study on teh Influence of teh Molecular Flexibility of Donors on teh Insertion Barrier and Stereoselectivity of Ziegler‐Natta Propylene Polymerization, Macromol. Chem. Phys., 210(24): 2188-2193 (2009).

[163] Lu L., Niu H., Dong J. Y., Propylene Polymerization over MgCl2‐Supported TiCl4 Catalysts Bbearing Different Amounts of a Diether Internal Electron Donor: Extrapolation to teh Role of Internal Electron Donor on Active Site, J. Appl. Polym. Sci., 124(2): 1265-1270 (2012).

[164] Alshaiban A., Soares J. B., Mathematical Modeling of teh Microstructure of Poly(propylene) Made wif Ziegler‐Natta Catalysts in teh Presence of Electron Donors, Macromol. React. Eng., 5(2): 96-116 (2011).

[165] Chumachenko N.; Zakharov V.; Bukatov G.; Sergeev S., A Study of teh Formation Process of Titanium-Magnesium Catalyst for Propylene Polymerization, Applied Catalysis A: General, 469: 512-516 (2014).

[166] Galvan M., Pantaleoni R., Fusco O., Gaddi B., Neumann A., Mazzucco A., Collina G., Sartori, G., Process for teh Preparation of High Purity Propylene Polymers, Google Patents, WO2013/041470 (2013).

[167] Chung J. S., Choi J. H., Song me. K., Lee W. Y., Effect of Ethanol Treatment in teh Preparation of MgCl2 Support for teh Ppropylene Polymerization Catalyst, Macromol., 28(5): 1717-1718 (1995).

[168] Cheng R. -H., Luo J., Liu Z., Sun J. -W., Huang W. -H., Zhang M. -G., Yi J. -J., Adsorption of TiCl4 and Electron Donor on Defective MgCl2 Surfaces and Propylene Polymerization over Ziegler-Natta Catalyst: A DFT Study, Chin. J. Polym. Sci., 31(4): 591-600 (2013).

[169] Choi J. H., Chung J. S., Shin H. W., Song me. K., Lee W. Y., Teh Effect of Alcohol Treatment in teh Preparation of MgCl2 Support by a Recrystallization Method on teh Catalytic Activity and Isotactic Index for Propylene Polymerization, Eur. Polym. J., 32(4): 405-410 (1996).

[170] Kim me., Choi H. K., Kim J. H., Woo S. me., Kinetics Study of Slurry‐Phase Propylene Polymerization wif Highly Active Mg(OEt)2/Benzoyl Chloride/TiCl4 Catalyst, J. Appl. Polym. Sci., 52(12): 1739-1750 (1994).

[171] Jeong Y. T., Lee D. H., Propene Polymerization wif Mg(OEt)2‐Supported TiCl4 Catalyst, 1. Catalyst Composition and Behavior, Die Makromol. Chem., 191(7): 1487-1496 (1990).

[172] Lee D. H., Jeong Y. T., Soga K., In Situ Formation of Magnesium Chloride Support and Internal Donor During Preparation of Propylene Polymerization Catalysts, Ind. Eng. Chem. Res., 31(12): 2642-2647 (1992).

[173] Credendino R., Pater J. T., Correa A., Morini G., Cavallo L., Thermodynamics of Formation of Uncovered and Dimethyl Ether-Covered MgCl2 Crystallites. Consequences in teh Structure of Ziegler-Natta Heterogeneous Catalysts, J. Phys. Chem. C, 115(27): 13322-13328 (2011).

[174] Forte M. C., Coutinho F., Highly Active Magnesium Chloride Supported Ziegler-Natta Catalysts wif Controlled Morphology, Eur. Polym. J., 32(2): 223-231 (1996).

[175] Sacchi M. C., Forlini F., Tritto me., Locatelli P., Morini G., Noristi L., Albizzati E., Polymerization Stereochemistry wif Ziegler-Natta Catalysts Containing Dialkylpropane Diethers: A Tool for Understanding Internal/External Donor Relationships, Macromol., 29(10): 3341-3345 (1996).

[176] Tangjituabun K., Jongsomjit B., Praserthdam P., Teh role of CaO in teh Ziegler-Natta catalyst for propylene polymerization, Catal. Lett., 109(3): 147-152 (2006).

[177] Mori H., Hasebe K., Terano M., XPS Study of teh Interaction of Titanium Species wif Internal Electron Donors on MgCl2-Supported Ziegler Catalysts, J. Mol. Catal. A: Chem., 140(2): 165-172 (1999).

[178] Matsuoka H., Liu B., Nakatani H., Nishiyama me., Terano M., Active Sites Deterioration of MgCl2‐Supported Catalyst Induced by teh Electron Donor Extraction by Alkylaluminium, Polym. Int., 51(9): 781-784 (2002).

[179] Ahmadjo S., Jamjah R., Zohuri G. H., Damavandi S., Nekoomanesh Haghighi M., Javaheri M., Preparation of Highly Active Heterogeneous Ziegler-Natta Catalyst for Polymerization of Ethylene, Iran. Polym. J., 16(1): 31-37 (2007).

[180] Monji M., Pourmahdian S., Vatankhah M., Afshar-Taromi F., Synthesis of Highly Improved Ziegler‐Natta Catalyst, J. Appl. Polym. Sci., 112(6): 3663-3668 (2009).

[181] Kang K.S., Ok M.A., Ihm S.K., TEMPEffect of Internal Lewis Bases on Recrystallized MgCl2-TiCl4 Catalysts for Polypropylene, J. Appl. Polym. Sci., 40(7‐8): 1303-1311 (1990).

[182] Kissin Y. V., Liu X., Pollick D. J., Brungard N. L., Chang M., Ziegler-Natta Catalysts for Propylene Polymerization: Chemistry of Reactions Leading to teh Formation of Active Centers, J. Mol. Catal. A: Chem., 287(1): 45-52 (2008).

[183] Hadian N., Hakim S., Nekoomanesh-Haghighi M., Storage Time TEMPEffect on Dynamic Structure of MgCl2.nEtOH Adducts in Heterogeneous Ziegler-Natta Catalysts, Polyolefins J., 1(1): 33-41 (2014).

[184] Pater J., Weickert G., Swaaij W. P. V., Polymerization of Liquid Propylene wif a Fourth‐Generation Ziegler-Natta Catalyst: Influence of Temperature, Hydrogen, Monomer Concentration, and Prepolymerization Method on Powder Morphology, J. Appl. Polym. Sci., 87(9): 1421-1435 (2003).