Effects of Ti/Mg molar ratio on bi-supported SiO2/MgCl2 (ethoxide type)/TiCl4 catalysts in ethylene homopolymerization and ethylene/1-hexene copolymerization
SiO2/MgCl2 (ethoxide type)/TiCl4 Ziegler-Natta catalysts for use in ethylene polymerization and ethylene/1-hexene copolymerization have been prepared using silica with a supported layer of magnesium ethoxide (Mg(OEt)2) as a catalyst precursor, followed by treating with TiCl4 at different Ti/Mg molar ratios, which showed significant effects on the active centers and pore structures of the catalysts. The formation amount of β-MgCl2 carrier increased to a maximum with increasing the Ti/Mg molar ratio from 1.50 to 2.25, and then decreased with the further increasing of Ti/Mg molar to 2.50. When the Ti/Mg molar ratio reached 2.25, the catalyst showed the best performance of polymerization, which could be attributed to the most active centers, high surface area and loose surface structure, mainly owing to the high conversion of Mg(OEt)2 to β-MgCl2. The polymers obtained showed medium and high molecular weight (Mw) with medium molecular weight distribution (MWD). In contrast to the conventional Mg(OEt)2-based ZN catalysts, the sphericity of particles was easy to control in this bi-supported catalyst. Furthermore, the prepared catalysts exhibited rather high activity, good copolymerization ability and hydrogen response.
Claverie JP, Schaper F (2013) Ziegler-Natta catalysis: 50 years after the Nobel Prize. MRS bull 38: 213-218
Kashiwa N, Tokuzumi T, Fujimura H (1973) Process for the polymerization and/or copolymerization of olefins with the use of Ziegler-type catalysts supported on carrier. US Patent 3,759,884
Mayr A, Galli P, Susa E, Drusco GD, Giachetti E (1972) Polymerizaton of olefins. GB Patent 1,286,867
Kashiwa N (2004) The discovery and progress of MgCl2-supported TiCl4 catalysts. J Polym Sci Pol Chem 42: 1–8
Kioka M, Kashiwa N (1993) Role of electron donor in propylene polymerization using magnesium chloride-supported titanium tetrachloride catalyst. J Mol Catal 82: 11-16
Kashiwa N, Yoshitake J (1983) Propylene polymerization with a high activity catalyst system: MgCl2/TiCl4-Al(C2H5)3. Makromol Chem Rapid Commun 4: 41-44
Kashiwa N, Yoshitake J (1984) Kinetic study on propylene polymerization with MgCl2/TiCl4 -AlEt3/PhCO2 Et System-the role of ethyl benzoate. Polym Bull 12: 99-104
Ahmadjo S, Jamjah R (2007) Preparation of highly active heterogeneous Ziegler-Natta catalyst for polymerization of ethylene. Iranian Polym J 16: 31-37
Taniike T, Chammingkwan P, Terano M (2012) Structure–performance relationship in Ziegler–Natta olefin polymerization with novel core–shell MgO/MgCl2/TiCl4 catalysts. Catal Commun 27: 13-16
Chammingkwan P, Thang VQ, Terano M, Taniike T (2014) MgO/MgCl2/TiCl4 core–shell catalyst for establishing structure–performance relationship in Ziegler–Natta olefin polymerization. Top Catal 57: 911-917
Wang J W, Cheng RH, He XL, Liu Z, Tian Z and Liu BP (2015) A Novel (SiO2/MgO/MgCl2)- TiClx Ziegler-Natta catalyst for ethylene and ethylene/1-hexene polymerization. Macromol Chem Phys 216: 1472-1482
Wang J W, Cheng RH, He XL, Liu Z, Tian Z and Liu BP (2016) Vanadium modification effects on the (SiO2/MgO/MgCl2)-TiClx Ziegler-Natta polyethylene catalyst. Macromol React Eng 10: 246-260
Huang F, Wang JW, Cheng RH., He XL, Liu Z, Zhao N and Liu BP (2016) Optimization of the preparation temperature for the novel (SiO2/ MgO/MgCl2)-TiClx Ziegler-Natta polyethylene catalyst. Macromol React Eng 10: 567-576
Böhm L L (1978) Ethylene polymerization process with a highly active Ziegler-Natta catalyst: 1. Kinetics. Polymer 19: 562-566
Böhm LL (2003) The ethylene polymerization with Ziegler catalysts: Fifty years after the discovery. Angew Chem Int Ed 42: 5010-30
Funako T, Chammingkwan P, Taniike T, Terano M (2015) Alternation of pore architecture of Ziegler-Natta catalysts through modification of magnesium ethoxide. Macromol React Eng 9: 325–332
Taniike T, Funako T, Terano M (2014) Multi lateral characterization for industrial Ziegler– Natta catalysts toward elucidation of structureperformance relationship. J Catal 311: 33-40
Zohuri GH, Jamjah R, Ahmadjo S (2003) Polymerization of propylene using the high-activity 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
Zohuri GH, Jamjah R, Nekomanesh Haghighi M, Mehtarani R, Ahmadjo S (2003) Slurry polymerization of ethylene using bisupported Ziegler- Natta catalyst of SiO2/MgCl2(ethoxide type)/ TiCl4/TEA system. Iran Polym J 12: 31-36
Zohuri GH, Jamjah R, Ahmadjo S (2004) Copolymerization of ethylene-propylene using high-activity bi-supported Ziegler-Natta TiCl4 catalyst. J Appl Polym Sci 93: 2597-2605
Zohuri GH, Jamjah R, Ahmadjo S (2006) Comparative study of propylene polymerization using monosupported and bisupported titanium-based Ziegler–Natta catalysts. J Appl Polym Sci 100: 2220–2226
Seger MR, Maciel GE (2004) Quantitative 13C NMR analysis of sequence distributions in poly(ethylene-co-1-hexene). Anal Chem 76: 5734-5747
Dashti A, Ramazani SAA, Hiraoka Y, Kim S Y, Taniike T, Terano M (2009) Kinetic and morphological study of a magnesium ethoxide-based Ziegler-Natta catalyst for propylene polymerization. Macromol Symp 58: 40-45
van Grieken R, Carrero A, Suarez I, Paredes B (2007) Effect of 1-hexene comonomer on polyethylene particle growth and kinetic profiles. Macromol Symp 259:243–252
McDaniel MP, Schwerdtfeger ED, Jensen MD (2014) The “comonomer effect” on chromium polymerization catalysts. J Catal 314: 109-116
Mikenas TB, Zakharov VA, Echevskaya LG, Matsko MA (2001) Ethylene polymerization with supported vanadium-magnesium catalyst: Hydrogen effect. Macromol Chem Phys 202: 475-481
Zhu, L., He, X., Cheng, R., Liu, Z., Zhao, N., & Liu, B. (2018). Effects of Ti/Mg molar ratio on bi-supported SiO2/MgCl2 (ethoxide type)/TiCl4 catalysts in ethylene homopolymerization and ethylene/1-hexene copolymerization. Polyolefins Journal, 5(1), 1-13. doi: 10.22063/poj.2017.1470
MLA
Liang Zhu; Xuelian He; Ruihua Cheng; Zhen Liu; Ning Zhao; Boping Liu. "Effects of Ti/Mg molar ratio on bi-supported SiO2/MgCl2 (ethoxide type)/TiCl4 catalysts in ethylene homopolymerization and ethylene/1-hexene copolymerization". Polyolefins Journal, 5, 1, 2018, 1-13. doi: 10.22063/poj.2017.1470
HARVARD
Zhu, L., He, X., Cheng, R., Liu, Z., Zhao, N., Liu, B. (2018). 'Effects of Ti/Mg molar ratio on bi-supported SiO2/MgCl2 (ethoxide type)/TiCl4 catalysts in ethylene homopolymerization and ethylene/1-hexene copolymerization', Polyolefins Journal, 5(1), pp. 1-13. doi: 10.22063/poj.2017.1470
VANCOUVER
Zhu, L., He, X., Cheng, R., Liu, Z., Zhao, N., Liu, B. Effects of Ti/Mg molar ratio on bi-supported SiO2/MgCl2 (ethoxide type)/TiCl4 catalysts in ethylene homopolymerization and ethylene/1-hexene copolymerization. Polyolefins Journal, 2018; 5(1): 1-13. doi: 10.22063/poj.2017.1470