Vanadium-modified (SiO2/MgO/MgCl2)•TiClx Ziegler-Natta catalysts were prepared through co-impregnation of water-soluble magnesium and vanadium salts under different pH values. Several key factors such as pH value of co-impregnation solution during catalyst preparation, catalyst performances including catalytic activity, ethylene/1-hexene copolymerization and hydrogen response were investigated. It is found that the components, structures and performance of the catalysts are obviously affected by changing the pH value (pH=5, 7 and 9) of co-impregnation solution. An appropriate pH value (pH=7) can maximize catalytic activity and hydrogen response, while lower pH value (pH=5) is beneficial to the 1-hexene incorporation. The GPC results show that the polymers obtained have high average molecular weight.
Kashiwa N (2004) The discovery and progress of MgCl2 -supported TiCl4 catalysts. J Polym Sci Pol Chem 42: 1-8
Kashiwa N, Yoshitake J (1984) The influence of the valence state of titanium in MgCl2 –supported titanium catalysts on olefin polymerization. Makromol Chem 185: 1133-1138
Kashiwa N, Fujimura H, Tokuzumi Y (1968) Process for the polymerization and/ or copolymerization of olefins with the use of Ziegler-type catalysts supported on carrier. JP Patent 1,031,698
Galli P, Luciani L, Cecchin G (1981) Advances in the polymerization of polyolefins with coordination catalysts. Die Angew Makromol Chem 94: 63-89
Mayr A, Galli P, Susa E, Drusco GD, Giachetti E (1968) Polymerization of olefins. GB Patent 1,286,867
Böhm LL (2003) The ethylene polymerization with Ziegler catalysts: Fifty years after the discovery. Angew Chem Int Ed 42: 5010-5030
Stevens J, George M (1974) Catalysts and process for the polymerization of olefins. US Patent 3,787,384
Matta A, Zeng Y, Taniike T, Terano M (2012) Vanadium-modified bimetallic Phillips catalyst with high branching ability for ethylene polymerization. Macromol React Eng 6: 346-350
Wagner BE, Gokek GL, Karol FJ (1981) Process for the preparation of high density ethylene polymers in fluid bed reactor. US Patent 4,303,771
Chamla C, Daire E (1991) Supported polyolefin catalyst for the (co-)polymerization of ethylene in gas phase. EP Patent 0,453,088
Wang J, Cheng R, He X, Liu Z, Tian Z, Liu B (2015) A novel (SiO2 /MgO/MgCl2 )•TiClx ZieglerNatta catalyst for ethylene and ethylene/1-hexene polymerization. Macromol Chem Phys 216: 1472-1482
Hsieh JT, Pruden AL (1995) Mixed chromium catalyst, and alkene and alkyl aluminum hydridemodified Ziegler catalyst for multimodal HDPE. US Patent 5,408,015
Hsieh JT (1994) Mixed Ziegler and chromium catalyst and process for preparing a broad molecular weight distribution HDPE. US Patent 5,330,950
Ciaccia E, Vittorias I, Mihan S, Lukesova L, Lilge D, Salinas MH, Meier G, Mannebach G (2011) Process for the polymerization of ethylene, and ethylene polymers having broad molecular weight distribution and long-chain branching. US Patent 0,251,360
Bazvand R, Bahri-Laleh N, Nekoomanesh M, Abedini H (2015) Highly efficient FeCl3 doped Mg(OEt)2 /TiCl4 -based Ziegler–Natta catalysts for ethylene polymerization. Des Monomers Polym 18: 599-610
Garoff T, Leinonen T (1996) Mn doping of the Ziegler-Natta PP catalyst support material. J Mol Catal A-Chem 104: 205-212
Fregonese D, Bresadola S (1999) Catalytic systems supported on MgCl2 doped with ZnCl2 for olefin polymerization. J Mol Catal A-Chem 145: 265-271
Phiwkliang W, Jongsomjit B, Praserthdam P (2014) Synergistic effects of the ZnCl2 -SiCl4 modified TiCl4/MgCl2/THF catalytic system on ethylene/1-hexene and ethylene/1-octene copolymerizations. Chinese J Polym Sci 32: 84-91
Chen Y, Fan Z (2006) Ethylene/1-hexene copolymerization with TiCl4/MgCl2/AlCl3catalyst in the presence of hydrogen. Eur Polym J 42: 2441-2449
Chen Y, Fan Z, Liao J, Liao S (2006) Molecular weight distribution of polyethylene catalyzed by Ziegler–Natta catalyst supported on MgCl2 doped with AlCl3. J Appl Polym Sci 102: 1768-1772
Wang J, Cheng R, He X, Liu Z, Zhao N, Liu B (2015) Vanadium modification effects on the (SiO2 /MgO/MgCl2)•TiClx Ziegler-Natta polyethylene catalyst. Macromol React Eng 10: 246-260
Wang J, Cheng R, He X, Liu Z, Zhao N, Liu B (2015) Introduction of chromium species into the (SiO2 /MgO/MgCl2 )•TiClx Ziegler–Natta catalyst for better catalytic performance. J Organomet Chem: 299-310
Fu T, Cheng R, He X, Liu Z, Tian Z, Liu B (2016)Modification of the (SiO2/MgO/MgCl2)•TiClx Ziegler-Natta polyethylene catalysts using third metal elements. Chinese J Polym Sci 35: 1-13
Wunderlich B, Czornyj G (1977) A study of equilibrium melting of polyethylene. Macromolecules 10: 906-913
Seger MR, Maciel GE (2004) Quantitative 13C NMR analysis of sequence distributions in poly(ethylene-co-1-hexene). Anal Chem 76: 5734-5747
Huang F, Wang J, Cheng R, He X, Liu Z, Zhao N, Liu B (2016) Optimization of the preparation temperature for the novel (SiO2/MgO/MgCl2)•TiClx Ziegler-Natta polyethylene catalyst. Macromol React Eng 10: 567-576
Fu T, Cheng R, He X, Liu Z, Tian Z, Liu B (2016)Imido-modified SiO2 -supported Ti/Mg ZieglerNatta catalysts for ethylene polymerization and ethylene/1-hexene copolymerization. Polyolefins J 3: 103-117
Gao J, Guo J, Liang D, Hou Z, Fei J, Zheng X (2008) Production of syngas via autothermal reforming of methane in a fluidized-bed reactor over the combined CeO2 –ZrO2/SiO2 supported Ni catalysts. Int J Hydrogen Energy 33: 5493-5500
Andoni A, Chadwick JC, Niemantsverdriet HJW, Thüne PC (2007) A preparation method for welldefined crystallites of MgCl2 -supported ZieglerNatta catalysts and their observation by AFM and SEM. Macromol Rapid Commun 28: 1466-1471
Senso N (2010) The influence of mixed activators on ethylene polymerization and ethylene/1- hexene copolymerization with silica-supported Ziegler-Natta catalyst. Molecules 15: 9323-9339
Fan Z, Zhang L, Xia S, Fu Z (2011) 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
Kissin YV, Rishina LA (2008) Kinetics of propylene and ethylene polymerization reactions with heterogeneous Ziegler-Natta catalysts: Recent results. Polymer Sci A 50: 1101-1121
Hassan Nejad M, Ferrari P, Pennini G, Cecchin G (2008) Ethylene homo- and copolymerization over MgCl2 -TiCl4 catalysts: Polymerization kinetics and polymer particle morphology. J Appl Polym Sci 108: 3388-3402
Kim JH, Jeong YT, Woo SI (1994)Copolymerization of ethylene and 1-butene with highly active TiCl4 /THF/MgCl2, TiCl4/THF/MgCl2/SiO2, and TiCl31/3AlCl3 catalysts. J Polym Sci Pol Chem 32: 2979-2987
Yang H, Huang B, Fu Z, Fan Z (2015) Ethylene/1-hexene copolymerization with supported Ziegler–Natta catalysts prepared by immobilizing TiCl3 (OAr) onto MgCl2. J Appl Polym Sci 132: DOI: 10.1002/app.41329
Novokshonova LA,Zakharov VA (2013)Kinetics of olefin polymerization and activesites of heterogeneous Ziegler-Natta catalysts. In: Polyolefins: 50 years after Ziegler and Natta I: Polyethylene and polypropylene, Ed. W Kaminsky. Springer, Berlin, 99-134
Hindryckx F, Dubois P, Jérôme R, Mattib MG (1998) Ethylene polymerisation by a high activity MgCl2 supported Ti catalyst in the presence of hydrogen and/or 1-octene. Polymer 39: 621-629
Marques MMV, Nunes CP, Tait PJT, Dias AR (1993) Polymerization of ethylene using a highactivityZiegler–Natta catalyst. I. Kinetic studies. J Polym Sci Pol Chem 31: 209-218
Guastalla G, Giannini U (1983) The influence of hydrogen on the polymerization of propylene and ethylene with an MgCl2 supported catalyst. Makromol Chem Rapid Commun 4: 519-527
Fu, T., Cheng, R., He, X., Liu, Z., Tian, Z., & Liu, B. (2018). How can pH value during catalyst preparation affect the performance of vanadium-modified (SiO2/MgO/ MgCl2)•TiClx Ziegler-Natta polyethylene catalysts. Polyolefins Journal, 5(1), 31-45. doi: 10.22063/poj.2017.1492
MLA
Ting Fu; Ruihua Cheng; Xuelian He; Zhen Liu; Zhou Tian; Boping Liu. "How can pH value during catalyst preparation affect the performance of vanadium-modified (SiO2/MgO/ MgCl2)•TiClx Ziegler-Natta polyethylene catalysts". Polyolefins Journal, 5, 1, 2018, 31-45. doi: 10.22063/poj.2017.1492
HARVARD
Fu, T., Cheng, R., He, X., Liu, Z., Tian, Z., Liu, B. (2018). 'How can pH value during catalyst preparation affect the performance of vanadium-modified (SiO2/MgO/ MgCl2)•TiClx Ziegler-Natta polyethylene catalysts', Polyolefins Journal, 5(1), pp. 31-45. doi: 10.22063/poj.2017.1492
VANCOUVER
Fu, T., Cheng, R., He, X., Liu, Z., Tian, Z., Liu, B. How can pH value during catalyst preparation affect the performance of vanadium-modified (SiO2/MgO/ MgCl2)•TiClx Ziegler-Natta polyethylene catalysts. Polyolefins Journal, 2018; 5(1): 31-45. doi: 10.22063/poj.2017.1492