Temperature Programmed Decomposition of Silica-Supported MgCl<SUB>2</SUB>/THF/TiCl<SUB>4</SUB> Catalyst and Effect of Thermal Treatment on Ethylene Polymerization Rate

Ko YS; Han TK; Woo SI

Korean Journal of Chemical Engineering, Vol.14, No.5, 390-393, September, 1997

Temperature Programmed Decomposition of Silica-Supported MgCl₂/THF/TiCl₄ Catalyst and Effect of Thermal Treatment on Ethylene Polymerization Rate

Ko YS, Han TK, Woo SI

Silica supported MgCl₂/THF/TiCl₄ catalyst (SiO₂/MgCl₂/THF/TiCl₄) was prepared, and then decomposed thermally. The amount of produced gas [tetrahydrofuran (THF) and 1,4-dichlorobutane (DCB)] was measured with gas chromatography (GC) and mass spectrometer. SiO₂/MgCl₂/THF/TiCl₄ catalyst started to decompose around 85℃, and further decomposed at 113, 10 and 213℃. THF was mainly produced, but very small amount of DCB evolved during temperature programmed decomposition (TPD), while unsupported MgCl₂/THF/TiCl₄ produced DCB significantly. Polymerization rate of ethylene with SiO₂/MgCl₂/THF/TiCl₄ decreased when it was preheated at 85 and 110℃ for 5 and 60 min, respectively, while that of unsupported MgCl₂/THF/TiCl₄ increased after same pretreatment condition. It can be suggested that Mg/Ti bimetallic complex anchored on the surface of silica through OH group of it has weak interaction between Mg and Ti species.

Keywords:Olefin Polymerization;Ziegler-Natta Catalyst;Thermal Treatment

[References]

Chien JCW, Hsieh JTT, J. Polym. Sci. A: Polym. Chem., 14, 1915 (1976)
Choi HK, Chung DW, Han TK, Woo SI, Macromolecules, 26, 452 (1993)
Han JD, Kim I, Woo SI, Polym.(Korea), 13(2), 147 (1989)
Kim I, Woo SI, Polym. Bull., 22, 239 (1989)
Kim I, Chung MC, Choi HK, Kim JH, Woo SI, "Homo and Co-Polymerization of Ethylene with the Highly Active TiCl₄/THF/MgCl₂ Catalyst," Catalytic Olefin Polymerization, Kodansha Ltd., Tokyo, 323 (1990)
Kim I, Kim JH, Woo SI, J. Appl. Polym. Sci., 39, 837 (1990)
Kim I, Woo SI, Korean J. Chem. Eng., 7(2), 95 (1990)
Kim JH, Jeong YT, Woo SI, J. Polym. Sci. A: Polym. Chem., 32(15), 2979 (1994)
Ko YS, Han TK, Woo SI, "Temperature Programmed Decomposition of MgCl₂/THF/TiCl₄ Bimetallic Complex Catalyst and its Effect on the Homo and Copolymerization of Ethylene," Catalyst Design for Tailor-Made Polyolefins, Kodansha Ltd., Tokyo, 163 (1994)
Ko YS, Han TK, Park JW, Woo SI, J. Polym. Sci. A: Polym. Chem., in press (1997)
Ko Ys, Han TK, Park JW, Sadatoshi H, Woo SI, J. Polym. Sci. A: Polym. Chem., in revision (1997)
Munoz-Escalona A, Hermandez JG, Gallrdo JA, J. Appl. Polym. Sci., 29, 1187 (1984)
Murata M, Nakano A, Furuhashi H, Imai M, "Development of SiO₂-Supported Type Catalyst for Propylene Polymerization," Catalytic Olefin Polymerization, Kodansha Ltd., Tokyo, 165 (1990)
Sobota P, Utko J, Polym. Commun., 29, 144 (1988)
Soga K, Ohnish R, Doi Y, Polym. Bull., 9, 299 (1983)
Wagner BE, Goeke GL, Karol FJ, Goorge KF, "Continuous Production of Ethylene (Co) Polymers by Contacting Monomer with Catalyst Containing Reaction Product of Magnesium Cpd. with Electron Donor," Eur. Patent, Appl. 0,055,605 (1981)

[1] Chien JCW, Hsieh JTT, J. Polym. Sci. A: Polym. Chem., 14, 1915 (1976)

[2] Choi HK, Chung DW, Han TK, Woo SI, Macromolecules, 26, 452 (1993)

[3] Han JD, Kim I, Woo SI, Polym.(Korea), 13(2), 147 (1989)

[4] Kim I, Woo SI, Polym. Bull., 22, 239 (1989)

[5] Kim I, Chung MC, Choi HK, Kim JH, Woo SI, "Homo and Co-Polymerization of Ethylene with the Highly Active TiCl₄/THF/MgCl₂ Catalyst," Catalytic Olefin Polymerization, Kodansha Ltd., Tokyo, 323 (1990)

[6] Kim I, Kim JH, Woo SI, J. Appl. Polym. Sci., 39, 837 (1990)

[7] Kim I, Woo SI, Korean J. Chem. Eng., 7(2), 95 (1990)

[8] Kim JH, Jeong YT, Woo SI, J. Polym. Sci. A: Polym. Chem., 32(15), 2979 (1994)

[9] Ko YS, Han TK, Woo SI, "Temperature Programmed Decomposition of MgCl₂/THF/TiCl₄ Bimetallic Complex Catalyst and its Effect on the Homo and Copolymerization of Ethylene," Catalyst Design for Tailor-Made Polyolefins, Kodansha Ltd., Tokyo, 163 (1994)

[10] Ko YS, Han TK, Park JW, Woo SI, J. Polym. Sci. A: Polym. Chem., in press (1997)

[11] Ko Ys, Han TK, Park JW, Sadatoshi H, Woo SI, J. Polym. Sci. A: Polym. Chem., in revision (1997)

[12] Munoz-Escalona A, Hermandez JG, Gallrdo JA, J. Appl. Polym. Sci., 29, 1187 (1984)

[13] Murata M, Nakano A, Furuhashi H, Imai M, "Development of SiO₂-Supported Type Catalyst for Propylene Polymerization," Catalytic Olefin Polymerization, Kodansha Ltd., Tokyo, 165 (1990)

[14] Sobota P, Utko J, Polym. Commun., 29, 144 (1988)

[15] Soga K, Ohnish R, Doi Y, Polym. Bull., 9, 299 (1983)

[16] Wagner BE, Goeke GL, Karol FJ, Goorge KF, "Continuous Production of Ethylene (Co) Polymers by Contacting Monomer with Catalyst Containing Reaction Product of Magnesium Cpd. with Electron Donor," Eur. Patent, Appl. 0,055,605 (1981)