„µ¦Á˜¦¸¥¤˜´ªÁ¦nŠž’·„·¦¥· µŸ­¤ Ziegler-Natta/Metallocene œ Mg(OH)2 ®¦º° Mg(OH)Cl ¨³„µ¦­´ŠÁ‡¦µ³®r¡°¨·Á°›·¨¸œ

Preparation of the Ziegler-Natta/metallocene hybrid catalysts on Mg(OH)2 or Mg(OH)Cl support and ethylene
polymerization
¼«´„—·Í ¡¼œ­ª´­—·1Í , ­¤®·Š ¨¸¨µš¦´¡¥rÁ‹¦·1, ¡´œ›„µœ˜r „oª°µ¬µ1
Choosak Poonsawat1, Somying Leelasubcharoen1, Puntakan Kaewarsa1
1
Department of Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand; E-Mail address
:puntakan@hotmail.com

š‡´—¥n°: Šµœª·‹´¥œ¸ÊÁž}œ„µ¦«¹„¬µ„µ¦­´ŠÁ‡¦µ³®r¡°¨·Á°›·¨¸œ ×¥­´ŠÁ‡¦µ³®rŗo‹µ„„µ¦Äo˜´ªÁ¦nŠž’·„·¦·¥µŸ­¤ Ž¹ÉŠÁ˜¦¸¥¤‹µ„˜´ªÁ¦nŠ Ziegler-Natta

¨³˜´ªÁ¦nŠ metallocene ¨³Äo­µ¦ž¦³„° alkyl aluminium ‡º° triethyl aluminium (TEA) Áž}œ˜´ªÁ¦nŠ¦nª¤ ‹µ„œ´Êœ‹³œÎµ˜´ªÁ¦nŠž’·„·¦·¥µŸ­¤š¸É
ŗoŞčoĜ„µ¦­´ŠÁ‡¦µ³®r¡°¨·Á°›·¨¸œ ×¥¤¸ Mg(OH)2 ¨³ Mg(OH)Cl Áž}œ˜´ª support ×¥‹³Á˜¦¸¥¤ Mg(OH)2 —oª¥ª·›¸ hydrothermal ¨³
Mg(OH)Cl ‹³Äoª·›¸Á˜¦¸¥¤Ã—¥˜¦Š ‹µ„œ´Êœ‹³«¹„¬µ¨´„¬–³…°Š˜´ª support ץčoÁš‡œ·‡ XRD Á¤ºÉ°Áž¦¸¥Áš¸¥ activity š¸Éŗo¡ªnµ ¡°¨·Á°›·¨¸œ
š¸É­´ŠÁ‡¦µ³®rŗo‹µ„„µ¦Äo˜´ªÁ¦nŠž’·„·¦·¥µŸ­¤ TMA/Cp2ZrCl2/Mg(OH)2 Ä®o‡nµ activity ¤µ„š¸É­»— ¦°Š¨Š¤µ‡º° Cp2ZrCl2/THF/Mg(OH)Cl
TMA/Cp2ZrCl2/TEA/Mg(OH)2 ,TiCl4/BuMgCl/TEA/Mg(OH)Cl ¨³ TiCl4/BuMgCl/Mg(OH)Cl ˜µ¤¨Îµ—´

Abstract: Polymerization of ethylene catalyzed by a mixture of Ziegler-Natta and Metallocene catalyst system and cocatalyzed with
alkyl aluminium compound such as triethyl aluminium (TEA) were carried out in stainless steel reactor. Hybrid catalysts investigated
were supported on Mg(OH)2 and Mg(OH)Cl. The Mg(OH)2 nanocrystalline was prepared by the hydrothermal method1 and
Mg(OH)Cl was prepared by direct method3. The XRD was used to characterize supports. The activities of the catalysts
TiCl4/BuMgCl/Mg(OH)Cl , TiCl4/BuMgCl/TEA/Mg(OH)Cl , TMA/Cp2ZrCl2/TEA/Mg(OH)2 and Cp2ZrCl2/THF/Mg(OH)Cl were
lower than the polyethylene obtained from the TMA/Cp2ZrCl2/Mg(OH)2 .

Methodology: Mg(OH)2 support was prepared by addition of 0.1 mol of Mg(NO3)2.6H2O into reactor and filled with dilute 0.1 M
NaOH solution. The mixture was kept at 80ÑC for 2 h. After cooling to room temperature, the white Mg(OH)2 powders were collected,
washed with distilled water and absolute ethanol and then dried in vacuum at 60ÑC for 4 h. Mg(OH)Cl support was prepared by
addition of MgO to a solution of MgCl2.6H2O. Slurry was agitated for 4 h and dried at 400qC for 24 h.
The hybrid catalysts were prepared by using Ziegler-Natta and Metallocene catalyst such as TiCl4, TMA and Cp2ZrCl2
supported on Mg(OH)2 and Mg(OH)Cl . Triethyl aluminium (TEA) was used as a cocatalyst. 50 ml of toluene was introduced under a
stream of N2 into glass reactor equiped with a stirrer and then 4 g of Mg(OH)2 was suspended. 40 ml of 2 mol TMA solution was added
dropwisely at 0qC and the mixture was allowed to react at 0qC for 2 h. The reaction mixture was then washed with toluene at 80ÑC.
The washed supports were suspended in 50ml of toluene and reacted with 0.1 g Cp2ZrCl2 at 50ÑC for 2 h. The resulted catalyst was
dried and prepared as a s lurr y in to luen e. 2.5 g of Mg(OH)Cl was mixed with 32 cm3 of Bu2MgCl in heptane and multiple
treatment of TiCl4 was used. The resulted catalyst was dried and prepared as a s lur r y in h ep tane .
Polymerization : In stainless steel reactor , 100 ml of toluene or heptane was introduced under nitrogen atmosphere; then, the
mixture of Ziegler-Natta and Metallocene catalyst system and TEA as cocatalyst were added .The reaction started by the addition of 2
atm of ethylene at temperature 60-70ÑC with a stirring speed of 700 rpm. After 2 h, the reaction was dried under vacuum.

Results, Discussion and Conclusion: Polyethylene was polymeried using Ziegler-Natta and metallocene catalyst such as TiCl4, TMA
and Cp2ZrCl2 impregnated on Mg(OH)2 and Mg(OH)Cl . The prepared support was activated by addition of Triethylaluminium (TEA).
The catalyst system and its activity were shown in the table below:

Catalyst Co-catalyst Activity (g-PE/molmetal.atm.h.)

TMA/Cp2ZrCl2/Mg(OH)2 do not use 139,850
TMA/Cp2ZrCl2/Mg(OH)2 TEA 74,587
TiCl4/BuMgCl/Mg(OH)Cl do not use 0
TiCl4/BuMgCl/Mg(OH)Cl TEA 15,966
Cp2ZrCl2/THF/Mg(OH)Cl do not use 107,655

Polymerrization condition : T = 60,70 ÑC, PC2H4 = 2 atm, stirr speed = 700 rpm., time = 2 h.

The XRD peak confirms the characteristic of Mg(OH)2 and Mg(OH)Cl . All Polymerization Kinetic Profiles were of decay
type. The TMA/Cp2ZrCl2/Mg(OH)2 catalyst gave the highest activity of 139,850 g-PE/mol-metal.atm.h.

Acknowledgement: This work was supported by the Postgraduate Education and Research Program in Chemistry (PERCH)

References: 1.Yi Ding, Guangtao Zhang, Hao Wu, Bin Hai, Liangbin Wang and Yitai Qian, J.Chem.Mater.13(2001)435-440.
2. Jin Suk Chung, Han Seock Cho, Young Gwan Ko, Wha Young Lee, J.Molecular Catalysis. A:Chem.144(1999)61-69.
3. Hsieh J.T.T,US Patent 4863886, 1989.

Keywords: Ziegler-Natta catalyst, metallocene, ethylene polymerization