• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.224-225
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• 2006

The Ethylene polymerization behavior of a series of polymethylene bridged dinuclear CGC $[Zr({\eta}^{5}:{\eta}^{1}-C_{9}H_{5}SiMe_{2}NCMe_{3})Me_{2}]_{2}[(CH_{2})_{n}]\;[_{n}=6(1),\;9(2),\;12(3)]$ in the cocatalytic activation with $Ph_{3}C^{+}B^{-}(C_{6}F_{5})_{4}\;(B_{1})\;or\;Ph_{3}C^{+}(C_{6}F_{5})_{3}B^{-}C_{6}F_{4}B^{-}(C_{6}F_{5})_{3}Ph_{3}C^{+}\;(B_{2})\;or\;B(C_{6}F_{5})_{3}\;(B_{3})$ were investigated to study the nuclearity effects as well as the counteranion effects. The ethylene polymerization and ethylene/1-hexene copolymerization were conducted at $30^{\circ}C$ It was found that both in ethylene polymerization and ethylene/1-hexene copolymerization, activities increased in the order of 1 < 2 < 3, which indicates the presence of longer bridge between two active sites contributes more efficiently to facilitate the polymerization activity.

• Macromolecular Research
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• v.12 no.3
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• pp.316-321
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• 2004

We have performed copolymerizations of ethylene with 1-hexene using various ansa-metallocene compounds in the presence of the non-coordinative [CPh$_3$][B(C$\_$6/F$\_$5/)$_4$ion pair as a cocatalyst. The metallocenes chosen for this study are isospecific metallocene diamide compounds, rac-(EBI)Zr(NMe$_2$)$_2$ [1, EBI = ethylene-l ,2-bis(1-indenyl)], rac-(EBI)Hf(NMe$_2$)$_2$ (2), rac-(EBI)Zr(NC$_4$H$\_$8/)$_2$ (3), and rac-(CH$_3$)$_3$Si(1-C$\_$5/H$_2$-2-CH$_3$-4-$\^$t/C$_4$H$\_$9/)2 Zr(NMe$_2$)$_2$ (4), and syndiospecific metallocene dimethyl compounds, ethylidene(cyclopentadienyl)(9-fluorenyl) ZrMe$_2$ [5, Et(Flu)(Cp )ZrMe$_2$] and isopropylidence (cyclopentadienyl)(9-fluorenyl)ZrMe$_2$ [6, iPr(Flu)(Cp)ZrMe$_2$]. The copolymerization rate decreased in the order 4 ＞1-3＞2 ＞5＞6. The reactivity of I -hexene decreased in the order 2 ＞6＞1- 3-5＞ 4. We characterized the microstructure of the resulting poly(ethylene-co-l-hexene) by $\^$l3/C NMR spectroscopy and investigated various other properties of the copolymers in detail.

• Macromolecular Research
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• v.14 no.2
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• pp.240-244
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• 2006

• Polymer(Korea)
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• v.35 no.6
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• pp.505-512
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• 2011

Effects of structural features of 4 dinuclear constrained geometry catalysts having paraxylene derivative bridge (DCGC) on copolymerization of ethylene and 1-hexene were investigated. The bridges of three catalysts have para-xylene backbone with a different substituent at benzene ring. The substituents were hydrogen (Catalyst 1), isopropyl (Catalyst 2), n-hexyl (Catalyst 3) and 1-octyl (Catalyst 4). It was found that Catalyst 1 having hydrogen as a substituent exhibited the greatest activity among the four dinuclear CGCs. On the other hand, Catalyst 2 containing isopropyl as a substituent showed the smallest activity. Very interestingly, Catalyst 2 was able to produce about 6 times higher molecular weight polymer than Catalyst 3 and 4. Catalyst 3 and 4 having a long alkyl chain substituent revealed the biggest comonomer response to generate polyethylene copolymer containing more than 40% 1-hexene contents. These results suggest that the control of the substituent of para-xylene bridge of dinuclear CGC can provide a proper method to adjust the microstructure of polyethylene copolymers.

• Journal of the Korean Chemical Society
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• v.62 no.3
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• pp.191-202
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• 2018

The aim of this work is to study Monte Carlo simulation of ethylene (co)polymerization over Ziegler-Natta catalyst as investigated by Chen et al. The results revealed that the Monte Carlo simulation was similar to sum square error (SSE) model to prediction of stage II and III of polymerization. In the case of activation stage (stage I) both model had slightly deviation from experimental results. The modeling results demonstrated that in homopolymerization, SSE was superior to predict polymerization rate in current stage while for copolymerization, Monte Carlo had preferable prediction. The Monte Carlo simulation approved the SSE results to determine role of each site in total polymerization rate and revealed that homopolymerization rate changed from site to site and order of center was different compared to copolymerization. The polymer yield was reduced by addition of hydrogen amount however there was no specific effect on uptake curve which was predicted by Monte Carlo simulation with good accuracy. In the case of copolymerization it was evolved that monomer chain length and monomer concentration influenced the rate of polymerization as rate of polymerization reduced from 1-hexene to 1-octene and increased when monomer concentration proliferate.

• Polymer(Korea)
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• v.31 no.6
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• pp.497-504
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• 2007

We have prepared the dinuclear half-sandwich CGC(constrained geometry catalyst) with polymethylene bridge $[Zr(({\eta}^5\;:\;{\eta}^1-C_9H_5SiMe_2NCMe_3)Me_2)_2\;[(CH_2)_n]$ [n=6(4), 9(5), 12(6)] by treating 2 equivalents of MeLi with the corresponding dichlorides compounds. To study the catalytic behavior of the dinuclear catalysts we conducted copolymerization of ethylene and 1-hexene in the presence of three kinds of boron cocatalysts, $Ph_3C^+[B(C_6F_5)_4]^-\;(B_1),\;B(C_6F_5)_3\;(B_3)$, and $Ph_3C^+[(C_6F_5)_3B-C_6F_4-B(C_6F_5)_3]^{2-}\;(B_2)$. It turned out that all active species formed by the combination of three dinuclear CGCs with three cocatalyst were very efficient catalysts for the polymerization of olefins. The activities increase as the bridge length of the dinuclear CGCs increases. At the same time the dinuclear cocatalyst exhibited the lowest activity among three cocatalysts. The prime observation is that the dinuclear cocatalyst gave rise to the formation of the copolymers with the least branches on the polyethylene backbone.

• Applied Chemistry for Engineering
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• v.29 no.4
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• pp.461-467
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• 2018

In this study, $(n-BuCp)_2ZrCl_2$, was supported on $SiO_2/MgCl_2$ binary support. Before supporting the catalyst, the $SiO_2/MgCl_2$ binary support was surface treated with three different alkyl aluminum compound, namely trimethylaluminum, triethylaluminum, and ethylaluminum sesquichloride. The synthesized surface-treated $SiO_2/MgCl_2$ supported metallocene catalysts were used for the copolymerization of ethylene and 1-hexene. Their catalytic properties and performances were analyzed through BET, XPS analysis, ICP-AES analysis, and FE-SEM. While the resulting copolymers were analyzed through DSC analysis, GPC analysis, 13C-NMR analysis, and FE-SEM. The analysis of synthesized surface-treated $SiO_2/MgCl_2$ supported metallocene catalysts showed that the Zr content of these catalysts is relatively lower compared to that of the catalyst supported on $SiO_2$. This could be attributed to the reduction in the surface area of $SiO_2$ due to the presence of recrystallized $MgCl_2$ and alkyl aluminum. Furthermore, they exhibited a better copolymerization activity compared to that of $SiO_2$ supported catalyst, particularly the EASC-surface treated binary support, which has the highest activity of 1.9 kg PE/($mmol-Zr^*hr$) because EASC acts as a strong Lewis acid. It could also be observed that the larger the ligand of alkyl aluminum used, the rougher the particle surface of the resulting polymer.

• Polymer(Korea)
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• v.25 no.4
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• pp.468-475
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• 2001

For copolymerization of ethylene and norbornene initiated by various metallocene catalysts such as $rac-Et(Ind)_2ZrCl_2,\;rac-Me_2Si(Ind)_2ZrCl_2,\;rac-Me_2Si(Cp)_2ZrCl_2,\;and\;(n-BuCp)_2ZrCl_2$ with modified methylaluminoxane(MMAO) cocatalyst, the ${\alpha}$-olefins such as 1-hexene(H), 1-octene and 1-decene were added as a 3rd monomer. In this situation, the effects of the polymerization condition, the catalyst structure as well as the structure and the amount of added ${\alpha}$-olefin on the catalyst activity as well as the properties and structure of polymer were examined. As results, it was found that the catalyst activity and thermal property of polymer depended on not only catalyst structure but also ${\alpha}$-olefin structure. For $rac-Et(Ind)_2ZrCl_2/MMAO$ catalyst system, it was possible to get high activity and controllable $T_g$ of polymer. Among ${\alpha}$-olefins, H as a 3rd monomer exhibited the maximum enhancement in catalyst activity.

• Elastomers and Composites
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• v.48 no.1
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• pp.10-17
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• 2013

Polyolefin-g-poly(t-butylstyrene) as one of the high-temperature polyolefin-based thermoplastic elastomers was synthesized by the graft-from anionic living polymerization from the styrene moieties of the linear poly(ethylene-ter-1-hexene-ter-divinylbenzene) as a soft block to form the hard end blocks, poly(t-butylstyrene). The chemistry of the anionic graft-from polymerization involved complete lithiation of the pendant styrene unit of the soft polyolefin elastomer with sec-BuLi/TMEDA followed by the subsequent graft anionic polymerization of 4-tert-butylstyrene with Mn=10,000~30,000 g/mol. The graft-from living anionic polymerization were very effective and the grafting size increased proportionally with increasing monomer concentration and the reaction times. The synthetic methodology for the multi-hydroxyl chain-end modified polyolefin-g-poly(t-butylstyrene) was proposed by using the thiol-ene click reaction between 2-mercaptoethanol and the polyolefin-g-[poly(t-butylstyrene)-b-high vinyl polyisoprene], which was obtained from the subsequent living block copolymerization using polyolefin-g-Poly(t-butylstyrene) with isoprene. The result indicated that this process produced a new well-defined functionalized graft-type polyolefin-based TPE with high $T_g$ hard block(> $145^{\circ}C$).