• Macromolecular Research
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• v.8 no.5
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• pp.238-242
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• 2000

The new trisiloxane-bridged heterometallic dinuclear metallocenes, hexamethyltrisiloxanediyl(cyclopentadienyltitanium trichloride) (cyclopentadienylindenyl zirconium dichloride) , $C_3ITi-Cp(CH_3)_2Si-O-Si(CH_3)_2-O-Si(CH_3)_2-Cp-ZrIndCI_2$ (1) and hexamethyltrisiloxanediyl (cyclopentadienylindenylhafnium dichloride) (cyclopentadienylindenyl zirconium dichloride), $C_2IndHf-Cp(CH_3)_2Si-O-Si(CH_3)_2-Cp-ZrIndCl_2$ 2) connecting two dissimilar metallocenes were synthesized and used for ethylene polymerization in the presence of modified methylaluminoxane (MMAO) cocatalyst. The catalytic activity of heterometallic dinuclear metallocenes, 1 and 2 was lower than that of corresponding mononuclear metal-locene as well as two physically mixed catalysts, $CpTiCl_2/Cp_2ZrCl_2 and Cp_2HfCl_2/Cp_2ZrCl_2$. On the tither hand, MWD of PE obtained with 1 and 2 was remarkably broader ($M_w/M_n$) became up to 9.4) than those of PEs prepared with the corresponding mononuclear metallocenes and mixed catalysts. With analysis by GPC and CFC, it was found that PE produced by the heterometallic dinuclear metallocenes exhibited the definite bimodal GPC curves that should cause the broadening of MWD.

• Bulletin of the Korean Chemical Society
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• v.18 no.6
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• pp.618-622
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• 1997

The polysiloxane-bridged dinuclear metallocenes $[(SiMe_2O)_n-SiMe_2(C_5H_4)_2][(C_9H_7)ZrCl_2]_2$ (n=1 (7), 2 (8), 3 (9)) have been generated as a model complex for the immobilized metallocene at silica surface by treating the respective disodium salts of the ligands with 2 equivalents of $(C_9H_7)ZrCl_3$ in THF. All three complexes are characterized by $^1H$ NMR and measurement of metal content through ICP-MS. It turned out that the values of ${\Delta}{\delta}=[{\delta}_d-{\delta}_p]$, the chemical shift difference between the distal $({\delta}_d)$ and proximal $({\delta}_p)$ protons, for the produced dinuclear compounds (0.47 for 7, 0.49 for 8, and 0.5 for 9) were larger than the Δδ value of the known ansa-type complex holding the same ligand as a chelating one, that is just the opposite to the normal trend. In order to compare polymerization behavior of the dinuclear metallocene with the corresponding mononuclear metallocene, (Cp)$(C_9H_7)ZrCl_2$ was separately prepared. To investigate the catalytic properties of the dinuclear complexes and mononuclear metallocenes ethylene polymerization has been conducted in the presence of MMAO. The polymerization results display the typical activity dependence on polymerization temperature for all complexes. The most important feature is that the polymers from the dinuclear metallocenes represent enormously improved molecular weight compared with the polymer from the corresponding mononuclear metallocene. In addition, the influence of the nature of the bridging ligand upon the reactivities of the dinuclear metallocenes has also been observed.

• Polymer Science and Technology
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• v.9 no.1
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• pp.24-36
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• 1998

• Macromolecular Research
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• v.9 no.2
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• pp.71-83
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• 2001

The metallocene compounds had been applied to the polymerizations of olefins and vinyl monomers with methylaluminoxane (MAO) cocatalyst, and they have usually one transition metal atom per molecule, i.e., mononuclear metallocene. Recently it has been found that the dinuclear metallocene compounds containing two transition metal atoms exhibit the peculiar polymerization behaviors for olefins and vinyl monomers. In this article, the dinuclear metallocenes are classified into four groups of dinuclear bent-metallocene, dinuclear ansa-metallocene, dinuclear constrained geometry catalyst and dinuclear half-metallocene, and then the synthesis of dinuclear metallocene of each group as well as the polymerization behaviors for ethylene, propylene, and styrene are described.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.556-556
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• 2012

Transition metal-based organometallic complexes have shown great talents as a catalyst in various reactions. Designing organic molecules and coordinating them to such active centers have been a promising route to control the catalytic natures. Metallocene, which has transition metal atoms sandwiched by aromatic rings, is one of the representative systems for organometallic catalysts. Group 4-based metallocene catalysts have been most commonly used for the production of polyolefins, which have great world-wide markets in the real life. Graphenes and carbon nanotubes (CNTs) were composed of extended $sp^2$ carbon networks, showing high electron mobility as well as have extremely large steric bulkiness relative to metal centers. We were inspired by these characteristics of such carbon-based nano-materials and assumed that they could intimately interact with active centers of metallocene catalysts. We examined this hypothesis and, recently, reported that CNTs dramatically changed catalytic natures of group 4-based catalysts when they formed hybrid systems with such catalysts. In conclusion, we produced hybrid materials composed of group-4 based metallocenes, $Cp_2ZrCl_2$ and $Cp_2TiCl_2$, and carbon-based nano-materials such as RGO and MWCNT. Such hybrids were generated via simple adsorption between Cp rings of metallocenes and graphitic surfaces of graphene/CNT. The hybrids showed interesting catalytic behaviors for ethylene polymerizations. Resulting PEs had significantly increased Mw relative to those produced from free metallocene-based catalytic systems, which are not adsorbed on carbon-based nano-materials. UHMWPEs with extremely high Mw were obtained at low Tp.

• Journal of the Korean Chemical Society
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• v.41 no.9
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• pp.502-517
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• 1997

This review deals with (1) the catalytic systems and mechanisms for the dehydropolymerization of silanes to polysilanes, (2) the dehydropolymerization of versatile silanes, (3) the preparation of polysilane derivatives, and (4) the applications of catalytic dehydropolymerizing systems to ceramics. The efforts to maximize the catalytic efficiency of group 4 metallocenes were introduced. Finally, the future of this dehydropolymerizing techniques of silanes was foreseen.

• 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.

• Bulletin of the Korean Chemical Society
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• v.20 no.11
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• pp.1269-1276
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• 1999

Metallocenes, whether using a cocatalyst or not, act as catalysts in ethylene polymerization. The positive charge on the transition metal of a metallocene might have an important role in polymerization as an active site in our model approach. Using semiempirical calculations in the absence of cocatalyst, we show one of the possibilities that the positive charge on a metallocene might be more easily transferred through the Cp ring of a ligand to the ethylene than to transfer directly from the transition metal to the ethylene. In these calculations, the charge on titanium in an eight C2H4 system is transferred and a polymer chain is produced. This reaction takes place only when ethylenes are arranged in a particular direction with respect to the ring, but does not take place for ethylenes near Ti or Cl atoms. The same mechanism is shown for a metallocene ligand which is sterically hindered or where the Cp ring is replaced by fluorenyl. These results suggest an entirely new polymerization mechanism in the absence of a cocatalyst in which the Cp ring is the active site.

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.759-761
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• 2006

The compound B(C6F5)3 and its variations have been widely employed as alkyl carbanion abstracting reagents to produce metallocene cations for olefin polymerization.1-3 Weakly coordinating anions containing boron can greatly improve the activity of metallocene catalysts used in industrial olefin polymerization4 and thus group IV and V metallocene complexes of the organohydroborate anions have been intensively investigated.5 Recently, many organohydroborate metallocene complexes have been reported by Shore and co-workers.6-8 A common structural feature of those complexes is the three-center two electron M-H-B bond, like that observed in transition metal tetrahydroborate complexes but the reactivity and fluxional behavior of organohydroborate complexes are unlike those of the tetrahydroborate analogues.6 Although many of those metallocenes have been synthesized, few complexes could be used in the olefin polymerization and then this laboratory has been involved in the chemistry of the cyclic organohydroborate anions, and their group IV metallocene derivatives for the catalyst.9 Described here is recent work that led to the preparation of a novel cyclic organohydroborate hafnocene complex (h5-C5H5)2Hf ？(μ-H)2BC8H14 ,Cl. The hafnocene complex contains the three-center two electron bond Hf-H-B10 in which the hydride abstraction for olefin polymerization may occur.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.236-242
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• 2014

Isospecific propylene polymerization behavior of meta- and para-Lewis base (E) functionalized unbridged zirconocenes ($[1-(E_n-Ph)-3,4-Me_2C_5H_2]_2ZrCl_2$, E = $NMe_2$, OMe; n = 1 or 2) was investigated under bulk conditions. Catalytic activity of the zirconocenes, and molecular weight and isotacticity of polypropylenes are found to be dependent on the position and number of the Lewis base functional groups in the zirconocenes. All the crude polypropylenes possess a broad molecular weight distribution and multi-melting transitions, indicating an involvement of multi-catalytic active species in the polymerization. The highest [mmmm] value of an isotactic portion of the polypropylenes reached 89%, which is higher than that (85%) from the well-known $C_2$-symmetric EBIZr (rac-$Et(Ind)_2ZrCl_2$) catalyst. These results support that the in situ generated, rigid rac-like cation-anion pair through the Lewis acid-base interactions between the functional groups of zirconocenes and methylaluminoxane anion is effective in the formation of isotactic polypropylene under bulk propylene polymerization conditions.