• 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.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.221-221
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• 2006

The stereochemical control in polypropylenes and styrene-ethylene copolymers based on homogeneous single-site polymerization catalysts has received great attention since the stereocpecificity is one of the key factors in tailoring the polymer properties. Thus, we have developed new tactics for isospecificity in propylene polymerization with the unbridged metallocenebased systems and syndiospecific styrene-styrene sequence in styrene-ethylene copolymerization with the group 4 metallocene system. Brief details of the synthesis, structures and the polymerization behavior of a set of new metallocene catalysts will be presented.

• Applied Chemistry
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• v.15 no.2
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• pp.89-92
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• 2011

We synthesized ethylene-styrene copolymer using pyrazolato-type metallocene catalysts. We observed the effects of ethylene contents on the catalytic activity, yield molecular weight and molecular weight distribution. We could also confirm living polymerization behavior through the changes of the M_n and M_w/M_n according to the yield.

• Polymer(Korea)
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• v.29 no.4
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• pp.321-330
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• 2005

In 1990's the Korean polyolefin industry boomed up through the development of magnificient polymerization catalysts. To understand the general situation of polymerization catalyst R & D, the various experimental results had been summarized for the investigation of not only the supported Ziegler-Natta catalyst used presently in polyolefin industry but also the metallocene catalysts applied for the preparation of special grade of polyolefin. In addition, it had been shown that the new polymeric materials were prepared by new developed catalyst, and the polymer in-situ nanocomposites could be obtained with the application of catalyst heterogenization procedures.

• 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.

• Applied Chemistry for Engineering
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• v.24 no.1
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• pp.55-61
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• 2013

Heterogeneous metallocene catalysts supported on montmorillonite (MMT), [$Cp_2ZrCl_2$/MMT, $Cp_2ZrCl_2$/MAO/MMT, and $Cp_2ZrCl_2$ + MAO/MMT], were prepared with three different methods of immobilization and tested for ethylene polymerization. The heterogeneous catalysts immobilized on organo clay (30B-MMT) showed the higher metal loading and polymerization activity than those immobilized on natural clay $Na^+-MMT$. These results suggest that the hydroxyl groups of organo clay interlayers react with the MAO and catalyst through the chemical bond. The metallocene catalyst supported directly on MMT showed lower activity for ethylene polymerization compared to the homogeneous systems, while MMT/MAO/$Cp_2ZrCl_2$, catalysts treated with MAO before impregnation, showed a higher activity. The polymers obtained from MMT-supported catalysts have higher melting point, molecular weight and molecular weight distributions than those of homogeneous catalysts. The polymer particles with increasing significant size. Ethylene polymerization over 30B-MMT/MAO/$Cp_2ZrCl_2$ catalyst was also performed varying the process variables to optimize the process conditions.

• Macromolecular Research
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• v.8 no.1
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• pp.34-43
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• 2000

The melt rheology of four binary blends of ethylene 1-octene copolymers (EOCs) which consist of one component by Ziegler-Natta and another by metallocene catalysts, was studied to elucidate miscibility in the melt by using torsion rheometer at 200$\^{C}$ and different shear rates. The four blend systems, designated into the FA+FM, SF+FM, RF+EN, and RF+PL blend, are divided and interpreted based on the melt index (MI), the density and the comonomer contents. The melt viscosity such asη', η", and η$\^$*/ is weight average value if the comonomer contents are similar, otherwise they show different manner. The experimental resole are analyzed based on the Cole-Cole plot of logη' uersus log η", the logarithmic plots of the dynamic storage modulus (G') versus the dynamic loss modulus (G") for various blend compositions, and the melt viscosity of 11', n", and f" as a function of blend compositions. As a cerise-quence, the FA+FM blend is miscible, but the SF+FM, RF+EN, and RF+PL blends are not in the melt. Thus miscibility of the blends studied in this communication is suggested to strongly influence by the comonomer contents rather than the density or the MI.

• Elastomers and Composites
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• v.46 no.4
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• pp.304-310
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• 2011

In this study, we prepared poly(ethylene-ter-1-hexene-ter-divinylbenzene) using briged rac-$Et[Ind]_2ZrCl_2$ or unbriged $Cp_2ZrCl_2$ metallocene catalysts. Bridged rac-$Et[Ind]_2ZrCl_2$ catalyst showed relatively good results compared with unbridged one. When cocatalyst/catalyst molar ratio was 3000, catalytic activity indicated more than 8000(kg of polymer/$mol{\cdot}h$) which was very remarkable value. As a polymerization time increased, the weight-average molecular weight of the terpolymer gradually increased to some degree. In the case of a polymerization time of 50 minutes, the state of the terpolymer became amorphous. The range of the weight-average molecular weight and the densities of the terpolymer was 110,000~200,000 and $0.85{\sim}0.89g/cm^3$, respectively. The thermal properties and the structure of the terpolymer were also identified.

• Polymer(Korea)
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• v.32 no.6
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• pp.566-572
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• 2008

Polyethylene has been prepared via metallocene catalysts [(TMDS)$Cp_2$]$ZrCl_2$, 1, and [$(n-Bu)_2Cp_2$]$ZrCl_2$, 2, in the presence of hydrogen as a chain transfer reagent. Increase of hydrogen flow to the polymerization reactor resulted in the drop of catalytic activity, reduction of molecular weight of polyethylene, getting narrow of molecular weight distribution of polyethylene, and melting point of the polyethylene wax. It should be noticed that it was possible to control molecular weight down to 1500 and melting temperature to 60 $^\circ$C of polyethylene wax using the catalyst 1 that has been developed by authors as well as the catalyst 2 from Exxon.

• Elastomers and Composites
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• v.55 no.4
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• pp.263-269
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• 2020

Novel flexible terpolymers with a reactive moiety were synthesized by coordination polymerization with a metallocene catalyst and a cocatalyst system. C2-symmetric rac-Et(Ind)2ZrCl2 and tri-iso-butylaluminum/dimethylanilinium tetrakis (pentafluorophenyl) borate were employed as the catalyst and cocatalyst, respectively. We synthesized reactive terpolymers consisting of ethylene, a high α-olefin content (1-hexene, 1-octene, 1-decene, and 1-dodecene), and divinylbenzene. The structure and composition of the terpolymers were characterized by 1H-nuclear magnetic resonance analysis. The catalytic activity, polymer yield, molecular weight, and molecular weight distribution were measured as functions of the chain length and high content of α-olefins. Furthermore, the thermal properties and crystallinity of the terpolymers were determined by differential scanning calorimetry and wide-angle X-ray scattering.