• Polymer(Korea)
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• v.30 no.5
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• pp.432-436
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• 2006

The new dinuclear CGC (constrained geometry complexes) with indenyl and methyl sub-stituted indenyl and polymethylene bridge have been synthesized, and the copolymerization of ethylene and styrene has been studied in the presence of methylalumionoxane. The activity of 12-methylene and 9-methylene bridged dinuclear CGC were 4 times higher than that of 6-methylene bridged dinucleay CGC. This result might be understood by the implication that the steric effect rather than the electronic effect nay play a major role to direct the polymerization behavior of the dinuclear CGC. The dinuclear CGCs are very efficient to incorporate styrene in backbone. The styrene contents in the formed co-polymers ranged from 6 to 45 mol% according to the polymerization conditions. The melting temperature of copolymers disappeared at high content of styrene (about 11 mol%) There is no styrene-styrene diblock sequence in copolymers. This result Indicates that the dinuclear CGC are very effective to generate random copolymer of ethylene and styrene.

• Korean Chemical Engineering Research
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• v.46 no.1
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• pp.137-141
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• 2008

Copolymerization of ethylene and ${\alpha}$-olefin using $rac-Et[Ind]_2ZrCl_2/MAO$ catalyst embedded onto polysty-rene was examined. The embedded catalyst was prepared by polymerizing a small amount of styrene with $rac-Et[Ind]_2ZrCl_2$. The catalytic activities of the embedded catalyst were higher than those of the homogeneous catalystregardless of comonomer type and the characteristic of the active sites of the embedded catalyst was not affected duringthe embedding process. Based on the DSC and NMR analyses of the produced copolymers, it was thought that theembedded catalyst had similar or slightly better comonomer incorporation ability. Furthermore, the copolymers produced by the embedded catalyst had higher bulk densities and better particle morphology than those by the homogeneous catalyst.

• 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.

• Journal of the Korean Chemical Society
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• v.53 no.6
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• pp.755-760
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• 2009

Styrene is broadly used as a polymer and a copolymer and is useful in manufacturing contact lenses due to its high refractive index. This study used styrene with the cross-linker EGDMA (ethylene glycol dimethacrylate), HEMA (2-hydroxyethyl methacrylate) and the initiator AIBN (azobisisobutyronitrile) for copolymerization. Measurement of the physical characteristics of the copolymerized material showed that the refractive index is 1.4412 - 1.4628, water content 20 - 35%, visible transmittance 82.6 - 87% and the tensile strength 0.143 - 0.344 Kgf. Also, measurements showed that the refractive index and tensile strength increased while the water content decreased as the ratio of styrene increased. Based on the results of this study, the produced copolymer can be estimated to be suitable for use as a material for high performance functional contact lenses.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.159-160
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• 2006

We developed novel catalyst, PHENICS composed of the combination of a cyclopentadienyl group to perform a high catalytic activity and a bulky phenoxy group, which performs the production of high molecular weight polyolefin. The polymerization activity of PHENICS at high temperature is higher than well-known CGC catalyst. PHENICS showed the excellent ability of comonomer incorporation into polymer chain. The obtained copolymer had a high molecular weight. The PHENICS catalyst is also active to the copolymerization of ethylene and several vinyl comonomers such as styrene, norbornen, and conjugated dienes. We will discuss new cocatalysts for PHENICS to improve activity and the ability of molecular weight control.

• Macromolecular Research
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• v.12 no.1
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• pp.100-106
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• 2004

We have prepared the polymethylene-bridged, dinuciear, half-sandwich constrained geometry catalysts (CGC)［Zr(η$\^$5/:η$^1$-C$\_$9/H$\_$5/SiMe$_2$NCMe$_3$)］$_2$［(CH$_2$)$\_$n/］［n=6(9), n=12(10)］by treating 2 equivalents of ZrCl$_4$with the corresponding tetralithium salts of the ligands in toluene. $^1$H and $\^$13/C NMR spectra of the synthesized complexes provide firm evidence for the anticipated dinuciear structure. In $^1$H NMR spectra, two singlets representing the methyl group protons bonded at the Si atom of the CGC are present at 0.88 and 0.64 ppm, which are considerably downfield positions relative to the shifts of 0.02 and 0.05 ppm of the corresponding ligands. To investigate the catalytic behavior of the prepared dinuciear catalysts, we conducted copolymerizations of ethylene and styrene in the presence of MMAO. The prime observation is that the two dinuclear CGCs 9 and 10 are not efficient for copo-lymerization, which definitely distinguishes them from the corresponding titanium-based dinuclear CGC. These species are active catalysts, however, for ethylene homopolymerization; the activity of catalyst 10, which contains a 12-methylene bridge, is larger than that of 9 (6-methylene bridge), which indicates that the presence of the longer bridge between the two active sites contributes more effectively to facilitate the polymerization activity of the dinuciear CGC. The activities increase as the polymerization temperature increases from 40 to 70$^{\circ}C$. On the other hand, the molecular weights of the polyethylenes are reduced when the polymerization temperature is increased. We observe that dinuciear metallocenes having different-length bridges give different polymerization results, which reconfirms the significant role that the nature of the bridging ligand has in controlling the polymerization properties of dinuclear catalysts.

• Journal of the Korean Chemical Society
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• v.54 no.3
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• pp.317-322
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• 2010

This study used 4-fluorostyrene with the cross-linker EGDMA (ethylene glycol dimethacrylate), HEMA (2-hydroxyethyl methacrylate) and the initiator AIBN (azobisisobutyronitrile) for copolymerization. Measurement of the physical properties of the copolymerized polymer showed that the water content was 19.98 ~ 31.08%, refractive index 1.443 ~ 1.475, visible transmittance 87 ~ 93% and tensile strength 0.246 ~ 0.311 kgf while the contact angle showed a distribution between $54.14^{\circ}$ and $66.95^{\circ}$. Therefore, the ophthalmic material produced using 4-fluorostyrene satisfied the basic physical properties required for contact lenses and also showed an increase in wettability and refractive index while having no significant change in water content with relation to styrene. Based on the results of this study, the produced copolymer is suitable for use as a material to high refractive index and wettability contact lenses.

• 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(> $145^{\circ}C$).

• Polymer(Korea)
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• v.35 no.1
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• pp.77-86
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• 2011

Polymerization properties of six dinuclear constrained geometry catalysts (DCGC) were investigated. The different length bridges of three catalysts were para-phenyl (Catalyst 1), para-xylyl (Catalyst 2), and para-diethylene phenyl (Catalyst 6). The other three DCGC have the same para-xylyl bridge with the different substituents at the phenyl ring of the bridge. The selected substituents were isopropyl (Catalyst 3), n-hexyl (Cataylst 4), and n-octyl (Catalyst 5), It was found that the longer catalyst not only exhibited a greater activity but also prepared a higher molecular weight copolymer. The catalyst 3 having a bulky isopropyl substituent revealed the lower activity but formed the highest molecular weight polymer comparing with the other alkyl substituted DCGCs. These results were able to be understood on the basis of the electronic and steric characteristics of the bridge. This study confirms that the control of the bridge structure of DCGC may contribute to control the microstructure of polymers.