• Elastomers and Composites
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• v.47 no.4
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• pp.329-335
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• 2012

In this study, we synthesized poly(ethylene-ter-high ${\alpha}$-olefin-ter-p-methylstyrene) using Zr metallocene catalyst/borate type cocatalyst system. Various effects of the high ${\alpha}$-olefin (1-hexene, 1-octene, 1-decene, and 1-dodecene) were observed. The structure and composition of the terpolymers were characterized using $^{13}C$ NMR and $^1H$ NMR. Catalytic activity, polymer yield, molecular weight and molecular weight distribution were analyzed according to the chain length of high ${\alpha}$-olefin. We determined morphology, crystallinity and thermal properties of the terpolymers.

• Membrane Journal
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• v.13 no.4
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• pp.246-256
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• 2003

For the olefin recovery from polyolefin off-gas, the permeation behaviors of olefins and nitrogen were investigated through three kinds of PDMS membranes - cross-linked PDMS membranes, a polysiloxaneimide membrane, and oligo-PDMS modified PDMS membranes. Their pure gas permeabilities were measured as a function of operation temperature(-20 to $50^{\circ}C$) and pressure(1 to 25 atm) with ethylene($C_2\;H_4$), propylene($C_3\;H_6$), butylene($C_4\;H_8$), and nitrogen($N_2$) gases. The permeabilities of olefins and nitrogen highly depended upon the nature of PDMS membranes. Among these membranes, cross-linked PDMS membranes showed stable and high olefin/nitrogen selectivities over a wide operation pressure range and further study in various test conditions. Their permeability of olefin and nitrogen were governed by the condensation temperature(solubility selectivity) and plasticization, not the order of the size(diffusivity selectivity) of gases, which matched well with the general permeation behavior of rubbery polymeric membranes for condensable and non-condensable gases. With increasing feed pressure or decreasing feed temperature, the permeabilities of more condensible olefins increase highly, presumably due to high solubility and plasticization, but that of non-condensible nitrogen decreases slightly and thus, the selectivities of olefin/nitrogen increase highly.

• 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.15 no.3
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• pp.204-209
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• 1994

Catalytic hydroacylation has been achieved by the reaction of 8-quinolinecarboxaldehyde (1) and various vinyl derivatives such as 2a, 2b and 2c with Wilkinson's complex (3) to give linear alkyl ketones, 4a, 4b and 4c, respectively. However, stoichiometric ligand-promoted hydroacylation of 2a and 2b with [$(C_8H_{14})_2RhCl]_2$ (5) resulted in a mixture of the branched alkyl ketones and the linear alkyl ketones in different ratios. Stoichiometric hydroacylation of some other olefin derivatives such as 6, 11, 12 and 26, produced functionalized alkyl ketone compounds.

• Macromolecular Research
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• v.14 no.2
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• pp.199-204
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• 2006

Remarkably high and stable separation performance for olefin/paraffin mixtures was previously reported by facilitated olefin transport through ${\pi}$-complex membranes consisting of silver ions dissolved in poly(hexamethylenevinylene) (PHMV). In this study, the ${\pi}$-complex formation of $AgBF_4,\;AgClO_4\;and\;AgCF_{3}SO_3$ with PHMV and their ionic interactions were investigated. FT-Raman spectroscopy showed that the C=C stretching bands of PHMV shifted to a lower frequency upon incorporation of silver salt, but the degree of peak shift depended on the counter-anions of salt due to different complexation strengths. The symmetric stretching modes of anions indicated the presence of only free ions up to [C=C]:[Ag]=1:1, demonstrating the unusually high solubility of silver salt in PHMV. Above the solubility limit, the ion pairs and higher-order ionic aggregates started to form. The coordination number of silver ion for C=C of PHMV was in the order $AgBF_4$ > $AgClO_4$ > $AgCF_{3}SO_3$, but became similar at [C=C]:[Ag]=1:1. The different coordination number was interpreted in terms of the different transient crosslinks of silver cations in the complex, which may be related to both the interaction strength of the polymer/silver ion and the bulkiness of the counteranion.

• Polymer(Korea)
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• v.24 no.5
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• pp.646-655
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• 2000

Polymerizations of higher $\alpha$-olefins were carried out in toluene by using highly isospecific catalyst, rac-(EBI)M(NMe$_2$)$_2$ (EBI=1,2-ethylenebis-(1-indenyl); M=Zr(rac-1); M=Hf(rac-2)) In the presence of Al(i-Bu)$_3$/[Ph$_3$C][B($C_{6}F_{5}$)$_4$]. The polymerization of high $\alpha$-olefin showed high activity and similar polymerization behavior. The polymerization activity was affected by both monomer size and lateral size of polymer chain. The conversion of monomer to polymer decreases with the increased lateral size in the order of 1-pentene>1-hexene>1-octene>1-decene. The same dependences of melting behavior and intrinsic viscosity of polyolefin on lateral size were observed according to the results obtained by differential scanning calorimetry and intrinsic viscosity. All poly($\alpha$-olefin)s showed very high isotacticity (triad) and the isotacticity increases in the order of poly(1-pentene)$^1H$ NMR and Raman spectra analysis showed that chain transfer to cocatalyst, which generates saturated methyl groups, Is a main chain termination. The $\beta$-hydride eliminations, which generate unsaturated vinylidene, tri-substituted, and vinylene end group. are found to be minor chain terminations.

• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.802-811
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• 1992

The conformations of several carbene-olefin-transition metal complexes[$(CO)_4M$-(CHX)olefin] (X: $OCH_3,\;NHCH_3,\;SCH_3$, M: C, Mo, W) have been studied by means of Extend Huckel calculations. In the case of $d^6$ transition metal octahedral complexes, it is shown that the two main factors which determine the optimal conformation are metal-to-ligand back-donation and direct ligand-ligand interaction at the metal, but the ligand-ligand interaction dominates the situation for a metal that is coordinated to $\pi$ acceptor ligands and to $\pi$ donor group on the carbene. The relative amounts of both factors depend strongly on the electronic nature of the ligands at the metal. The greater electron donating ability of nitrogen stabilizes amino-substituted carbene complexes compared with their alkoxyl substituted analogues. This interaction is optimal when the $\pi$ systems of the carbene and olefin are coplanar. The introduction of the $\pi$ donor group on the carbene carbon increases also the importance of the ligand-ligand interaction.

• 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.

• Bulletin of the Korean Chemical Society
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• v.16 no.6
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• pp.524-528
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• 1995

The reaction of [IrCl(cod)]2 with ppol ligand, Ph2PCH2CH2CH2P(Ph)CH2CH2CH=CH2, in ethanol gives an iridium complex, whose structure is converted from an ionic form, [Ir(cod)(ppol)]Cl·2C2H5OH (1),in polar solvents (ethanol, methanol and acetonitrile), to a molecular form, [IrCl(cod)(ppol)], in non-polar solvents (benzene and toluene). The cationic complexes, [Ir(cod)(ppol)]AsF6·1/2C2H5OH and [Ir(cod)(ppol)]PF6·1/2CH3CN, were prepared to compare with the ionic form by 31P NMR spectroscopy. When carbon monoxide is introduced to 1, cod is replaced by CO to give the 5-coordinated complex, [IrCl(CO)(ppol)]. Hydrogenation of 1-octene was not successful in the presence of 1. In order to verify the reason for 1 not behaving as a good catalyst for hydrogenation, electrophilic reactions with HCl, I2 and HBF4·etherate were performed, which yielded the oxidative addition product, [IrHCl2(ppol)], the substitution product, [IrI(cod)(ppol)], and another cationic product, [Ir(cod)(ppol)]BF4, respectively. Thus, the iridium complex is not sufficiently basic to activate hydrogen atoms or the olefin of the ppol ligand.

• Membrane Journal
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• v.16 no.4
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• pp.294-302
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• 2006

Silver polymer electrolytes are very promising membrane materials for the separation of olefin/paraffn mixtures. Olefin molecules are known to be transported through reversible complex formation with silver ions entrapped iii polymer matrix. However, they have poor long-term stability, which is very important fur the industrial application; the selectivity through the membrane decreases gradually with time mostly due to the reduction of silver ions ($Ag^+$) into silver nanoparticles ($Ag^0$). In this study, the stability of silver polymer electrolyte was investigated for poly(vinyl pyrrolidone) (PVP) and $AgBF_4$ system containing a surfactant, i.e. $C_{18}H_{35}(OCH_2CH_2)_{20}OH$ (Brij98) as a stabilizer. The reduction behavior of silver ions to silver nanoparticles in PVP was also investigated by atomic force microscopy (AFM) and UV-visible spectroscopy. It was found that the growth of silver nanoparticles was slower and selectivity of polymer electrolyte for propylene in propylene/propane was maintained longer time when Brij98 was added as a stabilizer.