• Macromolecular Research
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• v.15 no.2
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• pp.173-177
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• 2007

Living anionic and cationic polymerizations have been combined to prepare various types of comb-like copolymers composed of polystyrene (PS) and polyisoprene (PI) blocks, with a precisely controlled architecture. According to the relative placement of these elementary building blocks, combs with randomly distributed PS and PI or with poly(styrene-b-isoprene) diblock branches (I & II, respectively) can be prepared. The reaction procedure initially includes the synthesis of a poly(chloroethylvinyl ether) using living cationic polymerization, which is used as the reactive backbone to successively graft $PS^-Li^+$ and $PI^-Li^+$ or $PI-b-PS^-Li^+$ to obtain structures (I) or (II). The synthesis of Janus-type PS-comb-b-PI-combs (III) initially involves the synthesis of a diblock backbone using living cationic polymerization, which bears two distinct reactive functions having either a protected or activated form. Living $PS^-Li^+$ and $PI^-Li^+$ are then grafted, in two separate steps, onto each of the reactive functions of the backbone, respectively.

• Elastomers and Composites
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• v.53 no.3
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• pp.158-167
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• 2018

In this study, in-situ trans-selective polymerization of isoprene was carried out using titanium-based Ziegler-Natta catalysts. The catalysts were prepared by high-energy ball milling. Individually Large-inner-diameter carbon nanotubes (CNTL), and hydroxylated carbon nanotubes (CNTOH), along with magnesium chloride ($MgCl_2$) were used as the carriers for the catalysts. The optimum ball-milling time for preparing the $CNT/MgCl_2/TiCl_4$ Ziegler-Natta catalysts was 4 h. The $CNTOH/MgCl_2/TiCl_4$ catalyst showed a higher efficiency than that of the $CNTL/MgCl_2/TiCl_4$ catalyst, based on the rate of polymerization. The effects of the CNT-filler type on the isoprene polymerization behaviors and polymer properties were investigated. The morphologies of the trans-1,4-polyisoprene (TPI)/CNT and TPI/CNTOH nanocomposites exhibited a tube-like shape, and the CNTL and CNTOH fillers were well dispersed in the TPI matrix. In addition, the thermal stability of TPI significantly increased upon the introduction of a small amount of both CNTL/CNTOH fillers (0.15 wt%), owing to the satisfactory dispersion of the CNTL/CNTOH in the TPI matrix.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.71-72
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• 2006

We investigated a simultaneous living anionic polymerization process of isoprene (I) and 4styrene-d_8$ (S) in $benzene-d_6$ as a solvent with sec-buthyllithium as an initiator into polyisoprene(PI)-block-poly($styrene-d_8$)(PS) and the polymerization-induced molecular self-assembling process. This process was observed in-situ by time-resolved small-angle neutron scattering (SANS) experiment. The SANS profiles measured exhibited three time regions, where (i) the selective growth of PI chains occurs; (ii) the living chain ends switch from isoprenyllithium to styryllithium, and (iii) the SANS exhibited the polymerization induced disorder-to-order transition and order-to-order transition.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.326-326
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• 2006

The combination of living anionic and coordination polymerization techniques enabled to synthesize the polystyrene-b-polyisoprene-b-poly (butyl isocyanate) triblock polymers. Their microphase-separated structures were zig-zag structures for high ${\phi}_{PIC}$ samples, and hockey-puck structures were also observed. The phase diagram for PSt-b-PIp-b-PIC rod-coil polymers was different from that for PS-PBd-PMMA triblock polymers, and it was found that ${\phi}_{PIC}$ was the important factor to determine the microphase-separated structures.

• Macromolecular Research
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• v.11 no.3
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• pp.152-156
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• 2003

We investigated epitaxial relations of phase transitions between the lamellar (L), hexagonally perforated layers (HPL), and gyroid (G) morphologies in styrene-isoprene diblock copolymer (PSI) and polyisoprene (PI)/PSI blend using rheology and small angle X-ray scattering (SAXS) techniques. In HPLlongrightarrowG transitions, six spot patterns of G phase were observed in two-dimensitional SAXS pattern. On the other hand, in direct L-longrightarrowG transition without appearance of HPL phase, the polydomain patterns of G phase were observed. From present study, it was understood that direct LlongrightarrowG transition of blend may be suppressed by high-energy barrier of transition and mismatches in domain orientation between epitaxially related lattice planes.

• KOREAN JOURNAL OF PACKAGING SCIENCE & TECHNOLOGY
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• v.9 no.1
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• pp.19-24
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• 2003

We study on the phase diagram of the polymer blend. For this purpose, one PS (polystyrene) and two PI(polyisoprene) were employed whose molecular weights were low enough to make the experimental determinations possible. The weight-average molecular weight(Mw) of PS was 2514, and Mws of two PIs were 2700. Interaction energy density (IED) of the Flory-Huggins lattice theory was defined as a function of temperature and composition, and the consequent equations for the binodal, and critical points were derived. By fitting the experimental binodal points to the derived binodal curve with a nonlinear regression method, the expression for the IED was determined. And the expression for the IED obtained from this study was compared with those reported in the literatures. Also were discussed the importance of accuracy in the expression the IED, and the IED's dependency on the temperature, composition and molecular weights.

• Elastomers and Composites
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• v.44 no.1
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• pp.55-62
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• 2009

In this study, investigation on the polymerization characteristics of isoprene through nitroxide mediated controlled/"living" radical polymerization techniques was attempted. In the presence of acetol, linear increase of isoprene conversion with time and low polydispersities of the resulting polymers ($M_w/M_n$ < 1.5) were observed, which suggest successful controlled/"living" radical polymerization of isoprene. The microstructure of the resulting polyisoprene was composed of $\sim$ 22% of 3, 4, $\sim$30% of 1, 4-cis and $\sim$ 48% of 1, 4-trans. The optimum polymerization temperature was 145 $^{circ}C$, below which no significant polymerization behavior was observed. Non-cyclic nitroxide, such as di-tert-butyl nitroxide (DTBN) could not mediate the polymerization, whereas cyclic nitroxides (2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl (TEMPO) and 4-oxo-2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl (oxoTEMPO)) were successfully employed for the polymerization. However, isoprene dimerization reaction through Diels-Alder process was also observed at the given polymerization condition, which afforded a significant amount of limonene. Isoprene thermal autoinitiation was also possible, which was, however, considered to be not significant under the given polymerization condition.

• 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.25 no.5
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• pp.625-634
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• 2001

New polymeric photostabilizers containing hindered amine light stabilizer (HALS) were prepared by the reaction of liquid polyisoprene rubber grafted maleic anhydride (MAH) and 2,2,5,6-tetramethyl-4-piperidinol (TMPO). Their chemical composition and physical properties were characterized by titration, GPC and TGA analysis. The effects of polymeric HALS on the photooxidation of the styrene-butadiene rubber were studied from the UV, IR spectral changes, and photo-crosslinking was examined by the measurement of the insoluble fraction. The photooxidation of SBR upon irradiation was inhibited by addition of the new polymeric HALS. The extraction resistance of new polymeric photostabilizer was much better than that of the low molecular weight compound which is prepared by the reaction of MAH and TMPO. The new polymeric HALS ate fairly compatible with the SBR.

• Journal of Sensor Science and Technology
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• v.17 no.2
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• pp.143-146
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• 2008

Polymer-coated film SAW sensors have been fabricated and their sensing properties for toxic chemicals have been extensively investigated. Four types of the toxic chemical compounds of hydrogen cyanide(AC), carbonyl dichloride(CG), pinacolyl methylfluorophosphonate(GD), 2,2'-dichlorodiethylthio ether(HD) were used as target gases. SAW sensors using five different kinds of polymers were used to detect toxic chemicals and their gas sensing characteristics were investigated. The polymers used as the sensing materials were polyisobutylene(PIB), polyepichlorohydrin(PECH), polydimethylsiloxane(PDMS), polybutadiene(PBD) and polyisoprene(PIP). The recommendable mixing ratio of PIB, PECH, PDMS, PBD and PIP to solvents were 1:30, 1:40, 1:10, 1:30 and 1:30, respectively. The sensing characteristics of the SAW sensors were measured by using E-5061A network analyzer.