• Elastomers and Composites
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• v.11 no.1
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• pp.54-62
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• 1976

It has been studied the graft copolymerization of glycidyl-methacrylate monomer containing two functional groups (vinyl- & epoxyl-) to chloroprene rubber. The reaction occured in the manner of chain transfer mechanism was carried out by means of solution polymerization in toluene in the presence of benzoyl peroxide as the radical initiator. The graft copolymer obtained from this work was analyzed by using IR spectrum, and the physical properties of the polymer such as the thermal behavior were also studied according to TG-DTA methods, and the potency of adhesiveness for the purpose of commercial application was investigated. Experimental results for the graft copolymerization are summarized as follows. 1) A small amount of initiator (0.5%) and 50% of monomer showed the best result for the grafting of monomer to the polymer chain of rubber while the 15% of rubber solution was found to be most suitable to raise either for the grafting ratio or the polymerization ratio. 2) Optimum temperature for better yield of graft copolymer was proved to he at $75^{\circ}C\sim80^{\circ}C$ while those of reaction time was to be $1\sim2$ hours.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2000.05b
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• pp.316-319
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• 2000

In the case of immobilizing of glucose oxidase into polypyrrole (PPy) using electrosynthesis, the glucose oxidase (GOx) forms a coordinate bond with the polymer's backbone. However, because of intrinsic insulation and net-chain of the enzyme, the charge transfer and mass transport are obstructed during the film growth. Therefore, the film growth is dull. We synthesized the enzyme electrode by electropolymerization added some organic solvent, A formative seeds of film growth is delayed by adding the solvent. The delay is induced by radical transfer between the solvent and pyrrole monomer. In the case of adding ethanol, the radical transfer shares the contribution of dopant between electrolyte anion and GOx polyanion. This may lead to increase amount of immobilized the enzyme in ppy. However, adding tetrahydrofuran (THF), the radical transfer is more brisk, resulting in short chained polymer. Therefore, the doping level is lowered and then amount of immobilized of enzyme is decreased. For the UV absorption spectra of synthetic solution before synthesis and after, in the case of ethanol added, the optical density was slightly decreased for the GOx peaks. It suggests amount of GOx in the solution was decreased and amount of GOx in the film was increased. We established qualitatively that amount of immobilization can be improved by adding a little ethanol in the synthetic solution. It is due to radical transfer reaction. The radical transfer shares the contribution of dopant between small and fast electrolyte anion and big and slow GOx polyanion.

• Bulletin of the Korean Chemical Society
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• v.16 no.11
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• pp.1056-1059
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• 1995

The bulk photopolymerization of methyl methacrylate (MMA) with primary arylsilane (e.g., phenylsilane) and various primary alkylsilanes (e.g., benzylsilane, 3-phenoxyphenyl-1-silabutane, 3-naphthyl-1-silabutane, and 3-chlorophenyl-1-silabutane) was performed to produce poly(MMA)s containing the corresponding silyl moiety as an end group. It was found for the phenylsilane that while the polymerization yields increased and then decreased with a turning point at the molar ratio of MMA:silane=10:1 as the relative silane concentration increases, the polymer molecular weights decreased, and the TGA residue yields and the relative intensities of SiH IR stretching bands increased with increment of molar ratio of silane over MMA. The photopolymerization yield of MMA with the arylsilane was found to be higher than those with the alkylsilanes and without the silanes. Thus, the silanes seemed to significantly influence on the photopolymerization as both chain initiation and chain transfer agents.

• Macromolecular Research
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• v.14 no.1
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• pp.87-93
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• 2006

Copolymers composed of hyaluronic acid (HA) and poly(N-isopropylacrylamide) (PNIPAAm) were prepared to create temperature-sensitive injectable gels for use in controlled drug delivery applications. Semi-telechelic PNIPAAm, with amino groups at the end of each main chain, was synthesized by radical polymerization using 2-aminoethanethiol hydrochloride (AESH) as the chain transfer agent, and was then grafted onto the carboxyl groups of HA using carbodiimide chemistry. The result of the thermo-optical analysis revealed that the phase transition of the PNIPAAm-grafted HA solution occurred at around 30$\∼$33$^{circ}C$. As the graft yield of PNIPAAm onto the HA backbone increased, the HA-g-PNIPAAm copolymer solution exhibited sharper phase transition. The short chain PNIPAAm-grafted HA ($M_{w}$=6,100) showed a narrower temperature range for optical turbidity changes than the long chain PNIPAAm-grafted HA ($M_{w}$=13,100). PNIPAAm-grafted HA exhibited an increase in viscosity above 35$^{circ}C$, thus allowing the gels to maintain their shape for 24 h after in vivo administration. From the in vitro riboflavin release study, the HA-g-PNIPAAm gel showed a more sustained release behavior when the grafting yield of PNIPAAm onto the HA backbone was increased. In addition, BSA released from the PNIPAAm-g-HA gels showed a maximum concentration in the blood 12 h after being injected into the dorsal surface of a rabbit, followed by a sustained release profile after 60 h.

• Polymer(Korea)
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• v.27 no.1
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• pp.26-32
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• 2003

Poly(vinyl pivalate)(PVPi) telomer containing bifunctional end groups was synthesized through radical telomerization of vinyl pivalate. The number-average molecular weight ($\bar{M}$n) of the synthesized telomers was investigated by GPC, $^1$H-NMR, and viscometric methods. PVPi telomers having a number-average molecular weight ($\bar{M}$n) of 2400~1300 g/mol were obtained. In order to control the molecular weight of telomers, chain transfer constants ($C_s$) of telogen ($CCl_4$) were determined by using the Mayo equation and simulation, which were 1.15, 1.16, and 1.18 at 40, 50, and 6$0^{\circ}C$, respectively. $\bar{M}$n of the synthesized telomers at 6$0^{\circ}C$ were between 5100 and 5400 g/mol at conversion of increasing from 18 to 72%. Those are corresponding to simulation results.

• Bulletin of the Korean Chemical Society
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• v.17 no.4
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• pp.373-376
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• 1996

The bulk thermal and photopolymerization of methyl methacrylate(MMA) with phenylsilane were performed to produce poly(MMA)s containing phenylsilyl moiety presumably as an end group. It was found for both thermal and photopolymerization that while the polymerization yields and polymer molecular weights decreased as the relative phenylsilane concentration increases, the TGA residue yields and the relative intensities of SiH IR stretching bands increased with increasing molar ratio of phenylsilane over MMA. The polymerization yield, molecular weight, and TGA residue yield for the thermal polymerization were higher than those for the photopolymerization. Thus, the phenylsilane seemed to significantly influence on the polymerization as both chain initiation and chain transfer agents. However, an appreciable silane effect was not observed on the thermal and photopolymerization of 4-vinylpyridine, acrylonitrile, styrene, and vinyltrimethoxysilane.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.296-296
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• 2006

Highly temperature stable mesoporous materials have excellent properties and potential applications. Here we show a novel poly(vinyl)silazane-block-polystyrene diblock copolymer, which was synthesized by controlled/living free radical polymerization with reversible addition fragmentation chain transfer (RAFT) route. The obtained diblock copolymer occurs the phaseseparation on the nanoscale to form ordered nanostructure, which is converted to mesoprorous ceramic after heating at 800oC. This route demonstrates the preparation of highly temperature stable mesoporous silicon carbon nitrides (SiCN) ceramic film directed from highly cross-linking poly(vinyl)silazane blocks with high ceramic yield, which is different from previous pathway.

• 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.

• Proceedings of the Korean Fiber Society Conference
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• 2003.10a
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• pp.90-90
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• 2003

Living nature was appeared in the cationic polymerization of tort-butyl vinyl ether (TBVE), initiated by iodine, carried out in toluene at -78$^{\circ}C$. It was found that the number average molar mass of the resulting polymer (equation omitted) increases linearly as the conversion to polymer increase which reveals that there is no operation of chain transfer or termination process in this system. The polymers having narrow distribution and having molar mass of the resulting polymers are dependent on molar ratio of monomer and iodine.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.158-158
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• 2012

A new kind of organic-inorganic hybrid polymer, poly(tetraphenyl)silole siloxane (PSS), was invented and synthesized for realization of its unique charge trap properties. The organic portions consisting of (tetraphenyl)silole rings are responsible for electron trapping owing to their low-lying LUMO, while the Si-O-Si inorganic linkages of high HOMO-LUMO gap provide the intrachain energy barrier for controlling electron transport. Such an alternation of the organic and inorganic moieties in a polymer may give an interesting quantum well electronic structure in a molecule. The PSS thin film was fabricated by spin-coating of the PSS solution in THF organic solvent onto Si-wafer substrates and curing. The electron trapping of the PSS thin films was confirmed by the capacitance-voltage (C-V) measurements performed within the metal-insulator-semiconductor (MIS) device structure. And the quantum well electronic structure of the PSS thin film, which was thought to be the origin of the electron trapping, was investigated by a combination of theoretical and experimental methods: density functional theory (DFT) calculations in Gaussian03 package and spectroscopic techniques such as near edge X-ray absorption fine structure spectroscopy (NEXAFS) and photoemission spectroscopy (PES). The electron trapping properties of the PSS thin film of quantum well structure are closely related to intra- and inter-polymer chain electron transports. Among them, the intra-chain electron transport was theoretically studied using the Atomistix Toolkit (ATK) software based on the non-equilibrium Green's function (NEGF) method in conjunction with the DFT.