• Polymer(Korea)
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• v.33 no.5
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• pp.458-462
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• 2009

We have synthesized ABC linear triblock copolymers, i.e., polystyrene-b-poly(ethylene oxide)-b-polylactide, via sequential anionic and ring-opening polymerizations. In the first anionic polymerization step, styrene was polymerized in cyclohexane using sec-butyllithium as the initiator. Poly (styryl) lithium was hydroxylated by the addition of ethylene oxide, and the subsequent protonation with methanolic HCl. In the second anionic polymerization step, potassium naphthalenide was used to deprotonate the hydroxyl group of the PS to generate the macroinitiator of PS-$O^-K^+$. Polymerization of ethylene oxide was performed in THF and terminated with methanolic HCl. In the ring-opening polymerization step, the PS-b-PEO-$AlEt_2$ macroinitiator was prepared from an $AlEt_3$/pyridine system in THF, and the polymerization of lactide was performed at $90^{\circ}C$. The resulting block copolymers showed well-defined molecular weights and narrow molecular weight distributions as revealed by $^1H$- NMR spectroscopy and gel permeation chromatography (GPC).

• Polymer(Korea)
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• v.32 no.4
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• pp.385-389
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• 2008

Chain propagation and chain transfer in anionic polymerization of hexafluoropropylene oxide were investigated under various reaction conditions such as the stabilization of reaction temperature, the amount of hexafluoropropylene solvent, and the feeding rate of hexafluoropropylene oxide monomer. Anionic initiator for the polymerization was synthesized from cesium fluoride and hexafluoropropylene oxide in tetraethyleneglycol dimethylether. It was possible to obtain a high molecular weight poly(HFPO) ($M_w$ 14800) using the anionic initiator in conditions of stabilized reaction temperature, and optimized addition of solvent and monomer feeding (HFP/initiator mole ratio=31.5 and HFPO feeding rate=11.67 g/hr). Otherwise, chain transfer reaction in anionic polymerization was increased. From the results of molecular weight in various reaction conditions, it was found that chain propagation and chain transfer in anionic polymerization of HFPO were very sensitive to reaction conditions.

• Macromolecular Research
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• v.13 no.5
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• pp.367-372
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• 2005

As a preliminary work for the preparation of nylon 6/c1ay nanocomposites by reactive extrusion, nylon 6/c1ay nanocomposites were prepared by anionic polymerization in a flask. In order to investigate the effect of the intercalation of clay layers, the clay feeding times, such as in pre-mixing where the clay was fed before initiation of polymerization and in after-mixing method where the clay was fed after initiation of polymerization, were changed. The appearance of the WAXD peak of nanocomposites prepared by the pre-mixing method was obvious and the tensile strength was decreased compared with that of pure nylon 6, which indicates that the clay layers were not dispersed and distributed. During the preparation of the nanocomposites by the after-mixing method, disordering of the clay layers was observed with increasing clay addition time and was suspected to result from the rapid polymerization of nylon 6 within the clay layers.

• Composites Research
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• v.32 no.6
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• pp.375-381
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• 2019

Multiwalled carbon nanotubes (MWCNTs) are covalently functionalized with isocyanates by directly reacting commercial hydroxyl functionalized MWCNTs with excess 4,4'-methylenebis (phenyl isocyanate) (MDI) and hexamethylene diiosocyanate (HDI). HDI-modified MWCNTs results in a higher surface isocyanate density than MDI-modified MWCNTs. Anionic ring-opening polymerization of ε-caprolactam is conducted using a sodium caprolactam initiator in combination with a di-functional hexamethylene-1,6-dicarbamoylcaprolactam activator in the presence of isocyanate functionalized MWCNTs. This polymerization proceeds in a highly efficient manner at relatively low reaction temperature (150℃) and short reaction times (10 min). During the polymerization, the isocyanate functionalized MWCNTs act not only as reinforcing fillers but also as second activators. Nanocomposites with HDI modified MWCNTs exhibit higher reinforcement and faster isothermal crystallization than MDI modified MWCNTs. The results show that PA6 chains grow more effectively from HDI modified MWCNT surface than from MDI modified MWCNT surface, resulting in stronger interaction between PA6 and MWCNTs.

• Proceedings of the Korean Fiber Society Conference
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• 1995.04a
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• pp.6-7
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• 1995

• Journal of Environmental Science International
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• v.15 no.6
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• pp.593-600
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• 2006

SIS triblock copolymers, one of the major raw materials of oil gelling agent, were synthesized by living anionic polymerization and the resultant copolymers formed with various shapes and sizes were used to examine their oil gelling capacities. Coupling method was adapted to form final triblock products from diblock living polymers. Prior to polymerization, the impurities in monomers and solvents were throughly removed by killing technique. We experimentally investigated the effects of operating parameters of synthesis and forming of SIS triblock copolymers on oil gelling capacity. The photocatalytic decomposition of SIS triblock copolymer under ultraviolet circumstance was also investigated and it is found that the addition of P-25 enhances the photocatalytic decomposition.

• Elastomers and Composites
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• v.14 no.4
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• pp.231-252
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• 1979

Polymerization of 2-pyrrolidone was carried out through anionic mechanism using $SO_2/KOH$ as catalyst. The effects of KOH concentration, $SO_2/KOH$ mole ratio and temperature on polymerization were investigated. The conversion and viscosity of polymers were measured at various polymerization conditions. It was observed that as the concentration of KOH was increased, equilibrium conversion was also increased. It was, however, found that after the concentration of KOH was reached above 8 mole percent, the equilibrium conversion was decreased. The highest rate of polymerization and maximum conversion were obtained when $SO_2/KOH$ mole ratio was around 0.5. It was also found that the rate of polymerization and the equilibrium conversion were higher at $50^{\circ}C$. than at $30^{\circ}C$. but the viscosity of polymer solution at $50^{\circ}C$. was not so high as expected. The rate constant, $K_p$ of polymerization, was determined by least square method: the value of $K_p$ was observed as 16 liter/mole hour at $50^{\circ}C$. and 2.6 liter/mole hour at $30^{\circ}C$., respectively. The mechanism of polymerization was also discussed.

• Elastomers and Composites
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• v.47 no.1
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• pp.30-35
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• 2012

Novel bio-polybutadiene polymers with controlled molecular weight (MW), MW distribution, chemical composition and micro structure were synthesized by a living anionic polymerization of butadiene and the subsequent coupling reaction of the thus obtained living polybutadiene and a vegetable oil. Anionic polymerization of butadiene was carried out in THF solvent using n-BuLi initiator. The resulting living polybutadienyllithium polymer was then reacted with epoxidized soybean oil (ESO) to obtain a star-polymer of polybutadiene and vegitable oil. Three different bio-elastomers were prepared by coupling living polybutadienes of MWs 1000, 5000 and 1000g/mol with ESO. The molecular structure and MW of the polybutadienes and bioelastomers were characterized by $^1H$-NMR, FTIR and GPC techniques.

• Polymer(Korea)
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• v.25 no.1
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• pp.1-5
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• 2001

Monomer casting nylons were synthesized by casting anionic polymerization of ${\varepsilon}$-caprolactam. Polymerization rates, molecular weights of the products and the conversions were determined while varying the content of catalysts in the range of 0.2~0.6 mol% and 0.1~1.0 mol% for initiator. The polymerization rates were enhanced as the ratio of catalysts to initiator increased. The maximum molecular weight was observed when the ratio of catalysts to initiator was 0.8, and as the ratio increased the molecular weight decreased. On the other hand, when the ratio of catalysts to initiator was below 0.8, the conversions and the molecular weights were abruptly diminished due to the termination of growing chains.

• Journal of the Korean Chemical Society
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• v.21 no.2
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• pp.132-138
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• 1977

Anionic polymerization of ${\varepsilon}$-caprolactam via $SO_2$/KOH catalysis was attempted in order to find an optimal reaction condition and physical properties of the polymers. The yield of conversion was relatively low at low temperature and high at high temperature between $150^{\circ}C\;to\;180^{\circ}C$ regardless of $SO_2$/KOH mole ratio in polymerization of ${\varepsilon}$-caprolactam.The inherent viscosity of nylon 6 obtained via $SO_2$/KOH catalysis was 1.2∼2.7. The kinetic equation for the $SO_2$/KOH catalyzed polymerization has been derived and experimentally verified.