• Polymer(Korea)
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• v.34 no.2
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• pp.159-165
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• 2010

Dipyridine-terminated polystyrenes and polybutadienes were synthesized by the chain endfunctionalization reaction of polystyryllithium (PSLi) and polybutadienyllithium (PBDLi) with di(2-pyridyl) ketone(DPK) using a living anionic polymerization method in the Ar-glove box. Living polymeric lithiums with low molecular weights (Mw=1000~2000 g/mol) were used to investigate the chain end-functionalization yield with DPK and the degree of coupling reaction by the attack of organolithium to the pyridine ring in the presence of TMEDA using GPC, $^1H$-NMR, $^{13}C$ analysis. DPK-terminated PBD exhibited much higher functionalization yield and less amount of coupling reaction compared with DPK-terminated PS. 86% functionalization yield with 9% degree of coupling was obtained when the PBDLi was added dropwise to DPK solution at room temperature. The functionalization yield was increased as the reaction temperature decreased, however, no LiCl effect was observed in this chain end-functionalization reaction with DPK.

• Macromolecular Research
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• v.14 no.3
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• pp.287-299
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• 2006

To successively synthesize star-branched polymers, we developed a new iterative methodology which involves only two sets of the reactions in each iterative process: (a) an addition reaction of DPE or DPE-functionalized polymer to a living anionic polymer, and (b) an in-situ reaction of 1-(4-(4-bromobutyl)phenyl)-1-phenylethylene with the generated 1,1-diphenylalkyl anion to introduce one DPE functionality. With this methodology, 3-, 4-, and 5-arm, regular star-branched polystyrenes, as well as 3-arm ABC, 4-arm ABCD, and a new 5-arm ABCDE, asymmetric star-branched polymers, were successively synthesized. The A, B, C, D, and E arm segments were poly(4-trimethylsilylstyrene), poly(4-methoxystyrene), poly(4-methylstyrene), polystyrene, and poly(4-tert-butyldimethylsilyloxystyrene), respectively. All of the resulting star-branched polymers were well-defined in architecture and precisely controlled in chain length, as confirmed by SEC, $^1H$ NMR, VPO, and SLS analyses. Furthermore, we extended the iterative methodology by the use of a new functionalized DPE derivative, 1-(3-chloromethylphenyl)-1-((3-(1-phonyletheny1)phenyl) ethylene, capable of introducing two DPE functionalities via one DPE anion reaction site in the reaction (b). The number of arm segments of the star-branched polymer synthesized by the methodology could be dramatically increased to 2, 6, and up to 14 by repeating the iterative process.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.123-124
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• 2006

Ionic liquids (ILs) are collecting keen interests as an advanced substituent of electrolyte solution as well as novel solvents. In the present talk, I will introduce some strategies to fix IL structure on polymer chains to prepare polar polymers with low glass transition temperature. Namely, cationic, anionic, and zwitterionic monomers have been prepared, and they have been homopolymerized or copolymerized to prepare polymer electrolytes with different properties. The polymers themselves showed very poor ionic conductivity, but it was improved by suitable spacer between charged site and main chain. Other unique characteristics of functional ILs and new polymerized ionic liquids will also be mentioned.

• Journal of the Korean Wood Science and Technology
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• v.18 no.2
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• pp.36-48
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• 1990

This experiment was carried out to improve the quality of high absorbent polymer which has excellent absorptivity and water retention compared to pulp and absorption sheet, through absorption characteristics-absorptive power, water retention, absorption rate, gel strength, pH, particle size, and moisture content. - of six polymers, namely, anionic polyacrylamide, cationic polyacrylamide, polyacrylic, acid polyvinyle alcohol 500, and 1500, and a-cellulose. and to examine the possibility of substitution of amide groups for carboxyl group and/or hydroxyl group which were commercial high absorbent polymer by comparing the absorption characteristics of the polymers. Polyacrylamide has high absorptive power and water retention, but has low gel strength and poor absorption rate. The rest of polymers were similiar to ${\alpha}$-cellulose in every respect. Thus, polyacrylamides could be replaced with polyacrylic acid and polyvinyl alcohol which are presently a high absorbent polymers. In comparing the absorption characteristics and the absorptive power of the polymers-anionic polyacrylamide, cationic polyacrylamide, polyacrylic acid, polyvinyle alcohol. a-cellulose-the absorptive power was in inverse proportion to the gel strength and absorption rates, affected by the particle size and pH change.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.198-198
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• 2006

We have identified sodium benzanilide (Na-BA), sodium diphenyl amine (Na-DPA) and sodium deoxibenzoin (Na-DB) as very efficient initiators for the living anionic polymerization of HIC. It has a slow propagation rate with the additive function of chain end protection, offering in the process a perfect control over MW and MWD. The well-defined amphiphilic coil-rod, coil-rod-coil, and rod-coil-rod block-copolymers of PHIC and P2VP with controlled architecture have been synthesized for the first time with ${\sim}100\;%$ yields. The resulting block copolymers showed lamellar film, donuts, solid and hollow micelles, by simply varying the solvents and the block compositions.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.380-380
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• 2006

Styrene-Butadiene diblock or styrene-butadiene-styrene triblock copolymers are industrially important materials for asphalt modification and adhesives. A kinetic modeling study on non-isothermal anionic styrene-butadiene diblock copolymerization system is presented. The model deals with the association/dissociation reaction of initiator and propagating ion pairs in its kinetic scheme. By comparing model calculation results with real plant data, it is possible to obtain useful ideas for more efficient plant operation. For example, the model clearly provides important relation between the reaction temperature profile and the conversion of monomers.

• Polymer(Korea)
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• v.28 no.2
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• pp.111-120
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• 2004

The interaction between poly(diallyldimethylammonium chloride) (PDADMAC) of positive charge per repeating unit and anionic surfactant, sodium dodecyl sulfate (SDS) has been investigated by light scattering, turbidimetry and fluorescence. Chain behavior of PDADMAC in 0.3 M NaCl aqueous solution seems like neutral polymer chain In good solvent. By adding SDS into PDADMAC solution, strong attractive interaction develops between them, and can be described with two kinds of critical aggregation concentration(CAC). First, at [SDS]/]DADMAC] 0.06, intramolecular critical micellization of SDS occurs inside a single polymer chain. The maximum size of SDS-polymer complex is observed just before intramolecular CAC. Above intramolecular CAC, the size of this complex starts to shrink slowly due to involvement of polymer subchain in micelle. Second, intermolecular CAC is also observed at [SDS]/[DADMAC] 0.5 by means of turbidimetry. Strong aggregation of polymer chains decorated with many micelles occurs after the second CAC, and huge aggregates have formed.

• Korean Chemical Engineering Research
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• v.43 no.2
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• pp.299-304
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• 2005

There have been many efforts to use anionic hydrogels as oral protein delivery carriers due to their pH-responsive swelling behavior. The dynamic swelling behavior of poly(methacrylic acid-co-methacryloxyethyl glucoside) [P(MAA-co-MEG)] hydrogels was investigated to determine the mechanism of water transport through these anionic hydrogels. The exponential relation $M_t/M_{\infty}=kt^n$ was used to calculate the exponent, n, describing the Fickian or non-Fickian behavior of swelling polymer networks. The mechanism of water transport through these gels was significantly affected by the pH of the swelling medium. The mechanism of water transport became more relaxation-controlled in the swelling medium of pH 7.0 that was higher than the $pK_a$ of the gels. Experimental results of time-dependent swelling behavior of the gels were analyzed with several mathematical models. Using ATR-FTIR spectroscopy, the effect of ionization of the carboxylic acid groups in the polymer networks on the water transport mechanism was investigated.

• Macromolecular Research
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• v.14 no.3
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• pp.272-286
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• 2006

Dendritic hyperbranched poly(methyl methacrylate)s (PMMA)s, whose branched architectures resemble the 'dendron' part(s) of dendrimer, were synthesized by an iterative methodology consisting of two reactions in each iteration process: (a) a coupling reaction of u-functionalized, living, anionic PMMA having two tert-butyldimethylsilyloxymethylphenyl(SMP) groups with benzyl bromide(BnBr)-chain-end-functionalized PMMA, and (b) a transformation reaction of the introduced SMP groups into BnBr functionalities. These two reactions, (a) and (b), were repeated three times to afford a series of dendron-like, hyperbranched (PMMA)s up to third generation. Three dendron-like, hyperbranched (PMMA)s different in branched architecture were also synthesized by the same iterative methodology using a low molecular weight, functionalized 1,1-diphenylalkyl anion prepared from sec-BuLi and 1,1-bis(3-tert-butyldime-thylsilyloxymethylphenyl)ethylene in the reaction step (b) in each iterative process. Furthermore, structurally similar, dendron-like, hyperbranched block copolymers could be successfully synthesized by the iterative methodology using $\alpha$-functionalized, living, anionic poly(2-(perfluorobutyl) ethyl methacrylate) (PRfMA) in addition to $\alpha$-functionalized, living PMMA. Accordingly, the resulting block copolymers were comprised of both PMMA and PRfMA segments with different sequential orders. After the block copolymers were cast into films and annealed, their surface structures were characterized by angle-dependent XPS and contact angle measurements. All three samples showed significant segregation and enrichment of PRfMA segments at the surfaces.

• Polymer(Korea)
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• v.28 no.6
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• pp.502-508
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• 2004

Cationic liposomes for cancer treatment have been developed in the field of chemotharpy. It was well combined on the surface of anionic tumor cell membrane by electrostatic interaction. Thus, the object of this study was to prepare the cationic liposomes capable of forming an ionic complex with the anionic cell membrane. To prepare the cationic liposomes, 1,2-distearoyl-sn-glycero-3-phosphoethanolamine (DSPE) as a cationic lipid material and polyethylenimine (PEI) as a cationic polymer were synthesized. Ionic property on the surface of liposomes was determined by the zeta potential. The adsorption characteristics of plasma protein for liposome in bovine serum were determined by the particle size and turbidity change. To estimate the stability of liposome in buffered solution, the change of particle size was measured at room temperature for seven days. The cationic liposomes were absorbed a large amount of plasma protein in bovine serum because plasma protein having anionic charge was fixed on the surface of cationic liposomes. This result indicate that the modification on the surface of liposomes using cationic polyethylenimine enhances the protein adsorption in bovine serum. Additionaly, cationic liposomes showed good stability in buffered solution for seven days.