• Macromolecular Research
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• v.15 no.6
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• pp.541-546
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• 2007

The combination of atom transfer radical polymerization (ATRP) and click chemistry was employed for the efficient preparation of well-defined block copolymers. Bromo terminated poly(methyl acrylate) (pMA-Br) was prepared by an ATRP initiator, ethyl-2-bromoisobutyrate (EBiB). Subsequently, the bromine chain end of pMA-Br was converted to an azide group by simple nucleophilic substitution reaction. ${\alpha}-Alkyn-{\omega}-bromo-functionalized$ polystyrene was also synthesized by ATRP using the alkyn-functionalized initiator, propargyl-2-bromoisobutyrate (PgBiB). In both cases, the conversion was limited to a low level to ensure a high degree of chain end functionality. Then the coupling reaction between the azide end group in $pMA-N_3$ and alkyn-functionalized PgBiB-pSt was performed by Cu(I)catalysis. This coupling reaction was monitored by gel permeation chromatography (GPC). The synthesized block copolymer was characterized by FT-IR, $^1H-NMR$ spectroscopy and $^1H-^1H$ COSY correlation spectroscopy.

• 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.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.

• Macromolecular Research
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• v.17 no.10
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• pp.770-775
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• 2009

$\omega$-Anhydride-functionalized poly(ethylene oxide) (PEO) obtained from chain-end functionalization and anionic ring-opening polymerization of ethylene oxide using n-butyllithium with potassium t-butoxide in the presence of dimethylsulfoxide (DMSO) was found to be an efficient material for the preparation of water-soluble, polymeric pro-drugs. The reaction of $\omega$-anhydride-functionalized PEO with sulfonamide or with vancomycin provided an efficient method to produce corresponding, water-soluble, PEO-conjugated sulfonamide or PEO-conjugated, vancomycin pro-drugs. These were used successfully to prepare water-dispersible, silver nanoparticles. In this study, the particle sizes were in the range of $5{\sim}40$ nm. The resulting products were characterized by $^1H$ NMR spectroscopy, transmission electron microscopy, electron and X-ray diffraction, size exclusion chromatography, and UV/Visible spectroscopy.

• Macromolecular Research
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• v.8 no.1
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• pp.44-52
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• 2000

Styrenic macromonomers with/without a silyloxy-functional group were synthesizedvia chain-end functionalization using 4-vinylbenzyl chloride as a terminating agent insec-butyllithium-initiated polymerization of styrene. The yields were 92 mol% for the silyloxy group and 88 mol% for the styrenic unit. Crystalline polystyrene-g-amorphous polystyrenes were synthesized by (η$^{5}$ -indenyl)-trichlorotitanium ((Ind)TiCl$_3$)-catalyzed copolymerizations of the macromonomers with styrene in the presence of methyl-aluminoxane (MAO) in toluene at 4$0^{\circ}C$. The macromonomer having $\alpha$, $\alpha$'-bis (4-[tert-butyldimethylsilyl-oxy]phenyl) group was also utilized for the preparation of a precursor of hydroxyl-functionalized syndio-tactic polystyrene. The obtained polymers were characterized by a combination of$^1$H, $^{13}$ C NMR spectroscopic, size exclusion chromatographic, and differential scanning calorimetric analysis. The (Ind)TiCl$_3$-catalyzed copolymerization of styrene with the macromonomer carrying the silyloxy functional group was found to be an efficient method to modify syndiotactic polystyrene without a great loss of physica] property by controlling the feud ratio of the macromonomer.

• Proceedings of the Korean Society For Composite Materials Conference
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• 2003.10a
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• pp.1-2
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• 2003

While aromatic polyimides and polyamides have found widespread use as high performance polymers, the present work addressed the need for organosoluble materials through the use of a hyperbranching scheme. The $AB_2$ monomers were prepared. The $AB_2$ monomers were then polymerized via aromatic fluoride-displacement and Yamazaki reactions to afford the corresponding hydroxyl-terminated hyperbranched polyimides (HT-PAEKI) and amine-terminated hyperbranched polyamides, respectively. HT-FAEKI was then functionalized with allyl and propargyl bromides as well as epichlorohydrin to afford allyl-terminated AT-PAEKI, propargyl-terminated PT-PAEKI, and epoxy (glycidyl)-terminated ET-PAEKI, in that order. All hyperbranched poly(ether-ketone-imide)s were soluble in common organic solvents. AT-PAEKI was blended with a bisphenol-A-based bismaleimide (BFA-BMI) in various weight ratios. Thermal, rheological, and mechanical properties of these blend systems were evaluated. Two characteristic hyperbranched polyamides, which the one has para-electron donating groups to the surface amine groups and the other has para-electron withdrawing groups to the surface amine groups, were selected to compare BMI curing behaviors. The electron rich polymer displayed ordinary Michael addition type exothermic reaction, while electron deficient polymer did display unusual curing behaviors. Based on analytical data, the later system provided the strong evidences to support room temperature curing of BMI by reactive intermediates instead of reactive primary amine groups on the macromolecule surface.