• Polymer(Korea)
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• v.39 no.1
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• pp.165-168
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• 2015

Thermoresponsive polymers were successfully synthesized by a combination of atom transfer radical polymerization (ATRP) and Cu(I)-catalyzed 1,3-dipolar cycloaddition of azide and alkynes (click chemistry). Poly(2-hydroxyethyl methacrylate) (PHEMA) was synthesized by ATRP, followed by introduction of alkyne groups using pentynoic acid, leading to HEMA-alkyne. Homopolymers having secondary amine groups, tertiary amines with hydroxyethyl and hydroxypropyl groups were synthesized by adding 2-azido-N-ethyl-ethanamine, 2-[(2-azidoethyl)amino]ethanol, and 2-[(2-azidoethyl)amino]propanol, respectively, to the PHEMA-alkyne backbone using click chemistry. Molecular weight (MW), molecular weight distribution (MWD), and click reaction efficiency were determined by gel permeation chromatography (GPC) and $^1H$ NMR spectroscopy. The transmission spectra of the 1.0 wt% aqueous solutions of the resulting polymers at 650 nm were measured as a function of temperature. Results showed that the lower critical solution temperature (LCST) could be easily controlled by the length of the hydroxyalkyl groups.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.126.2-126.2
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• 2010

The "grafting from" technology to prepare the well-defined microphase-separated structure of polymer using atom transfer radical polymerization (ATRP) will be introduced in this presentation. Various amphiphilic comb copolymers were synthesized through this approach using poly (vinylidene fluoride) (PVDF), poly (vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-co-CTFE) and poly(vinyl chloride) (PVC) as a macroinitiator. Hydrophilic side chains such as poly (styrene sulfonic acid) (PSSA) or poly (sulfopropyl methacrylate) (PSPMA) were grafted from the mains chains using direct initiation of the chlorine atoms. The structure of mass transport channels has been controlled and fixed by crosslinking the hydrophobic domains, which also provides the greater mechanical properties of membranes. Successful synthesis and microphase-separated structure of the polymer were confirmed by $^1H$ NMR, FT-IR spectroscopy and TEM. The grafted/crosslinked membranes exhibited good mechanical properties (400 MPa of Young's modulus) and high thermal stability (up to $300^{\circ}C$), as determined by a universal testing machine (UTM) and TGA, respectively.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.270-273
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• 2009

A comb-like copolymer consisting of a poly(vinylidene fluoride-co-chlorotrifluoro-ethylene) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. P(VDF-co-CTFE)-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP) using CTFE units as a macroinitiator. Successful synthesis and a microphase-separated structure of the copolymer were confirmed by proton nuclear magnetic resonance (1H-NMR), FT-IR spectroscopy, and transmission electron microscopy (TEM). This comb-like polymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the -OH groups of PHEA and the -COOH groups of IDA. Upon doping with phosphoric acid ($H_3PO_4$) to form imidazole-$H_3PO_4$ complexes, the proton conductivity of the membranes continuously increased with increasing $H_3PO_4$ content. A maximum proton conductivity of 0.015 S/cm was achieved at $120^{\circ}C$ under anhydrous conditions. In addition, these P(VDF-co-CTFE)-g-PHEA/IDA/$H_3PO_4$ membranes exhibited good mechanical properties (765 MPa of Young's modulus), and high thermal stability up to $250^{\circ}C$, as determined by a universal testing machine (UTM) and thermal gravimetric analysis (TGA), respectively.

• Korean Chemical Engineering Research
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• v.52 no.2
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• pp.209-213
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• 2014

A graft copolymer of poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-POEM) was synthesized via atom transfer radical polymerization (ATRP) and used as a structure-directing agent to prepare $Al@Fe_2O_3$ core-shell nanocomposites through a sol-gel process. The amphiphilic property of PVC-g-POEM allows for good dispersion of Al particles and leads to specific interaction with iron ethoxide, a precursor of $Fe_2O_3$. Secondary bonding interaction in the sol-gel composites was characterized by Fourier transform-infrared (FT-IR) spectroscopy. The well-organized morphology of $Al@Fe_2O_3$ core-shell nanocomposites was observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Energy dispersive X-ray (EDX) and X-ray diffraction (XRD) were used to analyze the elemental composition and crystallization structure of the composites.

• Membrane Journal
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• v.18 no.3
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• pp.219-225
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• 2008

In this research, polydimethylsiloxane-polymethylmethacrylate (PDMS-PMMA) block copolymer was synthesized from polydimethylsiloxane (PDMS) and methylmethacrylate (MMA) monomer using atom transfer radical polymerization (ATRP). The synthesis characterization of the PDMS-b-PMMA copolymer membrane was carried out by a FT-IR, $^1H$-NMR, GPC and DSC. The permeabilities of nitrogen and hydrogen gases were observed being $1.2{\sim}l.5$ barrer and $6.2{\sim}10.5$ barrer, respectively. Simultaneously, selectivities of hydrogen against nitrogen were $5.3{\sim}6.9$. The permeability and selectivity of PDMS-b-PMMA copolymer membrane were showed lower than the PDMS membrane, but higher than the PMMA membrane.

• Polymer(Korea)
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• v.27 no.1
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• pp.17-25
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• 2003

Using atom transfer radical polymerization (ATRP), polystyrene macroinitiators and polystyrene-b-poly(t-butyl acrylate) (PS-b-P(tBA) block copolymers were synthesized by CuBr/PMDETA catalyst system in solution. After hydrolysis, polystyrene-b-poly(acrylic acid), amphiphilic block copolymers, were formed. Subsequent neutralization of polyacid block led to the block ionomers. The molecular weight of the synthesized PS-b-P(tBA) block copolymers was easily-controlled to 5000-10000 and their distributions were less than 1.2. The chemical structures of the synthesized block copolymers were characterized by $^1$H-NMR and FT-IR. In the DSC thermograms, $T_g$ appeared in the vicinity of 100 $^{\circ}C$ because of higher styrene content. In addition, the phase separation of the block ionomers was observed by TEM.

• Macromolecular Research
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• v.16 no.2
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• pp.103-107
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• 2008

Carbon nanodots were prepared by the pyrolysis of a triblock copolymer. The triblock copolymer, poly(methyl methacrylate)-b-polystyrene-b-poly(methyl methacrylate) was synthesized by atom transfer radical polymerization using an initiator containing a diacetylene group. A polymer thin film on a mica substrate was prepared by spin-casting at 2,000 rpm from a 0.5 wt% toluene solution of the triblock copolymer. After drying, the cast film was vacuum-annealed for 48 h at $160^{\circ}C$. The annealed film formed a spherical morphology of polystyrene domains with a diameter of approximately 30 nm. The film was exposed to UV irradiation to induce a cross-linking reaction between diacetylene groups. In the subsequent pyrolysis at $800^{\circ}C$, the cross-linked polystyrene spheres were carbonized and the poly(methyl methacrylate) matrix was eliminated, resulting in carbon nanodots deposited on a substrate with a diameter of approximately 5 mn.

• Macromolecular Research
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• v.16 no.2
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• pp.169-177
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• 2008

This paper reports a facile synthesis of new water-soluble poly(ethylene oxide) (PEO)-based amphiphilic block copolymers showing pH sensitive phase transition behaviors. The copolymers were prepared by atom transfer radical polymerization (ATRP) of methacrylamide type of monomers carrying a sulfonamide group using a PEO-based macroinitiator and a Cu(I)Br/$Me_6TREN$ catalytic system in aqueous media. The resulting polymers were characterized by a combination of $^1H$-NMR, size exclusion chromatography, and UV/Visible spectrophotometeric analysis. The micellization of the block copolymers as a drug-loading mechanism in aqueous media using fluorescein salt was examined as a function of pH. The stable micelle formation and its loading efficacy suggest that the block copolymers can be used as precursors for drug-nanocontainers.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.324-324
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• 2006

In copolymerization of methyl acrylate (MA) and methyl methacrylate (MMA) with various ratios of MA to MMA and $[CuCl]/[PMDETA]/[PVAc-CCl_{3}]$ catalyst system in bulk at $80^{\circ}C$ via ATRP, several terpolymer with different copolymer composition, were synthesized. The atom transfer radical copolymerization of MA and MMA with macroinitiator, is very sensitive to molecular weight and its distribution. In this work it was possible to calculate the molecular weight of the terpolymers and show that it is close to the experimentally determined number average molecular weight from GPC.

• Polymer(Korea)
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• v.33 no.5
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• pp.452-457
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• 2009

Hybrid nanomaterials consisting of multi-walled carbon nanotube(MWNT) and/or PEDOT of conductive polymer were prepared in this study. In the presence of catalyst and ligand, the MWNT-Br compound prepared by the successive surface treatment reaction was mixed with MMA to initiate the atom transfer radical polymerization process. PMMA was covalently linked to the surface of MWNT for the formation of MWNT/PMMA nanocomposites. The EDOT and oxidant were added in the aqueous emulsion of PS produced via a miniemulsion polymerization process and then it proceeded to carry out the oxidative chemical polymerization of EDOT for the preparation of PEDOT/PS nanoparticles with the core-shell structure. The aqueous dispersion of PEDOT:poly(styrene sulfonate) (PSS) was mixed with the silica particles treated with a silane compound and thus PEDOT:PSS-clad silica nanoparticles were prepared by the surface chemistry reaction. The hybrid nanomaterials were analyzed by using TEM, FE-SEM, TGA, EDX, UV, and FT-IR.