• Polymer(Korea)
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• v.34 no.6
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• pp.501-506
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• 2010

Natural chitosan has high molecular weight and the poor solubility in water. Water-soluble chitosan with low molecular weight was prepared by the hydrolysis method. In order to develop an efficient gene delivery carrier, chitosan was conjugated with lipoic acid to form the comb-type copolymer. The copolymer with the amphiphilic property formed the self-assembled nanoparticles in the aqueous solution. The average size of nanoparticles was 217.6 nm and the average size of nanoparticles/DNA complex was 170 nm. New chitosan-lipoic acid copolymer showed the low cytotoxicity and 10 times higher transfection efficiency than that of the pure chitosan.

• Membrane Journal
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• v.19 no.2
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• pp.89-95
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• 2009

A comb-like copolymer consisting of a poly(vinyl chloride) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. PVC-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP). This comb-like copolymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the -OH groups of PHEA in the graft copolymer and the -COOH groups of IDA. Upon doping with phosphoric acid (PA, $H_3PO_4$) to form imidazole-PA complexes, the proton conductivity of the membranes continuously increased with increasing PA content. A maximum proton conductivity of 0.011 S/cm was achieved at $100^{\circ}C$ under anhydrous conditions. The PVC-g-PHEA/IDA/PA complex membranes exhibited good mechanical properties, i.e. 575 MPa of Young's modulus, as determined by a universal testing machine (UTM). Thermal gravimetric analysis (TGA) shows that the membranes were thermally stable up to $200^{\circ}C$.

• 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.

• Membrane Journal
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• v.29 no.4
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• pp.223-230
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• 2019

In this paper, we develop a polymeric blend membrane based on $CO_2$-philic poly(2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] ethyl methacrylate)-poly(oxyethylene methacrylate) (PBEM-POEM) comb copolymer, which was synthesized by facile free radical polymerization. The PBEM-POEM (PBE) comb copolymer was blended with a commercial oligomer, low-molecular-weight poly(ethylene glycol) (PEG, $M_w=200gmol^{-1}$) with various ratios to prepare $CO_2/N_2$ separation membranes. From the result of $CO_2/N_2$ separation test of the PBE/PEG blend membranes with the various PEG contents, we could conclude that with increasing PEG content, the $CO_2/N_2$ selectivity significantly increased while the CO2 permeability decreased showing trade-off relationship. However, when comparing the performance of the PBE/PEG (9 : 1) with the PBE/PEG (7 : 3) membrane, the $CO_2$ permeance decreased by only 8.3%, while the $N_2$ permeance decreased by 69.1%. Therefore, the $CO_2/N_2$ selectivity dramatically increased from 33.8 to 100.3. This could be because the POEM chains, which account for 80% of the PBE copolymer, favorably interact with PEG and lead to a more compact chain structure, which was confirmed by FT-IR, XRD and SEM analysis. The PBE/PEG (7 : 3) blend membrane had the most optimal gas separation performance, showing a $CO_2$ permeance of 170.5 GPU and $CO_2/N_2$ selectivity of 100.3.

• Membrane Journal
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• v.18 no.2
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• pp.132-137
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• 2008

Nanofiltration membranes were prepared based on coating a sulfonated comb-like copolymer layer on top of a poly(vinylidene fluoride) (PVDF) support. The comb-like copolymer comprising poly(vinyl chloride) backbone and poly(styrene sulfonic acid) side chains, i.e. PVC-g-PSSA was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of PVC. The successful synthesis of graft copolymers were confirmed by nuclear magnetic resonance ($^1H$-NMR), FT-IR spectroscopy and wide angle X-ray scattering (WAXS). Composite nanofiltration membranes consisting PVC-g-PSSA as a top layer exhibited the increase of both rejections and solution flux with increasing PSSA concentration. This performance enhancement is presumably due to the increase of SO3H groups and membrane hydrophilicity. The rejections of composite membranes containing 71 wt% of PSSA were 88% for $Na_2SO_4$ and 33% for NaCl, and the solution flux were 26 and $34L/m^2h$, respectively, at 0.3 MPa pressure.

• Journal of the Korean Chemical Society
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• v.47 no.1
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• pp.59-66
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• 2003

The comb-type grafted polymer hydrogels, which composed of N-isopropylacrylamide monomer and oligo(N-isopropylacrylamide-co-tert-butylacrylamide) [oligo(NIPAAm-co-t-BAM)], were synthesized by redox polymerization in 5~10% methanol aqueous solution using ammonium peroxodisulfate (APS) at 4 oC for 24h. The lower critical solution temperatures (LCSTs) of the comb-type grafted hydrogels were decreased with increase of t-BAM content in the grafted copolymer. We observed the effect of crosslinker and concentration of oligo(NIPAAm-co-t-BAM) on the shrinking/swelling ratio of hydrogels. Changes of shrinking/swelling ratio were decreased with increase of concentration of crosslinker. The increase of grafted oligo(NIPAAm-co-t-BAM) in the hydrogel shows an fast changes of shrinking/ swelling rate. The comb-type grafted hydrogels are expected to be valuable for the sensing materials of time-temperature labels(TTLs).

• Membrane Journal
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• v.27 no.6
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• pp.499-505
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• 2017

The increasing number of natural disasters resulting from anthropogenic greenhouse gas emissions has prompted the development of a gas separation membrane. Carbon dioxide ($CO_2$) is the main cause of global warming. Organic polymeric membranes with inherent flexibility are good candidates for use in gas separation membranes and poly(dimethyl siloxane)(PDMS) specifically is a promising material due to its inherently high $CO_2$ diffusivity. In addition, poly(vinyl pyrrolidine)(PVP) is a polymer with high $CO_2$ solubility that could be incorporated into a gas separation membrane. In this study, poly(dimethyl siloxane)-poly(vinyl pyrrolidine)(PDMS-PVP) comb copolymers with different compositions were synthesized under mild conditions via a simple one step free radical polymerization. The copolymerization of PDMS and PVP was characterized by FTIR. The morphology and thermal behavior of the produced polymers were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Composite membranes composed of PDMS-PVP on a microporous polysulfone substrate layer were prepared and their $CO_2$ separation properties were subsequently studied. The $CO_2$ permeance and $CO_2/N_2$ selectivity through the PDMS-PVP composite membrane reached 140.6 GPU and 12.0, respectively.

• 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.

• Membrane Journal
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• v.29 no.2
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• pp.88-95
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• 2019

Hydrocarbons containing carbon double bonds are generally called olefins and it is extensively used in petro-chemical industry as essential base material. Especially, olefins are essential in polymer synthesis and thus the effective separation and purification of olefins from gas mixture are very important and it gives significant positive effect on the future industrial development. In this study, we fabricated polymeric composite membrane based on poly(1-trimethylsilyl-1-propyne) (PTMSP) for propylene/nitrogen separation and enhancement of its separation performance by grafting amphiphilic copolymer. Furthermore, to accelerate facilitated transport for propylene molecules, Ag salt ($AgBF_4$) and ionic liquid ($EMIM-BF_4$) was incorporated to polymer composite membranes. The neat PTMSP membrane exhibited extremely high gas permeance and low gas selectivity due to its high free volume. To address this issue, PTMSP was grafted with poly(oxyethylene glycol methacrylate) (POEM) and poly(ethylene glycol) behenyl ether methacrylate (PEGBEM). Additionally, the additives such as $AgBF_4$ and $EMIM-BF_4$ further increased the propylene permeance, resulting in increment of propylene/nitrogen selectivity.

• Membrane Journal
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• v.30 no.4
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• pp.252-259
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• 2020

Olefins are industrially important materials used for the synthesis of various petrochemicals. During the polymerization process, unreacted olefin monomers are discharged together with a large amount of nitrogen. For economic benefits, these olefin gases should be efficiently separated from nitrogen. In this study, a poly(glycidyl methacrylate-co-methyl methacrylate) (PGM) comb-like copolymer was synthesized and 4,4'-diaminoazobenzene (DAAB) was introduced to the copolymer to prepare a cross-linked membrane for C₃H₆/N₂ separation. PGM and DAAB were readily reacted at room temperature through an epoxide-amine reaction without additional thermal treatment. PGM-based membrane, which is a glassy polymer, showed a faster permeation of N₂ compared to C₃H₆. The pristine PGM membrane exhibited the N₂ permeability of 0.12 barrer and the high N₂/C₃H₆ selectivity of 32.4. As DAAB was introduced as a cross-linker, the thermal stability of the membrane was significantly improved, which was confirmed by TGA result. The N₂/C₃H₆ selectivity was decreased at 1 wt% of DAAB content, but the N₂ permeability increased by approximately 4.7 times. We analyzed N₂/C₃H₆ gas separation properties through a glassy polymer-based membrane, which has not been widely studied. Also, we proposed that thermal stability of the membrane can be greatly improved by the cross-linking method.