• Korean Chemical Engineering Research
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• 제52권2호
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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.

• Macromolecular Research
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• 제16권2호
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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.

• Bulletin of the Korean Chemical Society
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• 제35권9호
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• pp.2694-2698
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• 2014

A multisegmented polystyrene (PS) with pH-cleavable ester and carbamate linkages was 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). ATRP was employed to synthesize polystyrene from hydroxyl-terminated initiator using CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA) as the catalyst. The reaction of the resulting PS with sodium azide yielded the azido-terminated polymer. The hydroxyl group in the other end of the polymer was reacted with 4-nitrophenyl chloroformate (NPC), followed by reaction with propargylamine to produce an alkyne end group with a carbamate linkage. The PS with an alkyne group in one end and an azide group in the other end was then self-coupled in the presence of CuBr/2,2'-bipyridyl (bpy) in DMF to yield a desired multisegmented PS. Molecular weight and molecular weight distribution of the self-coupled polymer increased with time, as in the typical step-growth-type polymerization processes. Finally, we demonstrated that the ester and carbamate linkages of the multisegmented PS were hydrolyzed in the presence of HCl to yield individual PS chains.

• Macromolecular Research
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• 제15권6호
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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.

• 멤브레인
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• 제20권1호
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• pp.1-7
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• 2010

원자전달 라디칼 중합을 이용하여 poly(styrene sulfonic acid) 47 wt%를 가진 poly(vinylidene fluoride-co-chlorotrifluoroethylene)-g-poly(styrene sulfonic acid) (P(VDF-co-CTFE)-g-PSSA) 가지형 공중합체를 합성하였다. 티타늄 아이소프로폭사이드(TTIP)와 가지형 공중합체를 졸-겔 공정을 통하여 $TiO_2$/가지형 공중합체 복합막을 제조하였다. TTIP는 가지형 공중합체의 친수성을 가진 PSSA 영역에만 선택적으로 결합하였으며 그곳에 $TiO_2$ 나노 입자가 형성되어 성장하였다. 이와 같은 결과를 적외선과 자외선 분광학으로 확인할 수 있다. 함수량과 이온 교환 능력 (IEC)는 TTIP의 함량에 따라 감소하였고 이것은 막이 가진 술폰산의 수가 감소하기 때문이었다. TTIP가 5 중량%일 때, 막의 기계적 강도는 증가하고 수소이온 전도도도 유지되었다.

• 멤브레인
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• 제19권2호
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• pp.89-95
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• 2009

Poly(vinyl chloride) (PVC) 주사슬과 poly(hydroxyethyl acrylate) (PHEA) 곁사슬로 구성된 빗살모양의 PVC-g-PHEA 공중합체를 원자전달라디칼 중합을 통해 합성하였다. 이렇게 합성된 PVC-g-PHEA의 OH 그룹과 이미다졸 디카르복실릭산 (IDA)의 COOH 그룹과의 에스테르 반응에 의하여 가교된 전해질막을 제조하였다. 인산(PA)을 도핑하여 이미다졸-인산 착체를 형성한 결과, PA함량이 증가함에 따라 고분자 전해질막의 수소 이온 전도도가 증가하였다. 특히 100도 비가습 조건에서 수소 이온 전도도는 최대 0.011 S/cm까지 증가하였다. 만능 재료 시험기(UTM) 측정결과, 제조된 PVC-g-PHEA/IDA/PA 전해질막은 575 MPa의 높은 Young 모듈러스 및 기계적 강도를 보여주었다. 열분석 결과(TGA) 전해질막은 $200^{\circ}C$까지 열적으로 안정함을 확인하였다.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.501-504
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• 2014

A thermoresponsive polymer, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), was successfully synthesized by atom transfer radical polymerization (ATRP). Different amounts of 1,3-propanesultone were used as quaternization agent to transit the PDMAEMA into partially modified poly(zwitterions), resulting in p[DMAEMA-co-3-dimethyl(methacryloyloxyethyl)ammonium propanesulfonate] (PDMAEMA-co-PDMAPS). Molecular weight, molecular weight distribution, and degree of quarternization 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) and the upper critical solution temperature (UCST) could be easily controlled by the different composition of dimethylamino and zwitterion groups. The effect of partial quaternization on thermoresponsive properties was also studied by dynamic light scattering (DLS) with the same aqueous concentration (1.0 wt %) as employed for turbidimetry studies. The LCST and UCST values measured by DLS correlated well with those determined by turbidimetry.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.226-226
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• 2006

Ethylene was polymerized with a catalyst having sterically hindered pentamethylcyclopentadienyl ligand, $Cp^{\ast}_{2}ZrCl_{2}/MAO$, and the polymerization mixture were treated with dry oxygen (oxidative workup) to produce hydroxyl-terminated polyethylenes (PE-OH). Polyethylene-block-Poly (${\Box}-caprolactone$) was synthesized from PE-OH and ${\cdot}\^{A}-caprolactone$A by using stannous octoate as a catalyst for ring opening polymerization of ${\cdot}\^{A}-caprolactone$. Polyethylene-block-Poly(methyl methacrylate) was obtained by transforming the hydroxyl-terminated polyethylenes to macroinitiators for atom transfer radical polymerization (ATRP) and by reacting them with MMA.

• 폴리머
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• 제38권5호
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• pp.671-675
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• 2014

본 연구에서는 잘 규정된 4-arm 스타형 및 선형 고분자를 합성하여 구조에 따른 구리 프탈로시아닌(CuPc)의 분산 안정성을 비교하였다. 분산제는 (2-dimethylamino)ethyl methacrylate(DMAEMA)와 poly(ethylene glycol) methyl ether methacrylate(PEGMA)를 사용하여 activators generated by electron transfer(AGET) 원자이동라디칼중합법(ATRP)으로 합성하였다. 합성된 고분자는 젤투과 크로마토그래피(GPC)와 핵자기 공명 분광법(NMR)을 사용하여 합성한 고분자들의 분자량 및 단량체의 조성을 결정하였다. 4-Arm 스타형 고분자 및 선형 고분자 분산제에서 stabilizing group인 PEGMA의 중합도를 조절하여 copper phthalocyanine(CuPc)의 분산 안정성에 미치는 영향을 연구하였다. PEGMA의 DP가 130인 4-arm 스타형 고분자를 사용한 경우 $25^{\circ}C$에서 7일 동안 CuPc의 분산상이 안정적으로 유지되었다.

• Macromolecular Research
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• 제17권11호
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• pp.926-930
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• 2009

A new method for encapsulating nanomaterials within intermediary layer cross-linked (ILCL) polymeric micelles using a bifunctional photo-cross-linking agent was developed. For ILCL polymeric micelles, an amphiphilic triblock copolymer of poly(ethylene glycol)-b-poly(2-hydroxyethyl methacrylate)-b-poly(methyl methacrylate) (PEG-PHEMA-PMMA) was synthesized via consecutive atom transfer radical polymerization (ATRP), Di(4-hydroxyl benzophenone) dodecanedioate (BPD) was used as a bifunctional photo-cross-linking agent. The PMMA-tethered Au nanoparticles and BPD, or pyrene and BPD were encapsulated in the PEG-PHEMA-PMMA micelles, and their intermediary layers were photo-cross-linked by UV irradiation for 1 h. The HEMA units donated labile hydrogens to the excited-state benzophenone groups in BPD, and they were subsequently cross-linked by BPD through radical-radical combination. The spherical structures of the PEG-PHEMA-PMMA micelles containing the Au nanoparticles or pyrene were unaffected by the photo-cross-linking process.