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Atom Transfer Radical Polymerization of [Poly(ethylene glycol)methyl ether] Methacrylate Using an Amide-Based Initiator (아미드기를 가지는 개시제를 이용한 [Poly(ethylene glycol)Methyl Ether] Methacrylate의 원자 이동 라디칼 중합)

  • Lee, Hyo-Kyung;Lee, Sun-Gu;Paik, Hyun-Jong
    • Polymer(Korea)
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    • v.31 no.6
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    • pp.550-554
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    • 2007
  • Atom transfer radical polymerization (ATRP) has been widely used in bioconjugation as it is an efficient and facile method to prepare polymers with pre-designed structures. Quite often, bioconjugation with proteins employs primary amines in proteins as a functional group to attach an initiator. When 2-bromoisobutryl bromide, the most widely used precursor for ATRP initiator, is used, ${\alpha}-halo$ amide initiating groups are formed in the proteins, which are known to exhibit slow initiation behavior in the ATRP process. Here we studied the ATRP of [poly(ethylene glycol)methyl ether] methacrylate (PEGMA) using amide-based initiator. PEGMA differs for both the nature and size of the polymer side branches and shows good solubility in water and a property that made it an ideal candidate for biomaterials. While normal ATRP produced ill-defined p(PEGMA) with amide based initiators, the halogen exchange method and the external additional of deactivator effectively improved the control of ATRP of PEGMA.

가교 폴리에틸렌의 성형 조건에 따른 전기.화학적 특성 변화

  • Jo, Dae-Hui;Ha, Yeong-Gil;Lee, Sang-Jin;Lee, In-Ho;Park, Wan-Gi
    • Proceedings of the KIEE Conference
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    • 1999.07d
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    • pp.1587-1589
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    • 1999
  • 초고압 XLPE(가교 폴리에틸렌) 절연 케이블의 절연사고를 방지하기 위해서는 여러열화 조건하에서 절연체의 수명을 예측하는 것과 아울러 절연체(XLPE)의 성능향상을 모색하는 것이 바람직하다. 이러한 노력의 일환으로 절연재료의 열화현상을 화학반응의 법칙으로 가정한 Arhenius 모델과 같은 열화이론이 확립되어지고 있다 하지만, 실제 케이블을 만드는 과정에서 절연체의 성형 조건에 따른 절연 성능 평가와 관련된 연구는 그렇게 많지 않다. 본 연구에서는 XLPE의 성형 조건(가교, 건조, 냉각)에 따른 화학적 물성의 변화와 절연성능 사이의 상관관계를 알아보기 위해 LDPE에 가교제(DCP)를 첨가한 컴파운드를 이용해 만든 몰드 시편의 물성을 DSC, 가교도 분석 및 전기 트리 개시 전압을 측정해 살펴보았다. 그 결과 가교나 건조 조건에 비해 냉각 조건에 따른 가교 폴리에틸렌의 결정화도가 트리 개시전압에 보다 큰 영향을 미침을 알 수 있었다.

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Melt Grafting of EPDM and Itaconic Acid: Effect of Reaction Conditions and Initiator Type/Concentration (Ethylene-propylene-diene terpolymer (EPDM)와 itaconic acid의 melt grafting: 반응조건과 개시제 종류 및 농도의 영향)

  • Kim, Ki-Jae;Bae, Jong-Woo;Kim, Jung-Soo;Lee, Jin-Hyok;Kim, Gu-Ni;Oh, Sang-Taek;Kim, Wonho
    • Elastomers and Composites
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    • v.49 no.3
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    • pp.181-190
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    • 2014
  • Melt grafting of itaconic acid (IA) onto an ethylene-propylene-diene terpolymer (EPDM) with various organic peroxide initiators was performed. Finding the optimum mixing conditions and concentration of ingredients is critical for effective grafting and optimum properties of grafted materials. This study focused on the effects of mixing conditions (temperature and time), initiator type/concentration and monomer concentration on the grafting degree and efficiency, melt flow index, and gel content of EPDM-g-IA. The initiator, 2,5-dimethyl-2,5-di(tert-butyl peroxy)-hexane (T-101), appeared to meet for the best grafting degree (1.91%). The grafting degree increased markedly by increasing the amounts of monomer IA and initiator T-101. The grafting degree also increased by increasing mixing temperature and time. The optimum monomer and initiator concentrations and reaction temperature and time were found to be about 5wt%/0.05wt% and $160^{\circ}C$/15min, respectively. It was found that the physical properties of EPDM-g-IA were higher than those of the pristine EPDM.

Zero-Length Crosslinking Study on Interactions of TBP, GAL4-AH, and TFIIB in the Preinitiation Complex (전사개시전 복합체에서 TBP, GAL4-AH, TFIIB의 상호작용에 대한 Zero-Length Crosslinking 실험)

  • 권혁만
    • The Korean Journal of Zoology
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    • v.39 no.4
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    • pp.393-399
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    • 1996
  • A zero-Iength croessinking procedure for studying protein-protein interactlons in preinitiation complex has heen developed. Preinltiadon complexes were assembled with immobilized DNA templates coupled to metal beads. Pudfied complexes were dIrectly crosslinked by 1-ethyl-3.(3-dimethylaminopropyl)carbodlimide (EDC). The reaction was stopped by addition of $\beta$-mercaptoethanol, and the complexes were isolated from EDC immedIately. An appllcatlion of this method with a preinltlation complex assembled with TBP, TFIIB, and GAL4-AH demonstrated that ThP dIrectly interacts with GAL4-AH and TFIIB in the prelnitlatlon complex. However, croeslinked produd between GAL4-AH and ThilB was not observed. These resutts lndlcate that GAL4-AH does not stably Interact with TFIIB In the GAL4-AH-TFIIB-TBP-DNA prelnitlatlon complex.

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Synthesis of Characterization of Poly(alkylene oxide) Copolyols by Catioinc Ring Opening Polymerization and Their Azide Functionalized Copolyols (양이온 개환중합에 의한 폴리알킬렌 옥사이드 코폴리올의 합성과 아지드화 코폴리올의 특성 연구)

  • Lee, Jae-Myung;Seol, Yang-Ho;Kwon, Jung-Ok;Jin, Yong-Hyun;Noh, Si-Tae
    • Applied Chemistry for Engineering
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    • v.31 no.3
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    • pp.267-276
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    • 2020
  • Poly(epichlorohydrin) copolyol series (PECH copolyols) were synthesized via cationic ring-opening copolymerization (ROCP) of oxirane-based monomers and effects of reaction temperature, solvent type, and initiator were studied. As a comonomer, two types of alkylene oxides were used, and polymerization conditions were conducted both with diethylene glycol (DEG) as an initiator in methylene chloride (MC) solvent and tripropylene glycol (TPG) in toluene solvent. In order to induce the active monomer (AM) mechanism in the ring-opening copolymerization reaction, the monomer was injected by an incremental monomer addition (IMA) method using a syringe pump, and the polymerization was performed at -5 ℃. PECH copolyol, a synthesized ephichorohydrin (ECH)-based copolyol, was converted to glycidyl azide-based energy-containing copolyol (GAP copolyol) by azadizing the ECH unit through a substitution reaction. It was confirmed that the synthesized azide copolyol had little effects on changes of the solvent and the initiator. Also, the molecular weight increased 500 after the azide reaction, thereby the GAP copolyol was polymerized as designed. As the content of the comonomer increased, both the Tg and viscosity tended to decrease due to the influence of the alkyl chain length. It is possible to fundamentally prevent CH3N3 amount produced in the azide reaction process, and it is expected that a large-scale process could be achievable.

Synthesis and Their Properties of PP Graft Copolymers by E-beam Radiation and Vapor Phase Reaction (전자선 조사 기상 반응에 의한 PP 기재 공중합체의 합성과 특성)

  • 황택성;박진원;이재천
    • Polymer(Korea)
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    • v.26 no.3
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    • pp.287-292
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    • 2002
  • Graft copolymerization of styrene and glycidyl methacrylate (GMA) to the peroxidized polypropylene (PP) fabric with E-beam in $O_2$ atmosphere was carried out in vapor phase with benzoyl peroxide (BPO) as an initiator. The degree of grafting of copolymers was increased with the increase of the reaction temperature and the highest degree of grafting was obtained at $70^{\circ}C$ with styrene, and at $80^{\circ}C$ with GMA. The highest degree of grafting of styrene grafted PP according to reaction time was higher than that of GMA grafted PP. In vapor phase graft polymerization, the degree of grafting of copolymers according to water composition in monomer mixture was effected by the boiling temperature of monomers.

MEK-PO 분해 폭발사고 사례 연구

  • 김관응;이근원;김기영;박상현
    • Proceedings of the Korean Institute of Industrial Safety Conference
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    • 2003.10a
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    • pp.54-59
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    • 2003
  • 유기과산화물은 분자구조내에 과산화결합(Peroxy, -O-O-)을 갖고 있는 유기화합물로서 매우 불안정한 과산화수소(H-O-O-H)의 유도체이다. 과산화물을 특징짓는 산소-산소(-O-O-) 과산화결합은 C-H, C-O, C-C 등의 결합에 비하여 결합에너지가 작아서 열이나 빛에 의해서 쉽게 균형분해(Homolysis)가 일어나 두 개의 유리기인 라디칼(Free radical)을 생성하게 되는데, 이때 생성된 라디칼은 비닐중합반응을 개시시킬 수 있고, 또한 다른 자유 라디칼 반응을 유발시킬 수 있다.(중략)

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Photo-Induced Graft Copolymerization of Acrylonitrile onto Chitosan (Chitosan에 대한 아크릴로니트릴의 광개시 그라프트 공중합)

  • Kim, Wan-Young;Kim, Chong-Bae;Yug, Gyeong-Chang;Park, Sun-Ny
    • Applied Chemistry for Engineering
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    • v.3 no.1
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    • pp.172-178
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    • 1992
  • The graft copolymerization of acrylonitrile(AN) onto chitosan film by using $F^{3+}(FeCl_3{\cdot}6H_2O)$ as a photosensitizer in an aqueous medium was carried out under ultraviolet(UV) irradiation. The grafted copolymer was identified by using IR spectroscopy and scanning electron microscope. The effects of various polymerization parameters involving monomer concentration, photosensitizer concentration, polymerization time and polymerization temperature were investigated. As monomer concentration and photosensitizer concentration were increased, the percent grafting was increased up to limiting value. And also the percent grafting was found to increase by increasing the polymerization time and temperature.

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Polymerization of Vinyl Monomers Initiated by Cobalt (II) Chloride (염화코발트(Ⅱ)에 의한 비닐단위체의 중합)

  • Lee Dong-ho;Ahn Tae-oan
    • Journal of the Korean Chemical Society
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    • v.19 no.1
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    • pp.53-64
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    • 1975
  • The polymerization of methyl methacrylate initiated by cobalt(II) chloride in tetrahydrofuran has been studied. The conversion was increased liearly with polymerization time at initial stage of 6${\sim}$7% conversion and then the rate of polymerization was slightly reduced, and after that the autoacceleration was observed. The rate of polymerization was increased with the concentration of cobalt(Ⅱ) chloride, but at the concentration of cobalt(II) chloride higher than $3.4{\times}10^{-4}$ mole/l the rate of polymerization was decreased. The rate of polymerization was dependent on the 1.38 power of the concentration of methyl methacrylate. The effect of the radical inhibitor DPPH was observed and the inhibition time was increased with the concentration of DPPH. The apparent overall activation energy was calculated to be 13.2 kcal/mole. In the copolymerization of methyl methacrylate ($M_1$) and styrene ($M_2$), the monomer reactivity ratio was found to be $r_1$ = 2.35, $r_2$ = 0.78. From the above results. the initiation mechanism of polymerization was discussed and it was considered that the polymerization proceeds mainly via diradical mechaism.

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Monitoring photo-polymerization reaction using near-IR spectroscopic technique (Near-IR 분광법을 이용한 광 경화 중합반응 관찰)

  • Chung, Soo-Chung;Hong, Jin-Who;Yu, Jeong-A
    • Analytical Science and Technology
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    • v.15 no.4
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    • pp.341-345
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    • 2002
  • The extent of UV-curing photo-polymerization reaction was monitored by near-IR spectroscopic method. Acrylates containing quaternary ammonium salts and Darocur 1173 were used as reactive monomer and a photo initiator, respectively. The extent of photo-polymerization reaction was obtained from the conversion ratio of acrylate double bond calculated from the intensities of measured bands at 1615 nm and at 2105 nm. Near-IR spectroscopic methods can be an useful tool for the monitoring of the progress of photo-polymerization.