• 공업화학
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• 제19권4호
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• pp.370-375
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• 2008

비수계 분산(NAD : non-aqueous dispersion) 중합을 이용하여 친환경적인 아크릴 수지를 합성시 최적의 중합조건에 대해 연구하였다. 중합된 고분자 입자들 간의 응집을 방지하기 위한 안정제의 적정량은 20 wt%로 나타났고 안정된 NAD 상태를 유지하기 위한 혼합 용매의 적정 혼합비는 지방족과 방향족 용매의 비율이 80 : 20인 것으로 나타났다. NAD 수지의 점도는 반응시간뿐만 아니라 개시제의 양 및 교반 속도 등에 의해 영향을 받는 것으로 나타났다. 또한 NAD 수지의 입자 크기 및 분포도, 안정제의 양, 개시제의 농도 등에 의해 영향을 받는 것을 확인하였다. 단량체의 투입시기는 단량체를 초기에 모두 투입하면 용매의 극성이 증가하여 입자의 크기가 커져서 입자의 안정성이 저하되므로 단계별로 지속적으로 투입할 필요가 있는 것으로 관찰되었다.

• Macromolecular Research
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• 제13권6호
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• pp.467-476
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• 2005

The main objective of this study was to develop and characterize pH-sensitive biodegradable polymeric materials. For pH-sensitivity, we employed three kinds of moieties: 2-amino-3-(lH-imidazol-4-yl)-propionic acid (H), N-[4-( 4,6-dimethyl-pyrimidin-2ylsulfamoyl)-phenyl]succinamic acid (SM), and 2- {3-[ 4-( 4,6-dimethyl-pyrim­idin- 2-ylsulfamoyl)-phenylcarbamoyl]-propionylamino} -3-(3 H - imidazol-4-yl)-propionic acid (SH). The pH -sensitive diblock copolymers were synthesized by ring opening polymerization and coupling reaction from poly(ethylene glycol) (MPEG), $\varepsilon$-caprolactone (CL), D,L-lactide (LA) and pH-sensitive moieties. The pH-sensitive SH molecule was synthesized in a two-step reaction. The first step involved the synthesis of SHM, a methyl ester derivative of SH, by coupling reaction of SM and L-histidine methyl ester dihydrochloride, whereas the second step involved the hydrolysis of the same. The synthesized SM, SHM and SH molecules were characterized by FTIR, $^{1}H$-NMR and $^{13}C$-NMR spectroscopy, whereas diblock copolymers and pH-sensitive diblock copolymer were characterized by $^{1}H$-NMR and GPC analysis. The critical micelle concentrations were determined at various pH conditions by fluorescence technique using pyrene as a probe. The micellization and demicellization studies of pH-sensitive diblock copolymers were also done at different pH conditions. The pH-sensitivity was further established by acid-based titration and DLS analysis.

• 한국콘크리트학회:학술대회논문집
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• 한국콘크리트학회 2005년도 추계 학술발표회 제17권2호
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• pp.415-418
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• 2005

Nowadays the three major commercially available of organic chemical admixtures are modified lignosulfonates(LS), sulfonated naphthalene-formaldehyde resins (SNF) and sulfonated melamine-formaldehye (SMF). In this study, various sulfonated melamine-formaldehyde (SMF) superplasticizers were synthesized via four synthetic steps. Hydroxymethylation (Step 1), Sulfonation (Step 2), Polymerization (Step 3) and Neutralization and Stabilization (Step 4). In this synthesis of SMF, reaction conditions such as the mole ratio of melamine to formaldehyde and the amount of acid catalyst were changed. After application of SMF superplasticizer to cement paste and mortar, the physical properties including workability, slump loss, compressive strength were compared.

• 통합자연과학논문집
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• 제7권4호
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• pp.266-272
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• 2014

Oxocane high explosives substituted to explosive group such as azide (-CH2N3), nitrate (-CH2ONO2), and hydrazine (-CH2N2H3) are investigated theoretically the acid catalyzed reaction using the semiempirical MINDO/3, MNDO and AM1 methods to use as the guidelines of high explosives. The nucleophilicity and basicity of oxocane high explosives can be explained by the value of negative charge on oxygen atom of oxocane and the reactivity in propagation step can be represented by the value of positive charge on carbon atom and low electrophile LUMO energy. It was known that carbenium ion was favorable due to the stable energy (11.745~25.461 Kcal/mol) between oxonium ion and carbenium ion in the process of cyclic oxonium ion of oxocane high explosives being converted to open carbenium ion in oxocane high explosives. The value of concentration of cyclic oxonium ion and open carbenium ion in equilibrium status was found to be a major determinant of mechanism, it was expected to react faster in the prepolymer propagation step in SN1 mechanism than in that of SN2.

• 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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• 제14권3호
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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.

• 한국생물공학회:학술대회논문집
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• 한국생물공학회 2000년도 추계학술발표대회 및 bio-venture fair
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• pp.48-51
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• 2000

The poly(3-hydroxybutyrate) (PHB) synthase of Ralstonia. eutropha, which was produced by a recombinant strain E. coli and purified in one-step with a methyl-HIC column to a purity of more than 90%, was used to polymerize 3-hydroxypropionyl-CoA (3HPCoA) and to copolymerize 3HPCoA with 3-hydroxybutyryl-CoA (3HBCoA) in vitro. A $K_m$ of $189\;{\mu}M$ and a $k_{cat}$ of $10\;sec^{-1}$ were determined for the activity of the enzyme in the polymerization reaction of 3HPCoA based on the assumption that the dimer form of PHB synthase was the active form. Free coenzyme A was found to be a very effective competitive inhibitor for the polymerization of 3HPCoA with a $K_i$ of $85\;{\mu}M$. The maximum degree of conversion of 3HPCoA to polymer was less than 40 %. In the simultaneous copolymerization reactions of these two monomers, both the turnover number for the copolymerization reaction and the maximum degree of conversion of 3HPCoA and 3HBCoA to copolymers increased with an increase in the amount of 3HBCoA in the monomer mixture. However, the maximum conversion of 3HPCoA to a copolymer was less than 35 % regardless of the ratio of 3HPCoA to 3HBCoA. Block copolymers were obtained by the sequential copolymerization of the two monomers and these copolymers had a much narrower molecular weight distribution than those obtained by the simultaneous copolymerization of the same molar ratio of 3HPCoA and 3HBCoA.

• 공업화학
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• 제21권3호
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• pp.278-283
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• 2010

폭발성기를 가진 azido기($-CH_2N_3$), nitrato기($-CH_2ONO_2$) 그리고 hydrazino기(-$CH_2N_2H_3$)로 치환된 옥소란 고폭 화약류의 산 촉매 하에서 중합반응을 반경험적인 MINDO/3, MNDO, AM1 방법 등을 사용하여 이론적으로 고찰하였다. 옥소란 고폭 화약류의 친핵성 및 염기성은 옥소란 산소원자의 음전하크기로 설명할 수 있고, 중합하의 성장단계에서 옥소란의 반응성은 옥소란의 반응중심 탄소원자의 양전하크기와 친전자체의 낮은 LUMO 에너지에 좌우됨을 알 수 있다. 옥소란 고폭 화약류의 고리형 oxonium 이온형이 열린 carbenium 이온형으로 전환되는 과정은 oxonium 이온과 carbenium 이온 사이의 계산된 안정화 에너지(17.950~30.197 kcal/mol)에 의하면 carbenium 이온이 더 유리함을 예측 할 수 있다. 평형상태의 고리형 oxonium 이온과 열린 carbenium 이온의 농도 크기가 반응 메카니즘의 결정단계이며, 산 촉매 하의 형태와 계산을 기초로 하여 빠른 평형을 예상하여 볼 때 선폴리머(prepolymer) 성장단계에서 $S_N1$ 메카니즘이 $S_N2$ 메카니즘보다 빠르게 반응 할 것으로 예측된다.

• 폴리머
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• 제35권1호
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• pp.66-71
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• 2011

현탁중합에 이은 프리델 크래프츠 촉매에 의한 hyper crosslinking 반응 및 hydrolysis반응으로 hydroxyl 반응 관능기를 포함하는 hyper crosslinked polymer particle(HCPP)을 합성할 시, 1) 각 단량체의 함량 변화에 따른 HCPP의 표면 모폴로지, 기공 크기 및 분포도의 변화, 2) hyper crosslinking 반응조건 변화에 따른 HCPP의 BET 비표면적 값의 변화 및 3) $CO_2$ 초임계 건조공정을 이용한 HCPP에서의 미반응 잔류 단량체, 올리고머 및 촉매의 제거 등에 관해 연구하였다. 이번 연구를 통해 초기 HCPP의 합성 시 관찰되었던 고분자 입자 표면의 균열 및 파괴현상은 hyper crosslinking 과정 중에 진행되는 microphase separated domain간의 반응과 깊은 관계가 있음을 관찰하였고, 또한 hyper crosslinking 반응 시 반응온도 반응시간 및 사용 용매의 증가는 HCPP의 BET 비표면적 값의 증가에 기여함을 관찰하였다. 그리고 hyper crosslinking을 유발하는 단량체의 함량변화는 다른 단량체에 비해 HCPP의 BET 비표면적, 기공 크기 및 분포도에 상대적으로 큰 영향을 미침을 확인하였다. 또한 HCPP에서의 미반응 잔류 단량체, 올리고머 등의 제거에 $CO_2$ 초임계 건조공정이 매우 효과적임을 확인할 수 있었고 특히 이 과정에서의 보조용매(메탄올)의 첨가는 잔류촉매(Fe)의 제거에 있어 탁월한 효과를 나타내었다.

• 콘크리트학회논문집
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• 제17권5호
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• pp.811-818
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• 2005

플래쉬 콘크리트의 유동성 및 유동성 감소는 유기 화학혼화제의 종류에 영향을 받는다는 것은 잘 알려져 있다. 유기화학 혼화제는 콘크리트의 물성을 증가시킬 수 있다. 술포네이트 나프탈렌 포름알데하이드(SNF, Sulfonated Naphthalene-Formaldehyde) 고유동화제(superplasticizer)가 대표적으로 많이 사용되고 있으나, 유동성 감소의 문제점이 있다. 본 연구에서는 술포네이트 멜라민 포름알데하이드(SFM, Sulfonated Melamine-Formaldehyde) 고유동화제를 합성하여 SNF 고유동화제의 물리적 특성을 보완하고자 한다. SNF계 고유동화제를 4단계로 나누어 반응을 진행하였고, Step.1은 hyydroxymethylation 단계이고, Step.2는 sulfonation단계이고, Step.3은 중합단계이고, Step.4는 안정화 단계이다. SMF 고유동화제의 합성은 pH, 반응온도 및 반응시간에 영향을 받는다 본 합성에서 우리는 멜라민과 포름알데하이드의 몰비를 1:3, 1:4로 변화시키고, Step. 3에서 촉매의 양을 조절하면서 반응을 진행하였다. 그리고, SMF 고유동화제 및 SNF계 고유동화제와 혼합한 시료에 대해서 시멘트 대비 0.5, 1.0, 1.5wt% 첨가하여 물리적 특성을 비교하였다. 고유동화제를 첨가한 시료는 첨가하지 않은 시료 CEM보다 높은 압축강도, 슬럼프 값을 나타내었고, 미세한 기공과 낮은 기공율을 보였다.