• 한국복합재료학회:학술대회논문집
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• 한국복합재료학회 1999년도 추계학술발표대회 논문집
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• pp.73-76
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• 1999

Near infrared spectroscopy techniques were used to study the cure reactions of epoxy resin system based on diglycidyl ether of bisphenol A(DGEBA) resins cured with 4, 4' diaminodiphenyl sulfone (DDS) hardner. Stoichiometric DGEBA/DDS resin formulation was involved in this study. The infrared absorption spectra of the prepared formulation were obtained on an FTIR spectrometer operating in the region of 11000 to 4000$cm^{-l}$. The chemical group peaks of interest in a DFEBA/DDS spectrum were identified by a comparative study with individual spectra of DGEBA and DDS monomers. Where necessary, special model compounds were used to identify unknown bands, such as the primary amine band at 4535$cm^{-l}$. The absorption bands of interest were integrated to quantify the areas and then converted to molar concentrations. This series of quantitative analyses of the major chemical groups led us to understand not only the reaction mechanism but also the cure kinetics. In this paper, the reaction mechanisms observed in stoichiometric DGEBA/DDS resin formulation and the various properties of the resin system as a function of cure temperature are described.

• Korean Chemical Engineering Research
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• 제47권4호
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• pp.403-409
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• 2009

1906년 George Oenslager에 의해 처음으로 아닐린계 유기 가황 촉진제를 발견한 이 후 현재 많은 종류의 유기 가황 촉진제가 알려져 있으며 이들 유기 가황 촉진제를 그 특성에 맞도록 병용하면 더욱 효과적이고 이것을 2종 혹은 3종을 병용하면 또 다른 효과를 나타낸다. 최근 고무 산업의 많은 분야에서 생산성 향상 및 제조환경 개선 요구에 부응하기위하여 사출 기법이 도입되고 있으며 이를 위해서 고속 가류형 고무 컴파운드의 개발이 요구되고 있다. 따라서 적절한 가류 시간 확보를 위하여 다양한 종류의 촉진제에 대한 연구, 컴파운드의 적절한 저장 안정 기간 확보에 대한 연구, pellet 형상 제조 시 자중에 의한 autoadhesion 감소에 대한 연구가 활발히 진행되고 있다. 본 연구에서는 NR/BR compounds에 MBTS(2,2' Dithiobisbenzothiazole), TMTM(Tetramethylthiuram Monosulfide), ZDMC(Zinc dimethyldithiocarbamate), CBS(N-Cyclohexyl benzothiazolyl-2-sulfenamide), DPG(Diphenylguanidine)를 각각 병용하여 가황 고무의 가황 특성 및 기계적 물성을 비교 분석하였다. 촉진제 병용에 따른 NR/BR compounds를 평가한 결과 MBTS 1.5 phr, TMTM 0.5 phr, DPG 0.15 phr을 사용한 경우 가장 우수한 가황 특성($t_{90}$: 235 sec, $T_{max}$: 5.77 Nm)을 나타내었으며 100, 300% 모듈러스 및 인열 강도 값이 각각 2.180, 5.656 MPa, 59.58 kgf/cm으로 가장 우수한 결과를 나타내었다.

• Macromolecular Research
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• 제11권4호
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• pp.267-272
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• 2003

The isothermal cure reactions of blends of epoxy (DGEBA, diglycidyl ether of bisphenol A)/anhydride resin with polyamide copolymer (poly(dimmer acid-co-alkyl polyamine)) or PEI were studied using differential scanning calorimetry (DSC). Rheological measurements have been made to investigate the viscosity and mechanical relaxation behavior of the blends. The reaction rate and the final cure conversion were decreased with increasing the amount of thermoplastics in the blends. Lower values of final cure conversions in the epoxy/thermoplastic blends indicate that thermoplastics hinder the cure reaction between the epoxy and the curing agent. Complete miscibility was observed in the uncured blends of epoxy/thermoplastics up to $120^{\circ}C$ but phase separations occurred in the early stages of the curing process at higher temperatures than $120^{\circ}C$. According to the rheological measurement results, a rise of G' and G" at the onset of phase separation is seen. A rise of G' and G" is not observed for neat epoxy system since no phase separation is seen during cure reaction. At the onset of phase separation the rheological behavior was influenced by the amount of thermoplastics in the epoxy/thermoplastic blends, and the onset of phase separation can be detected by rheological measurements.

• 한국재료학회지
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• 제9권4호
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• pp.373-377
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• 1999

The cure mechanicsm and cure kinetics of diglycidyl ether of bisphenol A(DGEBA)/4,4'-methylene dianiline(MDA)/nitrile(MN, SN, GN) systems were studied by FT-IR and DSC to develop new applications in the biomedical polymer fields. The network structure of the DGEBA/MDA system was changed to the chain-extended network structure by the addition of nitriles. The reactions contributed to the chain extension were the primary amine-nitrile and hydroxyl-nitrile reactions. The chain-extended network structure could be indirectly proved by the decrement of T\ulcorner and the increment of impact strength with the increasing nitrile content. The cure rate of DGEBA/MDA/nitrile system was lower than that of DGEBA/MDA system due to the disturbance of nitrile group in the reaction of primary amine and epoxide groups.

• Bulletin of the Korean Chemical Society
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• 제18권11호
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• pp.1199-1203
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• 1997

The investigation of cure kinetics of biphenyl epoxy (4,4-diglycidyloxy-3,3,5,5-tetramethyl biphenyl)-xylok resin system with four different catalysts was performed by differential scanning calorimeter using an isothermal approach. All kinetic parameters of the curing reaction including the reaction order, activation energy and rate constant were calculated and reported. The results indicate that the curing reaction of the formulations using triphenylphosphine (TPP) and 1-benzyl-2-methylimidazole (1B2MI) as a catalyst proceeds through a first order kinetic mechanism, whereas that of the formulations using diazabicyloundecene (DBU) and tetraphenyl phosphonium tetraphenyl borate (TPP-TPB) proceeds by an autocatalytic kinetic mechanism. To describe the cure reaction in the latter stage, we have used the semiempirical relationship proposed by Chern and Poehlein. By combining an nth order kinetic model or an autocatalytic model with a diffusion factor, it is possible to predict the cure kinetics of each catalytic system over the whole range of conversion.

• 한국재료학회지
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• 제3권3호
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• pp.272-275
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• 1993

To modify the toughness of epoxy for matrix, succinonitrile(SN) was introduced to diglycidy1 ether of bisphenol-A (DGEBA)/methylene dianiline(MDA)system. Cure reaction mdchanism of the DGEBA/MDA/SN system was strdied through Fourier transform infrared(FT-IR) spectrometry. As a result, the reaction of nitrile group of SN with secondary amine and with hydroxy1 group prevented the reaction of hydroxy1 group with epoxide group from crossoinding. Nitrile groups produced amide group by reacting with hydroxy1 groups and made a lowered crosslind density in chain networks.

• 한국정밀공학회:학술대회논문집
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• 한국정밀공학회 2009년도 추계학술대회 논문집
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• pp.703-704
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• 2009

• Macromolecular Research
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• 제9권2호
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• pp.92-99
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• 2001

Silica-filled rubber compounds have slower cure characteristics than carbon black-filled ones due to the adsorption of curatives on the silica surface. Fatty acid was used as a cure activator along with zinc oxide in a sulfur cure system. Poly(ethylene glycol), PEG, was used in silica-filled rubber compounds to prevent adsorption of the curatives on the silica surface. In this study, influence of the size of fatty acid and PEG on properties of silica-filled NR compounds was investigated. It was found that the size of fatty acid and PEG affected the curt: characteristics and physical properties. The cure rate becomes faster as the PEG size increases. By increasing the size of fatty acid or PEG, the delta torque of the compound decreases while the Mooney viscosity increases. The modulus of the vulcanizate decreases with increasing the molecular weight of fatty acid or PEG. The experimental results were explained by the filler dispersion and by the prevention of the curative-adsorption on the silica surface.

• Bulletin of the Korean Chemical Society
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• 제21권6호
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• pp.628-634
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• 2000

Crosslink is the most important chemistry in a rubber vulcanizate. Degree and type of crosslinks of the vulcanizate determine its physical properties. Change of crosslink density and deformation of a rubber vulcanizate by thermal aging were studied using natural rubber (NR) vulcanizates with various cure systems (conventional, semi-EV, and EV) and different cure times (under-, optimum-, and overture). All the NR vulcanizates were deformed by the thermal aging at 60-100 $^{\circ}C.$ The higher the aging temperature is, the more degree of the deformation is. The undercured NR vulcanizates after the thermal aging were deformed more than the optimumand overcured ones. The NR vulcanizates with the EV cure system were less deformed than those with the conventional and semi-EV cure systems. The deformation of the NR vulcanizates was found to be due to change of the crosslink density of the vulcanizates. The crosslink densities of all the vulcanizates after the extraction of organic materials were also changed by the thermal ging. The sources to change the crosslink densities of the vulcanizates by the thermal aging were found to be dissociation of the existing sulfur crosslink and the formation of new crosslinks by free sulfur, reaction products of curing agents, and pendent sulfide groups.

• Elastomers and Composites
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• 제26권2호
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• pp.115-122
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• 1991

Polychloroprene rubber was moisture-cured after treating them with silane coupling agents such as 3-mercaptopropyltrimethoxysilane(MPS), 3-methacryloxypropyltrimethoxysilane(MAS) and vinyltriethoxysilane(VES), especially MPS. The cure reaction is composed of two steps. The first is the reaction between chlorine atoms of CR and silane coupling agents. The second is the formation of cross-links which are siloxane linkage. The linkage is formed by the condensation of silanol groups which are produced by the hydrolysis of alkoxysilyl groups. The first reaction was kinetically studied and the reactivity of CR to silane coupling agents was determined in previous literature. Crosslinking density and mechanical properties of the moisture-cured elastomer filled with silica or non-filled were studied and the feasibility of this cure system was discussed.