• Macromolecular Research
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• 제10권2호
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• pp.108-114
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• 2002

Poly(butylene succinate) (PBS) prepolymers were prepared by the condensation polymerization of 1,4-butanediol (1,4-BD) and succinic atid (SCA) in the presence of titanium (VI) isoproxide(TPI) catalyst. The PBS prepolymers reacted with 1,4-BD or SCA to obtain hydroxyl or carboxylic acid group terminated PBS. High molecular weight linear or branched PBS was synthesized by a coupling reaction between hydroxyl and carboxylic acid group terminated PBS, or by a branching reaction between carboxylic acid group terminated PBS and glycerol as a branching agent. The weight average molecular weight of the prepared linear or branched PBS was in the range of 100,000-220,000. Both melting point and thermal stability of the high molecular weight linear and branched PBSs were somewhat higher than those of general PBS. From a tensile behavior by Instron test, modulus, tensile strength and elongation at break improved with increase in the molecular weight of the prepared PBS through the coupling or the branching reaction. In particular, the high molecular weight linear PBS had about 2.5 times higher value in modulus than the branched one.

• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1181-1185
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• 1999

The reaction of FeC5H5+ ion with ferrocene molecule is investigated using FT-ICR mass spectrometry. FeC5H5+ ions are generated by dissociative ionization of ferrocenes using an electron beam. The reaction gives rise to the formation of the adduct ion, Fe2(C5H5)3+, in competition with charge transfer reaction leading to the formation of ferrocene molecular ion, Fe(C5H5)2+·. The branching ratio of the adduct ion increases as the internal energy of the reactant ion decreases and correspondingly the branching ratio for the charge transfer reaction product decreases. The observed rate of the addition reaction channel is slower than that of the charge transfer reaction. The observation of the stable adduct ions in the low-pressure ICR cell is attributed to the radiative cooling of the activated ion-molecule complex. The mechanism of the reaction is presented to account for the observed experimental results.

• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.833-838
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• 2014

The energy- and time-dependent branching to the competing dissociation paths are studied by theory for coupled unimolecular dissociations of the o-, m-, and p-chlorotoluene radical cations to $C_7{H_7}^+$ (benzylium and tropylium). There are four different paths to $C_7{H_7}^+$, three to the benzylium ion and one to the tropylium ion, and all of them are coupled together. The branching to the multiple paths leads to the multiexponential decay of reactant with the branching ratio depending on both internal energy and time. To gain insights into the multipath branching, we study the detailed kinetics as a function of time and internal energy on the basis of ab inito/RRKM calculations. The number of reaction steps to $C_7{H_7}^+$ is counted for each path. Of the three isomers, the meta mostly goes through the coupling, whereas the para proceeds with little or no coupling. In the beginning, some reactants with high internal energy decay fast to the benzylium ion without any coupling and others rearrange to the other isomers. Later on all three isomers dissociate to the products via long-lived intermediates. Thus, the reactant shows a multiexponential decay and the branching ratio varies with time as the average internal energy decreases with time. The reciprocal of the effective lifetime is taken as the rate constant. The resulting rate-energy curves are in line with experiments. The present results suggest that the coupling between the stable isomers is thermodynamically controlled, whereas the branching to the product is kinetically controlled.

• 대한기계학회논문집B
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• 제21권9호
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• pp.1174-1184
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• 1997

Extinction characteristics of pure hydrogen-oxygen diffusion flames, at high pressures in the neighborhood of the critical pressure of oxygen, is numerically studied by employing counterflow diffusion flame as a model flame let in turbulent flames in rocket engines. The numerical results show that extinction strain rate increases almost linearly with pressure up to 100 atm, which can be explained by comparison of the chain-branching-reaction rate with the recombination-reaction rate. Since contributions of the chain-branching reactions, two-body reactions, are found to be much greater than those of the recombination reactions, three-body reactions, extinction is controlled by two-body reactions, thereby resulting in the linearity of extinction strain rate to pressure. Therefore, it is found that the chemical kinetic behaviors don't change up to 100 atm. Consideration of the pressure fall-off reactions shows a slight increase in extinction strain rate, but does not modify its linearity to pressure. The reduced kinetic mechanisms, which were verified at low pressures, are found to be still valid at high pressures and show good qualitative agreement in prediction of extinction strain rates. Effect of real gas is negligible on chemical kinetic behaviors of the flames.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1535-1538
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• 2009

We present calculations for $S_N$2/E2 reactions in protic solvents (t-butyl alcohol, ethylene glycol). We focus on the role of the hydroxyl (-OH) groups in determining the $S_N$2/E2 rate constants. We predict that the ion pair E2 mechanism is more favorable than the naked ion E2 reaction in ethylene glycol. E2 barriers are calculated to be much larger (~ 9 kcal/mol) than $S_N$2 reaction barriers in protic solvents, in agreement with the experimental observation [Kim, D. W. et al. J. Am. Chem. Soc. 2006, 128, 16394] of no E2 products in the reaction of CsF in t-butyl alcohol.

• 한국연소학회:학술대회논문집
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• 한국연소학회 제26회 KOSCO SYMPOSIUM 논문집
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• pp.129-136
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• 2003

Numerical study with momentum-balanced boundary conditions has been conducted to grasp chemical effects of added $CO_{2}$ and $H_{2}O$ to fuel- and oxidizer-sides on flame structure and NO emission behavior in $CH_{4}$/Air counterflow diffusion flames. The dilution with $H_{2}O$ results in significantly higher flame temperatures and NO emission, but dilution with $CO_{2}$ has much more chemical effects than that with $H_{2}O$. Maximum reaction rate of principal chain branching reaction due to chemical effects decreases with added $CO_{2}$. but increases with added $H_{2}O$. The NO emission behavior is closely related to the production rate of OH, CH and N. The OH radical production rate increases with added $H_{2}O$ but those of CH, N decrease. On the other hand the production rates of OR CH and N decrease with added $CO_{2}$. It is found that NO emission behavior is considerably affected by chemical effects of added $CO_{2}$ and $H_{2}O$.

• 폴리머
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• 제36권2호
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• pp.245-250
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• 2012

장쇄분지(long chain branch, LCB)를 가지는 분지화된 폴리프로필렌(polypropylene, PP)이 세 종류의 분지제(branching agent)를 이용하여 고상(solid state)에서 제조하였다. 분지화된 PP의 화학구조, 비등온결정화 거동 및 복합점도를 적외선분광기(FTIR), 시차주사열용량분석기(DSC), 광학현미경 그리고 동적유변측정기(ARES)를 이용하여 관찰하였다. 분지화된 PP의 화학구조는 3100 $cm^{-1}$에서 나타나는 분지제의 =C-H 신축진동을 이용하여 확인하였다. PP-D-0-3과 PP-F-0-3의 경우 순수 PP와 비교하여 용융온도에 큰 변화를 보이지 않은 반면 HQ를 사용한 경우에는 용융온도의 감소를 나타내었다. 이는 분지화 반응보다 분해반응이 우세하여 나타나는 현상으로 해석되고, 복합점도의 감소를 통해 확인하였다. 분지화된 PP의 비등온결정화 거동은 Avrami 방정식을 이용하여 분석하였다. PP의 Avrami 지수는 3의 값을 나타내었고, DVB와 FS로 처리된 분지화 PP의 경우는 3보다 약간 작은 값을 나타내었다. Kissinger 방법에 의해서 계산된 분지화 PP의 활성화에너지는 순수 PP의 25 kJ/mol과 큰 차이를 보이지 않았다.

• 공업화학
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• 제22권6호
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• pp.679-684
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• 2011

고상(solid state) 반응과 용융(melt state) 반응을 이용하여 장쇄분지(long chain branch, LCB)를 가지는 분지화된 폴리프로필렌(branched polypropylene, LCB-PP)을 제조하였다. 분지제(branching agent)로는 divinylbenzene (DVB), 1,4-benzenediol (RES), furfuryl sulphide (FS)가, LCB-PP/실리케이트 복합체를 제조하기 위해서는 층상 실리케이트가 사용되었다. LCB-PP의 화학구조, 열적특성, 유변학적 특성을 적외선 분광기(FT-IR), 시차주사열용량분석기(DSC, TGA), 그리고 동적유변측정기(ARES)를 이용하여 분석하였다. LCB-PP의 화학구조는 $3100cm^{-1}$에서 나타나는 분지제의 =C-H 신축진동을 이용하여 확인하였다. DSC와 TGA의 결과로부터 고상반응보다 용융반응이 LCB-PP 제조에 보다 효과적이었고, 유변학적 특성을 통하여 추가 확인되었다. 분지제 중에서는 FS가 가장 효과적이었다. LCB-PP의 경우 낮은 전단속도 영역에서 점도와 shear thinning tendency가 증가하였고, G'-G" plot으로부터 탄성특성의 증가와 LCB의 도입에 의한 용융상태의 불균일성(heterogeneousness)을 확인할 수 있었다. LCB-PP/실리케이트 복합체의 실리케이트 함량에 따른 유변학적 특성을 관찰하였다. 실리케이트의 함량이 5 wt%인 경우 면찰 담화(shear thinning)와 G'-G" plot에서의 기울기 변화가 가장 크게 나타났다.

• 한국자동차공학회논문집
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• 제11권3호
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• pp.13-19
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• 2003

Mathematically simplified reaction scheme that simulates autoignitions of the end gases in spark ignition engines has been studied computationally. The five equation model is described, to predict the essential features of hydrocarbon oxidation. This scheme has been calibrated against autoignition delay times measured in rapid compression machines. The rate constants, activation temperatures, Ta, Arrhenius preexponential constants, A, and heats of reaction for stoichiometric n-heptane/air, iso-octane/air, and their mixtures have all been optimised. The optimisation has been guided by Morley's correlation of the ratio of chain branching to linear termination rates with octane number. Comparisons between computed and experimental autoignition delay times have validated the Present simplified reaction scheme and the influences of octane number upon autoignition delay times have been computationally investigated. It has been found that both cool flame and high temperature direct reactions can have an effect on autoignition delay times.

• Macromolecular Research
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• 제17권5호
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• pp.289-295
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• 2009

Low viscosity aromatic hyperbranched polyester epoxy resin (HTBE) was synthesized by the reaction between epichlorohydrin (ECH) and carboxyl-end hyperbranched polyester (HTB) which was prepared from inexpensive materials $A_2$ (1,4-butanediol glycol, BEG) and $B_3$ (trimellitic anhydride, TMA) by pseudo one-step method. The molar mass of the HTB was calculated from its acid value by "Recursive Probability Approach". The degree of branching (DB) of the HTB was characterized by model compounds and $^1H$ NMR-minus spectrum technology, and the DB of the HTB was about $0.47{\sim}0.63$. The viscosity and epoxy equivalent weight of the HTBE were $3,600{\sim}5,000\;cp$ and lower than 540 g/mol respectively. The reaction mechanism and structure of the $AB_2$ monomer, HTB and HTBE were investigated by MS, $^1H$ NMR and FTIR spectra technology. The molecular size of HTBE is under 8.65 nm and its shape is ellipsoid-like as determined by molecular simulation.