• 제어로봇시스템학회:학술대회논문집
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• 제어로봇시스템학회 1995년도 Proceedings of the Korea Automation Control Conference, 10th (KACC); Seoul, Korea; 23-25 Oct. 1995
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• pp.51-55
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• 1995

An adaptive unified predictive control (UPC) algorithm is applied to a batch polymerization reactor for poly(methyl methancrylate) (PMMA) and the effects of controller parameters are investigated. Computational studies are performed for a batch polymerization system model developed in this study. A transfer function in parametric form is estimated by recursive least squares (RLS) method, and the UPC algorithm is implemented to control the reactor temperature on the basis of this transfer function. The adaptive unified predictive controller shows a better performance than the PID controller for tracking set point changes, especially in the latter part of reaction course when gel effect becomes significant. Various performance can be acquired by selecting adequate values for parameters of the adaptive unified predictive controller; in other words, the optimal set of parameters exists for a given set of reaction conditions and control objective.

• Bulletin of the Korean Chemical Society
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• 제24권2호
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• pp.167-172
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• 2003

Alkyliron(Ⅲ) porphyrins, n-butyliron(Ⅲ) tetraphenylporphyrin, (TPP)Fe-Bu and n-butyliron(Ⅲ) tetrakis-(pentafluorophenyl)porphyrin, $(F_{20}TPP)Fe-Bu$ have been evaluated as suitable for olefin free-radical polymerization. Butyl radicals dissociated from n-butyliron(Ⅲ) porphyrin initiated the polymerization reaction, but the ratio of the propagation was low. The GCMS analysis of the reaction mixture of nbutyliron(Ⅲ) porphyrin and styrene has revealed several products containing two butyl groups, while traces of b-hydrogen-abstracted products were observed. The crystal structure of (TPP)Fe-Bu has been determined. The structure of the n-butyliron(Ⅲ) porphyrin reveals the compound containing five-coordinated iron with the average Fe-N distance of 1.973(1) Å and Fe-C of 2.030(2) Å. The iron atom is displaced by 0.137Å from a four nitrogen mean plane. Crystal system is triclinic, and space group is P-1.

• Elastomers and Composites
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• 제31권3호
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• pp.175-182
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• 1996

Polymer latices, prepared from the emulsion polymerization of vinyl monomer compounds, are widely used for many industrial applications. Included among these are uses in paints, adhesives, flocculants, and heavy-duty plastics as well as their original use in synthetic rubber compounds. The emulsion polymerization process with chemical initiator has chemical disadvantage such as removal of initiator which was left after polymerization. In this study, polystyrene latex was prepared by using ultrasonic irradiation which generate the free radical, and then it was analyzed by GPC. Reaction temperature hardly have an effect on average molecular weight. Average molecular weight is increased by increasing amount of surfactant, i.e. SDS, but polydispersity is decreased. After 90 minutes of reaction time, increase and decrease of average molecular weight Is repeated. It is proposed that monodisperse polymer is obtained by controlling ultrasonic irradiation time and surfactant concentration.

• Macromolecular Research
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• 제14권3호
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• pp.338-342
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• 2006

The kinetic features of polymerization with an active site comprising cobalt dihalides ($CoX_2$, where X=Cl, Br, I) activated by methylaluminoxane (MAO) were investigated in 1,3-butadiene polymerization. The catalytic system exhibited the characteristic features of living polymerization. The initiation ($k_i$) and propagation ($k_p$) rate coefficients were estimated using the kinetic model for slow initiation previously reported by Shiono et al. The energy of activation fur the propagation reaction was calculated to be 27-30 $kJmol^{-1}$. The marked changes in reaction rate observed with different halides could be adequately described in terms of variations in the initiation process, with the same Arrhenius curve fitting propagation rate coeffcients estimated from all three halides, suggesting that the halide does not participate in the growing chain end.

• 폴리머
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• 제24권4호
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• pp.437-444
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• 2000

본 연구는 metallocene 계열 촉매인 rac-Et(Ind)$_2$ZrCl$_2$촉매와 현재 상업용 공정에서 사용하고 있는 제3세대 Ziegler-Natta 촉매를 이용하여 반 회분식 반응기내에서 프로필렌 중합을 실시하였다. 이로부터 각 촉매계의 최적 중합 변수와 생성된 중합체의 각종 물성을 파악하였다. 두 촉매계로부터 생성된 중합체의 입자 크기 및 분포 결과와 중합 반응의 활성 측정 실험을 통해 Ziegler-Natta 촉매는 4$0^{\circ}C$에서, rac-Et(Ind)$_2$ZrCl$_2$는 5$0^{\circ}C$에서 각각 최적의 반응성을 나타냄을 알 수 있었다. 중합 온도는 추적의 중합 반응 활성 결과를 결정하는 중요한 인자이지만 과잉의 온도 조건에서는 중합체의 뭉침 현상이 현저함을 찰 수 있었다. 조촉매 농도 변화에 따른 중합 결과로부터 각 촉매계에서 조촉매의 농도 상한선을 구할 수 있었으며, 과량의 조촉매 농도는 오히려 중합 속도나 수율을 감소시킴을 알 수 있었다. Metallocene 촉매계에서 조촉매로 사용하는 methylaluminoxane (MAO)이나 triethylaluminum (TEAl)은 중합 활성에만 영향을 줄 뿐 중합체의 물성에는 영향을 주지 못하는 반면, Ziegler-Natta촉매계의 경우 para-ethoxyethylbenzoate (PEEB)는 중합 활성뿐 아니라 중합체의 입체 규칙성을 결정하는 중요한 인자로 작용함을 알 수 있었다. 본 실험에서는 단량체로 사용된 propylene의 분압과 중합체 수율간에는 1차의 선형관계가 성립됨을 발견할 수 있었다.

• 한국군사과학기술학회지
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• 제12권2호
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• pp.228-235
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• 2009

We synthesized glycidyl azide monomer(GAM) as a monomer for polymerization of glycidy azide polymer(GAP) which is a promising energetic prepolymer for a plastic-bonded explosive. Using quantitative real-tim in-situ infrared(in-situ IR) spectroscopy, kinetic study on the cationic ring opening polymerization of GAM was carried out. The reaction rate was obtained from monitoring the change of ether C-O stretching band($1050cm^{-1}$) in series IR spectra. The reaction was in accordance with the first-order reaction law for each of reaction temperature at 100/1 mole ratio of [GAM]/[$BF_3*etherate$]. In the ring opening polymerization of GAM, with ratio of [GAM]/[$BF_3*etherate$] to equal 100/1 at various temperature, the activation parameters obtained from the evaluation of kinetic data were ${\Delta}H^*$=14.34kcal/mol, ${\Delta}S^*=-12.31cal/mol{\cdot}K$ and $E_a$=14.89kcal/mol.

• Elastomers and Composites
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• 제43권3호
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• pp.157-165
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• 2008

현탁중합법을 이용하여 카본블랙을 함유하는 폴리뷰틸메타크릴레이트 복합체 입자를 합성하였다. 물을 반응매체로 선택하고 소수성실리카를 안정제로 azobisisobutyronitrile (AIBN)을 개시제로 선택하였다. 안정제의 농도는 물에 대하여 0.67 중량%에서 2.55 중량%까지 변화시켰으며, 개시제는 단량체에 대하여 0.25 중량%에서 3.00 중량%까지 변화시키면서 반응역학에 미치는 영향을 조사하였다. 모든 반응은 75$^{\circ}C$에서 진행하였다. 안정제의 농도는 반응속도에 무관하였으나, 개시제의 증가는 반응속도를 증가시켰다. 카본블랙을 단량체에 대하여 1, 3 및 5 중량% 유입하는 경우 반응전환율은 단계적으로 감소하였다. 폴리뷰틸메타크릴레이트 복합체 입자의 입경은 5-30 ${\mu}m$로 관찰되었다. 유리전이온도는 카본블랙의 유입 및 개시제, 안정제의 농도에 무관하게 23.8-24.7$^{\circ}C$로 측정되었다.

• 공업화학
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• 제17권1호
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• pp.33-36
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• 2006

광경화 접착제로 많이 사용되는 우레탄-아크릴레이트 올리고머의 광경화 거동을 자체촉매화 반응모델식을 통해 중합온도 및 올리고머의 관능성에 따른 영향을 확인하여 보았다. 중합온도가 증가함에 따라 최대중합속도는 감소하여 중합온도가 경화 거동에 대한 영향인자임을 확인할 수 있었으며, 반응속도상수 k는 온도증가에 따라 거의 일정한 값을 보이나 반응차수 m과 n은 증가하는 경향을 보였는데 이는 가교구조에 의한 반응성 기의 확산제한 및 유동성의 제한으로 인한 것으로 판단되어진다. 온도증가에 따른 중합속도의 감소는 주로 반응차수 n의 증가에 의해 진행되었다.

• 한국군사과학기술학회지
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• 제8권2호
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• pp.67-76
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• 2005

We synthesized an energetic prepolymer(glycidyl dinitro propyl formal, GDNPF) for plastic-bonded explosive and measured its thermodynamic parameters. Glycidyl dinitro propyl formal(GDNPF) as an energetic monomer was epoxidized from allyl-2,2-dinitro propyl formal which is reacted with dinitro propyl alcohol and excess allyl alcohol, and then energetic polymer of GDNPF was polymerized by cationic ring opening polymerization. Thermodynamic parameters were obtained from the ceiling temperature($T_c$) values of 1 mole monomer at reaction temperature. We varied feed rate of monomer, concentration of initiator and monomer to control molecular weight and polydispersity of prepolymer (GDNPF). The activated monomer polymerization has been executed with precisely controlled feed of GDNPF monomer to reactor in the complex state catalyst generated by $BF_3{\cdot}(C_3H_5)_2$ and 1,4-butanediol in $C_2H_4Cl_2$. Number average molecular weight(Mn), polydispersity(Pd), hydroxy number and glass transition temperature($T_g$) of prepolymer(GDNPF) were $2,500{\sim}3,000,\;1.2{\sim}1,3,\;0.6{\sim}0.8eq/kg\;and\;-20{\sim}-25^{\circ}C$ respectively.

• Fibers and Polymers
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• 제5권4호
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• pp.253-258
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• 2004

Living nature of photoinduced cationic polymerization of isobutyl vinyl ether (IBVE) in the presence of various combinations of diphenyliodonium halide (DPIX), a photocationic initiator and zinc halide $(ZnX_2)$ in methylene chloride has been investigated. Attainment of $100\%$ conversion and a linear relationship between $\%$conversion and number average molar mass of the resulting polymer, strongly suggests the living nature of this system. Livingness of the polymerization system was observed irrespective to the type of halide anion of the initiator and zinc salts unless the reaction temperature is not higher than $-30^{\circ}C$. The rate of polymerization decreases in the order of iodide > bromide > chloride when halide salt of DPIX and $ZnX_2$ are used. It is postulated that the cationic initiation is started by the insertion of weakly basic monomer in to the activated C-X terminal of the monomer adduct which is a reaction product of monomer and HX, a photolytic product of DPIX, formed in situ during the photo-irradiation process. It was concluded that polymerization is initiated by the insertion of weakly basic monomer into activated C- X terminal of monomer adduct due to the pulling action of$ZnX_2$, which successively producing a new polarized C-X terminal for the propagation in cationic nature. This led us to a conclusion that the living nature of this cationic polymerization is ascribable to the polarized C-X growing terminal, which is stable enough to depress the processes of chain transfer or termination process.