• Title/Summary/Keyword: 중합반응속도

Search Result 139, Processing Time 0.027 seconds

Kinetic Study on the Polycondensation Reaction of Bis-hydroxyethyl Naphthalate (Bis-hydroxyethyl Naphthalate의 축중합 반응에 관한 속도론적 연구)

  • 이성진;정성일
    • Polymer(Korea)
    • /
    • v.26 no.4
    • /
    • pp.422-430
    • /
    • 2002
  • The kinetics of polycondensation of bishydroxyethyl naphthalate has been studied in the range of 241 -$260^{\circ}C$ using antimony trioxide catalyst. The reaction was performed in a batch reactor and the concentration of reaction mixture was measured with HPLC. The activation energy values of forward and reverse reaction determined from molecular species model were found to be 19.7 and 31.4 kcal/mole, respectively, and the equilibrium constants were in the range of 1.4-2.0, which were larger than that of polycondensation of PET and varied to some degree with temperature. It was confirmed by applying the Flory's distribution function that the reaction rate of the hyroxyethyl group does not depend on the molecular size. By applying functional group model, we observed that there was few difference between the activation energy of the forward reaction and that of reverse reaction, therefore the equilibrium constant has almost constant value of 1.4. The rate constants obtained from functional group model was about 3-4 times larger than that from molecular species model, which showed that both model explains the reaction system well. Although the molecular species model should predict the concentration of as many as ten molecules, it fits for the experimental results well.

Estimation of Activation Energy for the Free Radical Polymerization by Using Isoconversional Analysis (등전환 분석(Isoconversional Analysis)를 이용한 자유라디칼 중합의 활성화 에너지 계산)

  • Chung, I.
    • Elastomers and Composites
    • /
    • v.39 no.4
    • /
    • pp.281-285
    • /
    • 2004
  • In this paper, the simple way to evaluate the value of the activation energy for the overall rate of free radical polymerization by using DSC thermograms was studied using free radical polymerization or butylacrylate as a model. Activation ehergies were determined at heating rates of 1, 2, 5, and $10^{\circ}C/min$ by applying the multiple scanning-rate methods of Kissinger, Osawa, and half-width methods as well as the single rate method of Barrett. The value of the overall activation energy measured was closely matched with the values calculated from individual data. This work also demonstrated that the use of the isoconversional method was a simple and effective way to estimate the activation energy for the overall free radical polymerization.

A Study on the Sol-Gel Reaction Kinetics of Sodium Silicate Solution (규산(硅酸)나트륨 수용액(水溶液)의 솔-젤 반응속도론적(反應速度論的) 고찰(考察))

  • Kim, Chul-Joo;Yoon, Ho-Sung;Jang, Hee-Dong
    • Resources Recycling
    • /
    • v.17 no.6
    • /
    • pp.34-42
    • /
    • 2008
  • The properties of sodium silicate solution were surveyed by using the yellow silicomolybdic method, and the formation of silica sol from sodium silicate solution and the growth of silica sol were investigated in this study. The $SiO_2$ content of 2 wt% in sodium silicate solution was proper to oxidize sodium silicate with sulfuric acid. After the removal of sodium ions in sodium silicate solution, the pH of silicate solution had to be controlled above 9 for the stabilization of silicate solution. The condensation between silicic acid species and silica nuclei surfaces has been studied at $20{\sim}80^{\circ}C$ and pH 10 in silicate solutions with silica nuclei. The reaction falls into two kinetics regimes, limited at high silicic acid species concentration by polymerization, but at lower concentration by a process whereby deposited silicic acid species condenses further to silica. The overall condensation is first-order in silicic acid species concentration, proceeded toward to pseudo equilibrium concentration, $C_x$, rather than the solubility of amorphous silica. The heat of solution of amorphous silica was 3.34 kcal/mol and exhibits an Arrhenius temperature dependence with an apparent activation energy of 3.16 kcal/mol in the range of $20{\sim}80^{\circ}C$.

Effect of Protonic Acids on the Reaction Rate in Chemical Polymerization of Polyaniline (폴리아닐린의 화학적 중합 시 반응속도에 미치는 양성자산의 영향)

  • Hong, Jang-Hoo;Jang, Beom Soon
    • Applied Chemistry for Engineering
    • /
    • v.16 no.5
    • /
    • pp.684-688
    • /
    • 2005
  • Aniline was polymerized in various protonic acid (HF, HC1, HBr, HI, $H_2SO_4$) aqueous solutions with different acidity. During the reaction, the dimer formation and the reaction rate were examined as functions of acidity (pH) and the size of counter ions. Open-circuit potential measurements were carried out to investigate the effect of protonic acid on the reaction rate. The results showed that polymerization rate in HF aqueous solution was very slow and polymerization did not occur in HI aqueous solution. These results were explained in terms of acidity and power of oxidation. The ratio of formation of dimers varied with the kind of protonic acid, and the results were explained with the nucleophilicity, solvation effect, and mobility of counter ions.

Polymerization of Methyl Methacrylate Initiated by Cobalt (II) Nitrate (질산코발트 (II)에 의한 Methyl Methacrylate의 중합)

  • Jang-oo Lee;Dong-ho Lee;Tae-oan Ahn
    • Journal of the Korean Chemical Society
    • /
    • v.19 no.6
    • /
    • pp.463-467
    • /
    • 1975
  • The polymerization of methyl methacrylate(MMA) initiated by cobalt (II) nitrate in tetrahydrofuran (THF) has been studied. From the results of kinetic studies, the overall polymerization rate (Rp) could be expressed as following; $R_p=k\;[cobalt(Ⅱ)\;nitrate]^{0.5}\;[MMA]^{1.5}$ By considering the effects of chelating agent on the polymerization rate, it could be assumed that the monomer, MMA might form a coordination complex with cobalt(II) nitrate. In the presence of radical inhibitor hydroquinone, the inhibition time was observed. And the apparent overall activation energy was calculated to be 14.0 kcal/mole.

  • PDF

Synthesis and Photopolymerization Characterization of Propenyl Ether Monomers (프로페닐 에테르 단량체들의 합성과 광중합 특성)

  • Kim, Ki-Sang;Shim, Sang-Yeon
    • Journal of the Korean Applied Science and Technology
    • /
    • v.34 no.2
    • /
    • pp.203-209
    • /
    • 2017
  • The propenyl ether-type monomers which are applicable for cationic photo-polymerization were synthesized by the condensation reaction of mono and di-functional alcohol with allyl bromide. To examine photo-curable reactivity, these monomers were combined with cationic photoinitiator to prepare coating composition. As a result, the initial rate of polymerization of POMB in mono propenyl ether type was 10.2, which was relatively lower than BPOB in di-propenyl ethers type. However, POMB containing 1.5mol% photoinitiator almost quantitatively reacted within 90 seconds. In addition, Sulfonium salt type photo-initiators containing long-alkyl group showed good solubility with monomers and apperaed to have comparatively higher rate of polymerization and conversion ratio when applying DPSA and DPST which have high acidity on all monomers.

Surface Morphology Control of Monodisperse Crosslinked-Polymer Particle (단분산 가교고분자 미립자의 표면 모폴로지 제어 연구)

  • Kim, Dong-Ok;Jin, Jeong-Hee;Oh, Seok-Heon
    • Polymer(Korea)
    • /
    • v.30 no.1
    • /
    • pp.50-55
    • /
    • 2006
  • When the monodisperse polystyrene(PS)/HDDA polymer particles were synthesized via one-step polymerization using polystyrene seed particles by dispersion polymerization, the effects of 1) the molecular weight of seed polymer particles, 2) the ratio of the absorbed HDDA to the seed polymer particles (swelling ratio) and 3) seeded polymerization rate on the surface morphology of PS/HDDA polymer particles were investigated. It was observed that the creation of the crater shaped defect on the surface of PS/HDDA polymer particles was irrespective of the molecular weight of seed polymer ant swelling ratio. But its surface morphology could be controlled by the change of the seeded polymerization rate.

Kinetics of Pholopolymerization of Acrylonitrile Using Sensitizer (광증감제에 의한 Acrylonitrile의 광중합 속도 (I))

  • Seul, Soo-Duk
    • Elastomers and Composites
    • /
    • v.34 no.1
    • /
    • pp.3-10
    • /
    • 1999
  • Kinetics of solution photopolymerization of acrylonitrile(AN) with sensitizer, such as $NaSCN,\;KSCN,\;Ba(SCN)_2,\;NH_4SCN,\;ZnCl_2$ and $Na_2SeO_3$, were studied using UV crosslinker at various monomer concentrations($1.8{\sim}7.58mo1/1$), sensitizer concentrations($10{\sim}60%$), reaction temperature($10{\sim}70^{\circ}C$), energy intensities($1,000{\sim}9,900{\mu}J/cm^2$) at isothermal condition under nitrogen atmosphere. Under the irradiation of high pressure mercury lamp(${\lambda}=365nm$). High conversion and uniform molecular weight were obtained compare to thermal polymerization at reaction temperature of $50^{\circ}C$, reaction time of 3hr and 50% NaSCN without any initiator. Their kinetic model was as follows : $R_p=0.0142[M]^{0.82}[I]^{0.49}[S]^{0.52}$ exp(-1.33/RT).

  • PDF

Thermal Hazards of Polystyrene Polymerization Process by Bulk Polymerization (벌크 중합법에 의한 폴리스티렌 중합공정의 열적위험성)

  • Han, In-Soo;Lee, Jung-Suk;Lee, Keun-Won
    • Journal of the Korean Institute of Gas
    • /
    • v.17 no.4
    • /
    • pp.1-8
    • /
    • 2013
  • The aim of this study is to assess thermal hazards of polystyrene polymerization process by bulk polymerization with accelerating rate calorimeter(ARC) and Multimax reactor system(MM). From this study, we found out that the polymerization process should be operated at reaction temperature of $120^{\circ}C{\sim}130^{\circ}C$. At reaction temperature over $130^{\circ}C$, there was a runaway reaction hazard due to the temperature control failure following a viscosity increase of reaction products. With a cooling failure of a reactor in the early stage of process operation at the reaction temperature ($120^{\circ}C{\sim}130^{\circ}C$), there was a high thermal hazard of burst of a reactor's rupture disk or explosion of a reactor caused by the rapid rise of temperature and pressure to $340^{\circ}C$, 5.3 bar respectively within 30 - 50 minutes.

Mechanism of Dextran Synthesis by Dextransucrase (Dextransucrase에 의한 Dextran 생성기작에 관한 연구)

  • 윤명희;구윤모
    • KSBB Journal
    • /
    • v.9 no.1
    • /
    • pp.1-7
    • /
    • 1994
  • A qualitative study was made on the mechanism of dextran synthesis by dextransucrase. Enzymatic synthesis of dextran was experimentally studied with initial sucrose concentration from 50g/$\ell$ to 150g/$\ell$. The molecular weight distribution of synthesized dextran was measured by using on-line gel Permeation chromatographic system Sucrose was observed not to work as a primer within the range of concentration tested. At the initial sucrose concentration of 50g/$\ell$, dextran with molecular weight of medium range ($10^4-2{\times}10^6$) was synthesized due to the mass transfer limitation of sucrose. The amount of the dextran of medium range decreased with the initial sucrose concentration. Dextran was likely to be synthesized by radical chain polymerization mechanism since the dextran of medium range was not produced at higher sucrose concentrations.

  • PDF