• Title/Summary/Keyword: reactivity ratios

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The Kinetics of Radical Copolymerization of Styrene with Alkyl Methacrylate in a CSTR (연속반응기에서 스티렌과 메타크릴산 알킬의 라디칼 공중합 반응속도론)

  • Kim, Nam Seok;Seul, Soo Duk;Cheong, Young Eon;Park, Keun Ho;Choi, Jong jueng
    • Applied Chemistry for Engineering
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    • v.10 no.5
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    • pp.796-803
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    • 1999
  • Solution copolymerization of styrene(St.) with methyl methacrylate(MMA), ethyl methacrylate(EMA) and n-butyl methacrylate(BMA) was carried out with benzoylperoxide(BPO) as an initiator in toluene at $80^{\circ}C$ in a continuous stirred tank reactor. Reaction volume and residence time were 0.6 liters and 3hours, respectively. The monomer reactivity ratios, $r_1(St.)$ and $r_2(RMA)$ determined by both the Kelen-Tudos method and the Fineman-Ross method were $r_1(St.)=0.60(0.61),\;r_2(MMA)=0.59(0.60);\;r_1(St.)=0.65(0.62),\;r_2(EMA)=0.55(0.52);\;r_1(St.)=0.75(0.67),\;r_2(BMA)=0.63(0.56)$. The cross-termination factor $\Phi$ of the copolymer over the entire St. compositions ranged from 0.26 to 0.96. The $\Phi$ factors of St.-RMA copolymer were increased with increasing St. content. The simulated conversions and copolymerization rates were compared with the experimental results. The average time to reach dynamic steady-state was three times and half of the residence time.

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Studies on Chemical Strutures and Adhesion Performance of pMDI Adhesives Modified by Ozonized Soybean Oil with Different Mixing Ratios (오존산화 콩기름의 구조분석 및 이를 이용한 변성 pMDI 접착제의 중량비에 따른 접착력 변화)

  • You, Young Sam;Lee, Hyun Jong;Lee, Taek Jun;Park, Heon
    • Journal of the Korean Wood Science and Technology
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    • v.37 no.1
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    • pp.56-64
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    • 2009
  • The purpose of this study was to investigate and develop an eco-friendly wood adhesive based on vegetable oil (especially soybean oil), the renewable and sustainable natural resources, using ozonification technology for the chemical structure modification. The soybean oil (SBO) was reacted with $O_3$ at the rate of 7.13 g/h for different times, 15 minutes, 30 minutes, 60 minutes, and 120 minutes. The investigation of the modified chemical structure of the ozonized SBOs were conducted using FT-IR, $^1H$-NMR, MALDI-TOF MS, and GC/MS. As ozonification time increased, the peak of the unsaturated double bonds was disappeared and aldehyde or carboxyl peak appeared because ozonification broke the oil into small molecules. The plywoods were made at $110^{\circ}C$ with 30 seconds/mm hot-press time using the different ozonized SBO/pMDI adhesives and were tested for the dry, wet, cyclic boil test according to the Korea Industrial Standard F3101 Ordinary plywood. The bond strengths gradually increased with increasing ozonification time. The weight ratio 1:1 (ozonized SBO/pMDI), all strengths in 15, 30 and 60 minuets, exceeded constantly the dry, wet, cyclic boiling standard requirement. The range of ozonification time and weight ratio can fulfil1 the requirment of the wet test standard were 30~60 minutes and more than 0.5 pMDI. From the comprehensive view on the results of above experiments, it could be confirmed through experiments that ozonized SBO/pMDI has characteristics of effective reactivity and wet stability showed as an excellent candidate of wood adhesive applications.

The Reactivity and Regiochemical Effect of Nitrosonium Species in the Nitrosation of N-Methyl-N'-Substituted Phenylureas (N-메틸-N'-치환페닐우레아화합물들의 니트로소화 반응에 있어서 니트로소화 화학종의 반응성 및 위치화학적 영향)

  • Jack C. Kim;In-Seop Cho;Soon-Kyu Choi
    • Journal of the Korean Chemical Society
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    • v.35 no.3
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    • pp.240-248
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    • 1991
  • The regioselectivity in the nitrosation of seven N-methyl-N'-substituted phenylureas ($CH_3NHCONHC_6H_4-G$; G = H, p-CH$_3$, m-CH$_3$, m-CH$_3$O, p-F, m-F, m-Br) was examined using NaNO$_2$ and 4 different acids (diluted HCl, HCOOH, CH$_3$COOH, CF$_3$COOH). In all cases, the two regioisomeric products, N-nitroso-N-methyl-N'-substituted phenylureas (A) and N'-nitroso-N-methyl-N'-substituted phenylureas (B) were observed to be formed as major products and product ratios were determined by the integration of their methyl peaks in $^1$H-NMR. Electron donating substitutent(G) on phenyl of the ureas generally led to increase the ratio of B to A. The data have revealed that the relative sensitivity of the nitrosonium species (HONO, HCOONO, CH$_3$COONO, CF$_3$COONO) toward the change of electron density on nitrogen with phenyl substitutents are 1.00 : 0.93 : 0.78 : > ∼ 0.7.

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Synthesis of Polyester Polyols by Using Double Metal Cyanide Catalyst and Physical Properties of Polyurethanes Produced by the Polyols (이중금속시안염 촉매에 의한 폴리에스테르 폴리올 제조 및 이를 이용한 폴리우레탄의 물성)

  • Kim, In-Ki;Seo, Hyun-Sook;Ha, Chang-Sik;Park, Dae-Won;Kim, Il
    • Clean Technology
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    • v.14 no.1
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    • pp.29-34
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    • 2008
  • Copolymerizations of propylene oxide (PO) and phthalic anhydride (PA) have been performed in the presence of double metal cyanide (DMC) catalyst as a means of incorporating ester groups in the polyol backbone. DMC catalyst was effective for the copolymerization and the reactivity ratios measured by modified Kelen-$T{\ddot{u}}d{\ddot{o}}s$ equation were $r_1(PA)\;=\;0$, and $r^2(PO)\;=\;0.248$. Four different Polyol samples containing 1.0, 2.1, 7.52, and 11.42 mol% of PA unit were utilized for the synthesis of thermoplastic polyurethanes of their hard segments of 19 wt%. As the incorporated amount of PA increases, the elongation of the resulting polyurethane decreases and the tensile strength and the tensile modulus increase. The modulation of the incorporated amount of PA into polyol backbone was proven to be a feasible way to tune the physical properties of polyurethanes.

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Analysis of Sensors' Behavior and Its Utility for Shallow Landslide Early Warning through Model Slope Collapse Experiment (붕괴모의실험을 통한 산사태 조기경보용 계측센서의 반응성 분석 및 활용성 고찰)

  • Kang, Minjeng;Seo, Junpyo;Kim, Dongyeob;Lee, Changwoo;Woo, Choongshik
    • Journal of Korean Society of Forest Science
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    • v.108 no.2
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    • pp.208-215
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    • 2019
  • The goal of this study was to analyze the reactivity of a volumetric water content sensor (soil moisture sensor) and tensiometer and to review their use in the early detection of a shallow landslide. We attempted to demonstrate shallow and rapid slope collapses using three different soil ratios under artificial rainfall at 120 mm/h. Our results showed that the measured value of the volumetric water-content sensor converged to 30~37%, and that of the tensiometer reached -3~-5 kPa immediately before the collapse of the soil under all three conditions. Based on these results, we discussed a temporal range for early warnings of landslides using measurements of the volumetric water content sensors installed at the bottom of the soil slope, but could not generalize and clarify the exact timing for these early warnings. Further experiments under various conditions are needed to determine how to use both sensors for the early detection of shallow landslides.

Removals of 1-Naphthol in Aqueous Solution Using Alginate Gel Beads with Entrapped Birnessites (버네사이트를 고정화한 알긴산 비드(Bir-AB)를 이용한 수용액 중 1-Naphthol의 제거)

  • Eom, Won-Suk;Lee, Doo-Hee;Shin, Hyun-Sang
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.4
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    • pp.247-256
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    • 2013
  • In this study, alginate beads containing birnessite (Bir-AB), a highly reactive oxidative catalyst for the transformation of phenolic compounds, was prepared and its 1-naphthol (1-NP) removal efficiency was investigated in a batch test. Based on scanning electron microscopy image, it can be inferred that the alginate gel cluster acts as a bridge which bind the birnessite particles together. Kinetic experiment with Bir-AB of different mixing ratios of birnessite to alginate (Bir : AG=0.25 : 1~1 : 1 w/w) indicate that pseudo-first order kinetic constants, $k(hr^{-1})$ for the 1-NP removals increased about 1.5 times when the birnessite mixing ratio was doubled. The removals of 1-NP was found to be dependent on solution pH and the pesudo-first order rate constants were increased from 0.331 $hr^{-1}$ at pH 10 to 0.661 $hr^{-1}$ at pH 4. The analysis of total organic carbon for the reaction solutions showed that a higher removal of dissolved organic carbon was achieved with Bir-AB as compared to birnessite. HPLC chromatographic analysis of the methanol extract after reaction of 1-NP with Bir-AB suggest that the reaction products could be removed through incorporation into the aliginate beads as a bound residue. Mn ions produced from the oxidative transformation of 1-NP by birnessite were also removed by sorption to Bir-AB. The Bir-AB was recovered quantitatively by simple filtration and was reused twice without significant loss of the initial reactivity.