• Title/Summary/Keyword: reactivity ratios

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Free-Radical Copolymerization of Glycidyl Methacrylate with Phthalimidoethyl Acrylate : Synthesis and Determination of Monomer Reactivity Ratios (GMA와 프탈이미드아크릴레이트의 공중합체 합성과 반응성비)

  • Oh, Seung-Min;Oh, Dae-Hee
    • Journal of the Korean Applied Science and Technology
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    • v.30 no.2
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    • pp.297-304
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    • 2013
  • Free-radical copolymerization of glycidyl methacrylate(GMA) and N-phthalimidoethyl acrylate(NPEA) were carried out at $60^{\circ}C$ in dimethylformamide(DMF) solution in the presence of benzoylperoxide(BPO) at low conversion. The polymers were characterized by IR and $^1H$-NMR. The compositions of the copolymer was analyzed by ultra violet(UV/Vis) spectrophotometry. The reactivity ratios of the monomer was determined by the application of Fineman-Ross(FR) and Kelen-T$\ddot{u}$d$\ddot{o}$s(KT) methods. The monomer reactivity ratios of the system and Alfrey-Price's resonance effect(Q) and polar effect(e) value for NIEA were determined as follow. The reactivity ratios of the monomer obtained from FR and KT are found to be $r_1$=0.87, $r_2$=0.98 and $r_1$=0.88, $r_2$=0.99 respectively. The Q and e values of poly(GMA-co-NPEM) calculated from $r_1$ and $r_2$ was Q= 1.31, e=0.75 respectively.

Properties of Urea-Formaldehyde Resin Adhesives with Different Formaldehyde to Urea Mole Ratios

  • Park, Byung-Dae
    • Journal of the Korean Wood Science and Technology
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    • v.35 no.5
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    • pp.67-75
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    • 2007
  • As a part of abating the formaldehyde emission of urea-formaldehyde (UF) resin adhesive by lowering formaldehyde to urea (F/U) mole ratio, this study was conducted to investigate properties of UF resin adhesive with different F/U mole ratios. UF resin adhesives were synthesized at different F/U mole ratios of 1.6, 1.4, 1.2, and 1.0. Properties of UF resin adhesives measured were non-volatile solids content, pH level, viscosity, water tolerance, specific gravity, gel time and free formaldehyde content. In addition, a linear relationship between non-volatile solids content and sucrose concentration measured by a refractometer was established for a faster determination of the non-volatile solids content of UF resin. As F/U mole ratio was lowered, non-volatile solids content, pH, specific gravity, water tolerance, and gel time increased while free formaldehyde content and viscosity were decreased. These results suggested that the amount of free formaldehyde strongly affected the reactivity of UF resin. Lowering F/U mole ratio of UF resin as a way of abating formaldehyde emission consequently requires improving its reactivity.

Copolymerization of N-Vinyl Pyrrolidone with Functionalized Vinyl Monomers: Synthesis, Characterization and Reactivity Relationships

  • Vijaykumar, S.;Prasannkumar, S.;Sherigara, B.S.;Shelke, N.B.;Aminabhavi, Tejraj M.;Reddy, B.S.R.
    • Macromolecular Research
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    • v.17 no.12
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    • pp.1003-1009
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    • 2009
  • Copolymers of N-vinylpyrrolidone (NVP) comonomer with styrene (St), hydroxypropyl methacrylate (HPMA) and carboxyphenyl maleimide (CPMI) were synthesized by free radical polymerization using 2,2'-azobisisobutyronitrile (AIBN) initiator in 1,4-dioxane solvent. The copolymers formed were characterized by FTIR, $^1H$ NMR and $^{13}C$ NMR techniques and their thermal properties were studied by DSC and TGA. Copolymer composition was determined by $^1H$ NMR and/or by elemental analysis and monomer reactivity ratios (MRR) were estimated by the linear methods of Kelen-Tudos (K-T) and extended Kelen-Tudos (EK-T) and the non-linear approach. Copolymers of St and HPMA with NVP formed blocks of one of the monomer units, whereas alternating copolymers were obtained in CPMI-NVP, depending upon the side chain substitution. The MRR values are discussed in terms of monomer structural properties such as electronegativity and electron delocalization. The sequence distribution of monomers in the copolymers was studied by statistical method based on the average reactivity ratios obtained by EK-T method.

Effectiveness of mineral additives in mitigating alkali-silica reaction in mortar

  • Nayir, Safa;Erdogdu, Sakir;Kurbetci, Sirin
    • Computers and Concrete
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    • v.20 no.6
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    • pp.705-710
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    • 2017
  • The effectiveness of mineral additives in suppressing alkali-silica reactivity has been studied in this work. Experimentation has been performed in accordance with the procedures prescribed in ASTM C 1567. In the scope of the investigation, a quarry aggregate which was reactive according to ASTM C 1260 was tested. In the experimental program, prismatic mortar specimens measuring $25{\times}25{\times}285mm$ were produced. Ten sets of production, three specimens for each set, were made. Length changes were measured at the end of 3, 7, 14 and 28 days and then expansions in percentage have been calculated. Fly ash, silica fume, and metakaolin have been used as cement replacement in different ratios for the testing of the alkali-silicate reactivity of the aggregate. In the mixes performed, the replacement ratios were 20%, 40%, and 60% for the fly ash, and 5%, 10%, and 15% for the silica fume, and 5%, 10%, and 15% for the metakaolin. Mixes without mineral additives were also produced for comparison. The beneficial effect in suppressing alkali-silica reactivity is highly noticeable as the replacement ratios of the mineral additives increase regardless of the type of the mineral additive used. Being more concise, the optimum concentrations of using silica fume and metakaolin in mortar in suppressing ASR is 10%, respectively, while it is 20% for fly ash.

Effects, of Catalyst Pore Structure on Reactivity in Simplified Reaction System

  • Rhee, Young-Woo;Son, Jae-Ek
    • Journal of Energy Engineering
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    • v.2 no.1
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    • pp.114-122
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    • 1993
  • A model describing the reaction rate and catalyst deactivation in a simplified reaction system was developed to investigate the significance of catalyst pore structure in terms of porosities, porosity ratios, and size ratios of reactants to pores. The model showed that the unimodal catalyst could give a better performance than the bimodal in certain circumstances and the crossover found in the reactivity curves resulted from a trade-off between surface area and diffusivity. Under the assumption of uniform coke buildup, the bimodal catalyst appeared to provide better resistance to deactation than unimodal catalyst.

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Synthesis and Monomer Reactivity Ratio of PNIPAAM-PMMA Random Copolymer (PNIPAAM-PMMA Random Copolymer의 합성 및 단량체 반응성비 측정)

  • 이창배;조창기
    • Polymer(Korea)
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    • v.24 no.2
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    • pp.168-173
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    • 2000
  • Radical copolymerization of N-isopropylacrylamide (NIPAAM) with methyl methacrylate (MMA) was carried out in 1,4-dioxane using 2,2'-azobisisobutyronitrile (AIBN). To investigate the reactivity ratios of NIPAAM and MMA at different reaction temperatures, the copolymerization was allowed to proceed to low conversion (less than 10 wt%), and the reaction temperatures were 50, 60, and 7$0^{\circ}C$. The monomer reactivity ratios of NIPAAM and MMA were estimated by the graphical methods according to the Finemann-Ross equation. The ${\gamma}$$_1$ and ${\gamma}$$_2$ values for NIPAAM-MMA were 0.259 and 2.782 at 5$0^{\circ}C$, 0.271 and 2.819 at 6$0^{\circ}C$, and 0.286 and 2.915 at 7$0^{\circ}C$, respectively. As the reaction temperature increased, the ${\gamma}$$_1$ and ${\gamma}$$_2$ values increased. The activation energy difference was estimated by comparing the reactivity ratios at different reaction temperatures.

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Methacrylate Polymers Having Pendant Chalcone Moieties: Monomer Reactivity Ratios, Thermal and Optical Properties (캘콘기를 가지는 메타크릴레이트 고분자: 모노머 반응성비와 열적 광학적 성질)

  • Barim, Gamze;Altun, Ozgul;Yayla, Mustafa Gokhun
    • Polymer(Korea)
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    • v.39 no.1
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    • pp.13-22
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    • 2015
  • A new methacrylate copolymer that includes chalcone as a side group, poly(4-methacryloyloxyphenyl-4'-methoxystyryl ketone-co-styrene) was synthesized by free radical copolymerization. FTIR and $^1H$ NMR spectroscopic techniques were used to characterize the homopolymers and copolymers. The copolymerizations were carried out to high conversions. Copolymer compositions were established by $^1H$ NMR spectra analysis. The monomer reactivity ratios for copolymer system were determined by the linearized Kelen $T{\ddot{u}}d{\ddot{o}}s$, and Extended Kelen $T{\ddot{u}}d{\ddot{o}}s$ methods and a non-linear least squares method. The molecular weights and polydispersity index of copolymers were measured by using the gel permeation chromatography (GPC). The effect of copolymer compositions on their thermal behavior were studied by differential scanning calorimetry and thermogravimetric analysis methods. The optical properties of the resulting copolymer were also investigated.

A Study on the Copolymerization Kinetics of Phenylethyl Acrylate and Phenylethyl Methacrylate

  • Lee, Han-Na;Tae, Gi-Yoong;Kim, Young-Ha
    • Macromolecular Research
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    • v.16 no.7
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    • pp.614-619
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    • 2008
  • Copolymers of phenyl alkyl acrylates/methacrylates are used clinically as soft materials for the foldable intraocular lens (IOL) to treat cataracts. In this study, copolymers of 2-phenylethyl acrylate (PEA) and 2-phenylethyl methacrylate (PEMA) of various compositions were prepared using free radical polymerization in solution. The composition of the copolymers was determined by $^1H$-NMR analysis. The reactivity ratios of the monomers were calculated using the conventional Fineman-Ross or Kelen-Tudos method. The reactivity ratio of PEA ($r_1$) and PEMA ($r_2$) were estimated to be 0.280 and 2.085 using the Kelen-Tudos method, respectively. These values suggest that PEMA is more reactive in copolymerization than PEA, and the copolymers will have a higher content of PEMA units. The glass transition temperature ($T_g$) of the copolymers increased with increasing PEMA content. The molecular weight and polydispersity indices ($M_w/M_n$) of the polymers were determined by GPC. Overall, these results are expected to be quite useful in applications to foldable soft IOL materials.

The Characteristics of Ozone Formation from a Gaseous Fueled SI Engine with Various Operating Parameters (여러 가지 운전조건에 따른 가스연료엔진 오존발생량 연구)

  • 김창업;강건용;배충식
    • Transactions of the Korean Society of Automotive Engineers
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    • v.11 no.6
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    • pp.86-92
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    • 2003
  • To analyze the characteristics of ozone formation, measurements of the concentrations of individual exhaust hydrocarbon species have been made under various engine operating parameters in a 2-liter 4-cylinder engine for natural gas and LPG. Tests were performed at constant engine speed, 1800 rpm for two compression ratios of 8.6 and 10.6, with various operating parameters, such as excess air ratio of 1.0~1.6, bmep of 250~800 na and spark timing of BTDC 10~$55^{\circ}$. It was found that the natural gas gave the less ozone formation than LPG in various operating conditions. This was accomplished by reducing the emissions of propylene($C_3H_6$), which has relatively high maximum incremental reactivity factor, and propane($C_3H_8$) that originally has large portion of LPG. In addition, the natural gas show lower values in the specific reactivity and brake specific reactivity. Higher compression ratio of the test engine showed higher non methane HC emissions. However, specific reactivity value decreased since fuel species of HC emissions increase. brake specific reactivity showed almost same values under high bmep, over 500kPa for both fuels. This means that the increase of non methane HC emissions and the decrease of specific reactivity with higher bmep affect each other simultaneously. With advanced spark timing, brake specific reactivity values of LPG were increased while those of natural gas showed almost constant values.

The Kinetics of Radical Copolymerization and Thremal Decoposition of Poly(Styrene-co-2- Hydroxypropylacrylate) (Poly(Styrene-co-2-Hydroxypropylacrylate)의 라디칼 공중합 및 열분해 속도론)

  • Kim, Nam-Seok
    • Journal of the Korean Applied Science and Technology
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    • v.26 no.2
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    • pp.205-212
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    • 2009
  • Solution copolymerization of Styrene(St.) with 2-Hydroxypropylacrylate(2-HPA) was carried out with Benzoylperoxide(BPO) as an initiator in toluene at $80^{\circ}C$ in a batch reactor. Reaction volume and reaction time were 0.3 liters, 8 hours respectively. The time to reach steady state was about the six time. The monomer reactivity ratios, $r_1$(St.) and $r_2$(2-HPA) were determined by both the Kelen-Tudos method and the Fineman-Ross method ; $r_1$(St.)=0.376(0.330), $r_2$(2-HPA)=0.408(0.778). The activation energy of thermal decomposition was in the range of $33{\sim}55kcal/mol$.