• Title/Summary/Keyword: chain transfer to polymer

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Vinyl Addition Polymerization Behavior of Poly(5-hexyl-2-norbornene-co-5-methylester-2-norbornene)s Using Cationic ${\eta}^3$-Allyl Palladium Catalyst (양이온성 ${\eta}^3$-알릴 팔라듐 촉매를 사용한 폴리(5-헥실-2-노보넨-co-5-메틸에스터-2-노보넨)의 비닐 부가 중합 거동)

  • 안재철;박기홍
    • Polymer(Korea)
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    • v.28 no.3
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    • pp.245-252
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    • 2004
  • We synthesized the vinyl addition-type polynorbomene copolymers using two monomers [5-hexyl-2-norbornene (HNB) and 5-methyleste-2-norbornene(MES-NB)] by means of a cationic ${\eta}^3$-allyl palladium catalyst system{[(${\eta}^3$-allyl)palladium(tricyclohexylphosphine) trifluoroacetate] and [lithium tetrakis(pentafluorophenyl) borate ${\cdot}$2.5 etherate]}. The molecular weights and yields of copolynorbomenes polymerized in various conditions were measured to investigate an optimum polymerization conditions to obtain highly ester-functionalized polynorbomenes. As a Pd catalyst content increased, the molecular weights (Mw) of polymers decreased while polymer yields increased. Also, as a Li cocatalyst content increased, the Mw’s and yields of polymers increased at the same time. The Mw’s of copolymers were also controlled by chain transfer agents such as 1-hexone, 1-octene and 1-decene, and we found that longer 1-decene and 1-octene were more efficient to reduce the Mw’s of polynorbornenes than 1-hexene. On the other hand, the content of chain transfer agents did not give influence significantly on polymer yields. From the $^1$H-NMR and GPC analysis of HNB/MES-NB(feed ratio of 40/60 mol%) copolymer, we found that this copolymer had an about 25 mol% of ester portion and a high molecular weight of 270,000.

Improvement on Enzyme Immobilization in Polypyrrole-Glucose Oxidase Enzyme Electrode using Organic Solvent Additive II. Electrochemical Analyses and Glucose Sensing (유기용매 첨가에 따른 Polypyrrole-Glucose Oxidase 효소전극의 효소고정화 향상 II. 전기화학적 분석 및 포도당 감지)

  • 김현철;구할본
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.15 no.7
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    • pp.621-626
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    • 2002
  • In the case of immobilizing of glucose oxidase (GOx) in polypyrrole (PPy) conducting polymer using electrosynthesis, the GOx obstructs charge transfer and mass transport during the film growth. This may lead to short chained polymer and/or make charge-coupling weak between the GOx and the backbone of the PPy. That is mainly due to insulating property and net chain of the GOx. Since being the case, it is useless to increase in amount of GOx mere than reasonable in the synthetic solution. We improved the amount of immobilized GOx into the PPy by adding a little ethanol in the synthetic solution without any more amount of GOx in the solution. We electrochemically analyzed an improvement in the immobilizing event. For the glucose sensing, when ethanol was added by 0.1 mol $dm^{-3}$ in the synthetic solution, the Michaelis constant of the resulting enzyme electrode was about 32 mmol $dm^{-3}$ and maximum current was about $146\mu A$.

Theoretical Models of Ethylene Polymerization

  • 장만채
    • Bulletin of the Korean Chemical Society
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    • v.20 no.11
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    • pp.1269-1276
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    • 1999
  • Metallocenes, whether using a cocatalyst or not, act as catalysts in ethylene polymerization. The positive charge on the transition metal of a metallocene might have an important role in polymerization as an active site in our model approach. Using semiempirical calculations in the absence of cocatalyst, we show one of the possibilities that the positive charge on a metallocene might be more easily transferred through the Cp ring of a ligand to the ethylene than to transfer directly from the transition metal to the ethylene. In these calculations, the charge on titanium in an eight C2H4 system is transferred and a polymer chain is produced. This reaction takes place only when ethylenes are arranged in a particular direction with respect to the ring, but does not take place for ethylenes near Ti or Cl atoms. The same mechanism is shown for a metallocene ligand which is sterically hindered or where the Cp ring is replaced by fluorenyl. These results suggest an entirely new polymerization mechanism in the absence of a cocatalyst in which the Cp ring is the active site.

Design and Properties of Laminating Waterborne PSA for Eco-friendly Flexible Food Packaging (식품연포장용 라미네이트 수성 감압점착제의 친환경적 적용에 대한 연구)

  • Lee, Jin-Kyoung;Shim, Myoung-Sik;Chin, In-Joo
    • Journal of Adhesion and Interface
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    • v.17 no.2
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    • pp.49-55
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    • 2016
  • In this study, we designed an environment friendly, water-based adhesive using the acrylic emulsion method as a replacement for solvent-based adhesives, which are most commonly used in layered laminates for flexible food packaging. We designed adhesives with different combinations of anionic, non-ionic, and phosphoric ester surfactants, and with different concentrations of chain transfer agent (CTA). We also examined the effect of the degree of cross-linking by synthesizing and comparing 8 test group adhesives with different types of functional monomers. Additionally, we synthesized 2 other test group pressure-sensitive adhesives (PSA) using styrene/alpha-methyl styrene/acrylic acid (SAA) semipolymer dispersing agents (with molecular weights of 13,000 g/mol and 8,600 g/mol, respectively) to replace the conventional surfactants. We evaluated whether the 10 test group pressure-sensitive adhesives met the basic physical property criteria required for flexible food packaging by carrying out a physical analysis of their glass transition temperature (Tg), particle size, adhesion, and molecular weight. In our test, 2 test group adhesives manufactured with the combination of anionic and non-ionic surfactants, CTA concentration of 0.2%, and functional monomers of hydroxyethyl acrylate (HEA) and glycidyl methacrylate (GMA) demonstrated molecular weight and flexibility suitable for flexible packaging, with low adhesiveness and small particle size.

THERMAL POLYMERIZATION OF 2-HYDROXYETHYL METHACRYLATE WITH PHENYLSILANS (PHENYLSILANS와 2-HYDROXYETHYL METHACRYLATE의 열중합)

  • Sung, A Young
    • Journal of Korean Ophthalmic Optics Society
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    • v.5 no.2
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    • pp.87-90
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    • 2000
  • Poly(HEMA)s have been used as the optometric material for the preparation of soft contact lens. The bulk thermal polymerization of 2-hydroxyethyl methacrylate (HEMA) with various hydrosilanes such as $phSiH_3$, $phMeSiH_2$, and $ph2SiH_2$ were performed to produce poly(HEMA)s containing phenylsilyl end moeity. It was found for thermal polymerization that while the polymerization yield and polymer molcular weights decreased as the relative phenylsilane concentration increases, the TGA residue yields and the relative intensities of SiH IR stretching bands increased as the relative hydrosilane concentration increases over HEMA. The polymerization yield, molecular weight, and TGA residue for the thermal polymerization were higher than those for the photo polymerization. Thus, the hydrosilanes significantly influence on the polymerization as both chain-initiation and chain-transfer agents.

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Amphiphilic Norbornene-Based Diblock Copolymers Containing Polyhedral Oligomeric Silsesquioxane Prepared by Living Ring Opening Metathesis Polymerization

  • Park, Su-Dong;Xu, Wentao;Chung, Chan-Hong;Kwon, Young-Hwan
    • Macromolecular Research
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    • v.16 no.2
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    • pp.155-162
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    • 2008
  • We report the successful synthesis of poly(NBECOOH-b-NBEPOSS) copolymers, taking advantage of the sequential, living ring opening metathesis polymerization of NBETMS and NBEPOSS using the $RuCl_2(=CHPh)(PCY_3)_2$/$CH_2Cl_2$/$20^{\circ}C$ system, followed by the hydrolysis of trimethylsilyl groups in poly(NBETMS-b-NBEPOSS) copolymers. The living behavior of ROMP of NBETMS was first investigated using two diagnostic plots, a first order kinetic plot and a $\bar{M}_n$ vs. conversion plot. The plots confirmed that no termination and chain transfer reaction had occurred during polymerization. Poly(NBECOOH-b-NBEPOSS) copolymers were prepared using the sequential monomer addition of NBEPOSS to living poly(NBETMS) chain ends, followed by the hydrolysis of trimethylsilyl groups in the poly(NBETMS-b-NBEPOSS) copolymers. The high structural integrity of poly(NBE-COOH-b-NBEPOSS) copolymers was confirmed by $^1H$-NMR, $^{13}C$-NMR spcctroscopy and GPC.

Studies on the Maximum Transfer Rate of Printing Ink (인쇄 잉크의 최대 전이율에 관한 연구)

  • 강상훈
    • Journal of the Korean Graphic Arts Communication Society
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    • v.13 no.1
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    • pp.1-12
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    • 1995
  • Polymeric mesogens having a regularly alternating rigid-flexible repeating structure in the main-chain polymer exhibit distinct even-odd oscillation in their thermodynamic quantities with respect to the number of methylene units in the spacer. The even-odd oscillation depends on the number of methylene groups in the spacer the entropy change at the NI(nematic-isotropic) phase transition becomes less distinct when the linking group is replaced by the carbonate. In our previous work, we have suggested that the characteristics arise from the geometrical arrangement of the linkage. In this work, we have prepared a series of carbonate-type monomer and dimer liquid crystals. The thermodynamic behaviors at the NI phase transition have been compared with those previous reported for the ether- or ester-type liquid crystals. For the dimer series, the orientational order parameter of the mesogenic core was determined by using H-NMR technique. The origin of the difference observed among linking groups was found to the geometrical characteristics of chemical structure.

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Ultrasonic Velocity and Absorption Measurements for poly (sodium 4-styrenesulfonate) and Water Solutions (Poly (sodium 4-styrenesulfonate)/ 물 이성분용액의 초음파 음속 및 흡수계수측정)

  • 배종림
    • The Journal of the Acoustical Society of Korea
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    • v.23 no.7
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    • pp.497-502
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    • 2004
  • Both ultrasonic velocity at 3 MHz and absorption coefficient in the frequency range of 0.2-2 MHz were measured for poly (sodium 4-styrenesulfonate) aqueous solution over the concentration range of 5 to 25 % by weight. Pulse echo overlap method was employed to measure the ultrasonic velocity over the temperature range of 10-90 ℃ and the high-a ultrasonic resonator method was used for the absorption coefficient measurement at 20 ℃. The velocity exhibited a maximum value at approximately 55. 59, 63. 67, and 71 ℃ in 25, 20. 15, 10. and 5 wt% solutions, respectively. The velocity increased with poly (sodium 4-styrenesulfonate) concentration at a given temperature. The concentrations dependences of the relaxation frequency and amplitude showed that the relaxation around 200 kHz is related to the structural fluctuations of polymer molecules, such as the segmental motions of the polymer chains and that around 1 MHz resulted from the proton transfer reaction of the oxygen sites of SO₃. Both the absorption and the shear viscosity increase with the Polymer concentration. but decrease with temperature.

Addtion Reaction of Phenyl Glycidyl Ether with Carbon Dioxide Using Phase Transfer Catalysts (상이동 촉매에 의한 Phenyl Glycidyl Ether와 이산화탄소의 부가반응)

  • Park, Dae-Won;Moon, Jeong-Yeol;Yang, Jeong-Gyu;Park, Sung-Hoon;Lee, Jin-Kook
    • Applied Chemistry for Engineering
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    • v.7 no.1
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    • pp.26-33
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    • 1996
  • This study is related to the investigation of the characteristics of phase transfer catalysts on the addition reaction of carbon dioxide and phenyl glycidyl ether(PGE). Quaternary ammonium salts showed a good conversion of PGE at l atm of $CO_2$. Among the quaternary ammonium salts tested, the ones with higher alkyl chain length and with more hydrophilic counter anion showed higher catalytic activity. Polyethylene glycol and crown ether were also effective catalysts when they are used with NaI. High pressure of $CO_2$increased the conversion of PGE by increasing solubility of $CO_2$in NMP. A mechanism of the reaction involving the role of phase transfer catalyst was also proposed.

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Studies on Telomerization (I) Telomerization of Vinyl Acetate with Chlorinated Hydrocarbons (Telomerization 에 關한 硏究 (I) Vinyl Acetate 와 Chlorinated Hydrocarbons 과의 Telomerization 에 關하여)

  • Shim, Jyong-Sup;Hong, Suck-Joo
    • Journal of the Korean Chemical Society
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    • v.6 no.1
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    • pp.88-93
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    • 1962
  • The telomerization of vinyl acetate with carbon tetrachloride, chloroform and monochlorobenzene were investigated with respect to the synthesis of those telomers, properties and molecular weights of the formed telomers, and reaction mechanisms. Vinyl acetate reacted with carbon tetrachloride and chloroform to form telomers at 70-90$^{\circ}C$ and 60-70$^{\circ}C$, respectively and it formed polymer with monochlorobenzene. As a chain transfer agent, carbon tetrachloride was more effective than chloroform. In the telomerization of vinyl acetate and carbon tetrachloride: 1) The average molecular weight of the telomer decreased as the mole ratio of carbon tetrachloride to vinyl acetate increased. The optimum conditions for the highest yield of the telomer were as follows: Mole ratio of carbon tetrachloride to vinyl acetate : 2.5 Reaction time : 20 hours. 2) As the reaction proceeded, the refractive index and average molecular weight of the telomer increased rapidly in the first 10 hours but the increase was slow through the next 10 hours, so that, the average recurring number(n) of taxogen in the final product reached an almost definite value, i.e., 3. The telomer formed in the telomerization of vinyl acetate with carbon tetrachloride and chloroform turned to brown color in the air due to decomposition or polymerization. The suggested telomerization mechanism was supported by the hexachloroethane detected in the course of reaction.

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