• Title/Summary/Keyword: Solution-polymerization route

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A Novel Synthetic Route to Highly Cross-Linked Poly(vinyl ethers): Ⅲ. Synthesis and Free Radical Polymerization of Aryloxyethyl Vinyl Ethers Having an Electron Acceptor in ortho- or meta-Position

  • 이주연;김무용;안광덕
    • Bulletin of the Korean Chemical Society
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    • v.18 no.3
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    • pp.318-323
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    • 1997
  • ο-(2-Vinyloxyethoxy)benzylidenemalononitrile (3a) and methyl ο-(2-vinyloxyethoxy)-benzylidenecyanoacetate (3b), m-(2-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl m-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b) were prepared by the condensation of ο-(2-vinyloxyethoxy)benzaldehyde (1) and m-(2-vinyloxyethoxy)benzaldehyde (2) with malononitrile or methyl cyanoacetate, respectively. Bifunctional vinyl ether monomers 3a and 3b polymerized quantitatively with radical initiators in γ-butyrolactone solution at 65 ℃, while meta-isomers 4a and 4b gave lower yields of polymers under the same conditions. The polymers 5-6 obtained from the monomers 3-4 were insoluble in common solvents due to cross-linking. Under the same polymerization conditions ethyl vinyl ether polymerized well with model compounds ο-methoxybenzylidenemalononitrile 7a, methyl ο-methoxybenzylidenecyanoacetate 7b, m-methoxybenzylidenemalononitrile 8a, and methyl m-methoxybenzylidenecyanoacetate 8b, respectively, to give 1:1 alternating copolymers 9-10 in high yields. Cross-linked polymers 5-6 showed a thermal stability up to 300 ℃, and showed a double phase degradation pattern in their TGA thermograms. Polymers 5-6 showed broad endothermic bands around 75-110 ℃ without any characteristic Tg peaks in DSC thermograms. Alternating copolymers 9-10, except copolymer 9b were soluble in common organic solvents. The inherent viscosities of polymer 9-10 were in the range of 0.35-0.62 dL/g. Polymer films cast from acetone solution were cloudy and tough and Tg values obtained from DSC thermograms were in the range of 118-165 ℃.

Leaching of Copper from Furnace Dust by Pure and Mixed Culture of Thiobacillus ferrooxidans and Thiobacillus thiooxidans

  • Son, Kee-Hang;Lee, Cheal-Gyu;Cho, Nam-Jun
    • Bulletin of the Korean Chemical Society
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    • v.28 no.10
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    • pp.1777-1780
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    • 2007
  • The synthesis of well-defined dendrons based on aliphatic polyether dendritic cores and glassy polystyrene peripheries is described. The synthetic route involves a combination of living anionic polymerization and a stepwise convergent method consisting of iterative Williamson etherification and hydroboration/oxidation reactions. On the basis of molecular weight, as characterized by gel permeation chromatography (GPC), the first generation dendron (Generation-1) shows a random coil conformation like a linear polystyrene, while higher generations (Generation-2 and 3) reveal globular forms in solution.

Effect of Composition and Synthetic Route on the Microstructure of Biodegradable Diblock Copolymer, Poly($\varepsilon$-caprolactone-co-L-lactide)-b-Poly(ethylene glycol)

  • Min, Youn-Jin;Lee, Seong-Nam;Park, Jung-Ki;Cho, Kuk-Young;Sung, Shi-Joon
    • Macromolecular Research
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    • v.16 no.3
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    • pp.231-237
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    • 2008
  • Biodegradable poly($\varepsilon$-caprolactone-co-L-lactide)-b-poly(ethylene glycol) (PCLA-b-PEG) copolymers were synthesized via solution polymerization by varying the feed composition of $\varepsilon$-caprolactone ($\varepsilon$-CL) and L-lactide (LLA) ($\varepsilon$-CL: LLA= 10:0, 7:3, 5:5, 3:7, 0: 10). The feed ratio based on weight is in accordance with the copolymer composition except for the case of $\varepsilon$-CL: LLA=3:7 (C3L7), which was verified by $^1H$-NMR. Two different approaches were used for the exceptional case, which is an extension of the reaction time or the sequential introduction of the monomer. A copolymer composition of $\varepsilon$-CL: LLA=3:7 could be obtained in either case. The chemical microstructure of PCLA-b-PEG was determined using the $^{13}C$-NMR spectra and the effect of the sequential structure on the thermal properties and crystallinity were examined. Despite the same composition ratio of the copolymer, the microstructure can differ according to the reaction conditions.

Growth and Electrochemical Behavior of Poly[Ni(saldMp)] on Carbon Nanotubes as Potential Supercapacitor Materials

  • Zhang, Yakun;Li, Jianling;Kang, Feiyu;Wang, Xindong;Ye, Feng;Yang, Jun
    • Bulletin of the Korean Chemical Society
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    • v.33 no.6
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    • pp.1972-1978
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    • 2012
  • The polymer of (2,2-dimethyl-1,3-propanediaminebis(salicylideneaminato))-nickel(II), Ni(saldMp), was deposited on multi-walled carbon nanotubes (MWCNTs) substrate by the route of potential linear sweep. The nano structures of poly[Ni(saldMp)] have been obtained by adjusting the monomer concentration of 0.1, 0.2, 0.5, 1.0 and 1.5 mmol $L^{-1}$. The poly[Ni(saldMp)] prepared in acetonitrile solution with monomer concentration of 1.0 mmol $L^{-1}$ shows the fastest growth rate. The effects of potential window on charge-discharge efficiency and electrodeposition scan number on capacitance performance were discussed. Poly[Ni(saldMp)] prepared with less electrodeposition scans exhibits higher capacitance, but this goes against the improvement of the whole electrode capacitance. Sample with 8 deposition scans is the best compromise with the geometric specific capacitance 3.53 times as high as that of pure MWCNTs, and 1.24 times for the gravimetric specific capacitance under the test potential window 0.0-1.0 V.