• Title/Summary/Keyword: Vinyl radical

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Synthesis and Characterization of Poly(vinyl alcohol-b-styrene) via Atom Transfer Radical Polymerization and Saponification

  • Li, Guang-Hua;Cho, Chang-Gi
    • Macromolecular Research
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    • v.10 no.6
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    • pp.339-344
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    • 2002
  • Poly(vinyl alcohol-b-styrene) (poly(VA-b-St)) diblock copolymer containing high syndiotactic poly (vinyl alcohol) (PVA) was synthesized by the saponification of poly(vinyl pivalate-b-styrene) (poly(VPi-b-St)). For the block copolymer, poly(vinyl pivalate) (PVPi) with trichloromethyl end group was obtained via telomerization of vinyl pivalate with carbon tetrachloride as a telogen and 2,2-azobisisobutyronitrile (AIBN) as an initiator. Then resulting poly(vinyl pivalate) with trichloromethyl end group was used as an effient macroinitiator for the synthesis of poly(VPi-b-St) using atom transfer radical polymerization (ATRP) in the presence of CuCl/2,2'-bipyridine at 130 $^{\circ}C$. The poly(vinyl pivalate) macroinitiator, poly(VPi-b-St), poly(VA-b-St) were characterized by GPC, FT-IR and $^1$H-NMR. And the analysis showed that integrity of the block copolymer was maintained during saponification reaction.

Radical Polymerization of Vinyl Monomers to Poly(vinyl)s having nBu3Sn end Groups with Biological Activity

  • Park, Jaeyoung;Lee, Beomgi;Kim, Seongsim;Cheong, Hyeonsook;Gwak, Gyeongja;Lee, Ki Bok;Woo, Hee-Gweon
    • Journal of Integrative Natural Science
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    • v.6 no.2
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    • pp.71-75
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    • 2013
  • $Bu_3Sn$-endded poly(vinyl)s with biological activity were obtained by the radical polymerization of vinyl monomers using thianthrene cation radical/$^nBu_3H$. Thianthrene cation and stannyl radicals promoted the homopolymerization and copolymerization of styrene and ethyl vinyl ether having number average molecular weights of 2000-3100. Tributyltin hydride functions as a chain transfer agent. Such polymereization by cationic thianthrene and stannyl radicals could provide some clues for the biological reaction in living animals. Plausible polymerization mechanisms were suggested.

New Radical Allylation Reactions Using 2-Bromo-3-(phenylthio)propene and Their Application to the Synthesis of Carbocyclic Compounds

  • 유병우;Dennis P. Curran
    • Bulletin of the Korean Chemical Society
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    • v.17 no.11
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    • pp.1009-1018
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    • 1996
  • A study on the application of vinyl radical cyclization via free radical allylation reaction in the synthesis of various carbocyclic compounds is described. In connection with this study, a new allyl transfer reagent, 2-bromo-3-(phenylthio)propene 1 is developed and it was shown that vinyl radical cyclization through free radical allylation reaction using reagent 1 provides a valuable approach to carbocyclic systems with a reactive exo-alkylidene moiety, which is advantageous for further transformations.

Polymerization of Vinyl Monomers Initiated by Thianthrene Cation Radical with Potential Biological Activity

  • Lee, Beomgi;Kim, Seongsim;Park, Jaeyoung;Cheong, Hyeonsook;Noh, Ji Eun;Woo, Hee-Gweon
    • Journal of Integrative Natural Science
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    • v.5 no.2
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    • pp.127-130
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    • 2012
  • Polymerization of vinyl monomers is promoted by thianthrene cation radical as a part of our research concerning the reactions of various agents with readily isolable, yet highly reactive species and elucidate the biological activity. Thianthrene cation radical initiated the homopolymerization and copolymerization of styrene and ethyl vinyl ether. The polymerization yields decreased as the concentration of phenylacetylene or diphenylethylene increased. Such polymereization by cationic thianthrene radical could provide some clues for the reaction in living animals. Comments on possible polymerization mechanisms were suggested.

Photopolymerization of Vinyl Monomers Using Organic Initiators

  • Kim, Myoung-Hee;Lee, Jun;Cha, Hyo Chang;Ham, Heui-Suk;Woo, Hee-Gweon
    • Journal of Integrative Natural Science
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    • v.2 no.1
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    • pp.1-12
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    • 2009
  • This miniaccount presents the selective examples of our recent discoveries in the photopolymerization of vinyl monomers using the organic initiators such as hydrosilanes, poly(hydroarylsilane)s, benzoin silyl ethers, and thianthrene cation radical. In the photopolymerization of vinyl monomers with silanes polysilanes, while the polymerization yields and polymer molecular weights of the poly(MMA)s containing the silyl moieties decreased, the TGA residue yields and intensities of SiH stretching IR bands increased as the mole ratio of the silanes over MMA increased. The hydroarylsilane and poly(hydroarylsilane) seemed to influence strongly on the photopolymerizaiton of olefinic monomers as both chain initiation and chain transfer agents. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. Benzoin silyl ethers and thianthrene cation radical also exhibit the photoinitiating ability in the photopolymerization of MMA.

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Copolymerization and Contact Lens Application of HEMA-Substituted Polyphosphazene (HEMA가 치환된 Polyphosphazene의 공중합 및 콘택트렌즈 응용)

  • Kim, Tae-Hum;Seong, A-Young
    • Journal of the Korean Chemical Society
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    • v.53 no.3
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    • pp.340-344
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    • 2009
  • HEMA/vinyl-substituted polyphosphazene was prepared by the ring-opening polymerization of phosphonitrillic chroride trimer at $200{\sim}300\;{^{\circ}C}$, followed by Grignard reaction with vinyl magnesium bromide and then by the reaction with HEMA(2-hydroxyethyl methacrylate). HEMA/vinyl-substituted polyphosphazene was copolymerized with EGDMA(ethylene glycol dimethacrylate; used as a cross-linker for the free-radical copolymerization), NVP (N-vinyl-pyrrolidone) in the presence of AIBN (azobisisobutyronitrile) as a radical initiator. The oxygen transmissibility, water content and visible-ray transmissibility of the resulting copolymer were measured to be Dk/t 88, 30.89% and 87%, respectively, indicating that the copolymer can be used as a good contact lens material.

Aromatic Formation from Vinyl Radical and Acetylene. A Mechanistic Study

  • Natalia, Debby;Indarto, Antonius
    • Bulletin of the Korean Chemical Society
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    • v.29 no.2
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    • pp.319-322
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    • 2008
  • The viability of acetylene addition in each step of aromatic formation initiated by vinyl radical and acetylene also with its competition with structure rearrangement is investigated by determining optimal geometries and barrier and reaction energies using quantum mechanical methods. In principle, the addition reaction has more difficult in term of free energy and enthalpy compared to geometry arrangement. Under combustion conditions, i.e. T = 1200 K, acetylene addition is unfavorable mechanism as the barrier energy values rise much higher than that of geometry arrangement. However, in longer chain hydrocarbon case, e.g. n-CxHx+1 where x ³ 8, C-C bond rotation is rather difficult and requires high energy to form a ring structure, elongation chain is preferable.

Copolymerization of 4′-vinylbenzo-15-crown-5 with Di(ethylene glycol) Ethyl Ether Acrylate

  • Jin, Long Yi;Mah, Soukil
    • Fibers and Polymers
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    • v.3 no.2
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    • pp.49-54
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    • 2002
  • Radical copolymerization behavior of 4'-vinylbenzo-15-crown-5, a vinyl monomer having a pendant 15-membared crown ether unit (VCE) with di(ethylene glycol) ethyl ether acrylate (DEGEEA) was carried out in toluene solution using 2,2-azobisisobutyronitrile (AIBN) as an initiator. The copolymers were characterized by means of FT-IR, $^1{H-NMR}$, and $^{13}{C-NMR}$ . The reactivity ratio of VCE and DEGEEA, determined by Fineman-Ross and Kelen-Tudos method, gave values 0.55 for VCE, and 0.11 for DEGEEA respectively.

Preparation of Poly(vinyl pivalate/vinyl acetate) Microspheres Using Suspension Copolymerization of Vinyl Pivalate and Vinyl Acetate and its characterization (피발산비닐과 아세트산비닐의 현탁공중합을 이용한 폴리(피발산비닐/아세트산비닐) 입자의 제조 및 특성)

  • Park, Chan-Sik;Kim, Joon-Ho;Lyoo, Won-Seok
    • Proceedings of the Korean Fiber Society Conference
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    • 2003.10b
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    • pp.46-48
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    • 2003
  • Poly(vinyl alcohol) (PVA) obtained from PVPi has the highest syndiotacticity among (PVA)s obtained via radical polymerization, and the s-diad content of PVA prepared by low temperature polymerization of vinyl pivalate (VPi)[1-5] comes to eve. 60%, Therefore, we an obtain (PVA)s with various tacticities through the copolymerization of vinyl acetate (VAc) and VPi and can examine the relation between physical properties of (PVA)s and their tacticities. (omitted)

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