• Title/Summary/Keyword: isomerization polymerization

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Characteristics of Ring-Opening Isomerization Polymerization of [4.3.0] Cyclic Pseudoureas ([4.3.0] 환상 유사 우레아의 이성화 개환중합과 특성평가)

  • Lee, Chan-Woo;Chung, Jin-Do
    • Polymer(Korea)
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    • v.35 no.4
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    • pp.308-313
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    • 2011
  • The ring-opening isomerization polymerization behavior of 2,5,6,7-tetrahydro-3H-imidazo[2,1-b] [1,3] oxazine(TII) has been studied under various conditions. The present study aimed at improving the low polymerizability of the above monomer (six-membered ring) up to a level comparable to that of 2,5,6-tetrahydroimidazo[2,1-b] [l,3] oxazole(TIO) (five-membered ring). The optimum result could be observed when methyl trifluoromethanesulfonate(MeOTf) and nitrobenzene were used as an initiator and a solvent in the polymerization at $60^{\circ}C$ for 24 h. Polymers were confirmed by$^1H$ NMR과$^{13}C$ NMR, and m measurements. The molecular weight obtained by gel permeation chromatography (GPC) corresponded to the molecular weight theoretically calculated from the feed ratio. The melting temperature ($T_m$) of TII was conspicuously different from that of TIO, because of the difference in the alkyl group.

Characteristics and Ring-Opening Isomerization Polymerization of 2-(1,3,3-Trimethyl-6-azabicyclo[3,2,1]-oct-6-yl)-4,5-dihydro-1,3-oxazoline (TAO) (2-(1,3,3-Trimethyl-6-azabicyclo[3,2,1]-oct-6-yl)-4,5-dihydro-1,3-oxazoline(TAO)의 개환이성화중합과 특성평가)

  • Lee, Chan-Woo;Chung, Jin-Do
    • Polymer(Korea)
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    • v.36 no.3
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    • pp.262-267
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    • 2012
  • 2-(1,3,3-Trimethyl-6-azabicyclo [3,2,1]-oct-6-yl)-4,5-dihydro-1,3-oxazoline (TAO) was polymerized at several conditions to clarify the influence of initiators, alkyl halide ($PhCH_2Br$, $PhCH_2Cl$, MeI) and sulfonate (MeOTf). The reactions were conducted at $100^{\circ}C$ for 24 h. The resultant polymer forms several kinds of structures with different combination of initiators. The sole MeOTf initiator caused chain transfer reaction to form the one-order structure for which the resultant polymer exclusively formed pendant structure, while alkyl halide and MeOTf formed two kinds of structures, pendant and main chain, which is caused by partly-proceeded double isomerization polymerization by highly reactive nucleophilic counter anion of halogen. Merrifield polymer was also utilized as an intiator and copolymerized with TAO, which produced a graft structure.

Photo-induced Isomerization and Polymerization of (Z,Z)-Muconate Anion in the Gallery Space of [LiAl2(OH)6]+ Layers

  • Rhee, Seog-Woo;Jung, Duk-Young
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.35-40
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    • 2002
  • Photoreaction of guest organic anions in layered organic-inorganic hybrid materials was investigated. The layered hybrids were synthesized by an anion-exchange reaction of $[LiAl_2(OH)_6]Cl{\cdot}yH_2O$ layered double hydroxide with aqueous (Z,Z)- and (E,E)-muconates under inert atmospheric condition, to give new organicinorganic hybrids of $[LiAl_2(OH)_6]_2[(Z,Z)-C_6H_4O_4]{\cdot}zH_2O$ and $[LiAl_2(OH)_6]_2[(E,E)-C_6H_4O_4]{\cdot}H_2O$, respectively. The basal spacings calculated by XRPD of intercalates indicate that muconate anions have almost vertical arrangements against the host $[LiAl_2(OH)_6]^+$ lattices in the interlayer of organic-inorganic hybrid materials. When UV light was irradiated on the suspension of $[LiAl_2(OH)_6]_2[(Z,Z)-C_6H_4O_4]{\cdot}zH_2O$, the (Z,Z)-muconate anions of the gallery space of hybrids were polymerized in the aqueous media while it was isomerized into more stable (E,E)-muconate in the methanollic suspension in the presence of catalytic amount of molecular iodine. All the products were characterized using elemental analysis, TGA, XRPD, FT-IR, $^1H$ NMR and $^{13}C$ CP-MAS NMR.