• Title/Summary/Keyword: $BF_3$.THF

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Synthesis of Novel Hydroxy-terminated Polyether for Solid Propellent Polyurethane Binder (고체 추진제용 폴리우레탄 바인더를 위한 새로운 폴리에테르 공중합체 디올(HTPE)의 합성)

  • Shin, Bum-Sik;Lee, Bum-Jae;You, Ho-Joon;Park, Young-Chul
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2008.05a
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    • pp.221-226
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    • 2008
  • Novel synthetic routes were proposed for hydroxy-terminated Poly(EO-co-THF) by Cationic ring-opening copolymerization of Tetrahydrofuran(THF) and Ethylene oxide(EO). It was carried out using Boron trfluoride tetrahydrofuranate($BF_3$ THF complex) as catalyst in the presence of 1,4-butandiol. The resultant products are well-defined linear polyetherpolyol. Polyurethane(TPU) were prepared using resultant polyetherpolyol with IPDI/N-100 as curing agent and TPB(Triphenylbismuth) /MA(Maleic anhydride) mixture as cure catalyst. Mechanical properties of TPU prepared from poly(EO-co-THF) polyol were investigated and compared with polyurethane using ATK HTPE.

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Synthesis of Glycidyl Azido Copolyetherdiol for Solid Propellant Polyurethane Binder (Glycidyl Azido Copolyetherdiol을 이용한 Polyurethane의 합성과 특성분석)

  • Shin, Bum-Sik;Lee, Bum-Jae;Park, Young-Chul;Hwang, Kab-Sung
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2008.11a
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    • pp.231-236
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    • 2008
  • The well-defined copolymers derived from Epichlorohydrin(ECH), Tetrahydrofuran(THF) were synthesized by Cationic ring-opening polymerization(CROP) with 1,4-Butandiol, a initiator, and $BF_3THF$ Complex, a catalyst via Activated monomer mechanism, which could lead to hydroxyl-terminated polyethers. The molecular weight of polymers were dependant on the ratio of [monomer]/[diol], Copolymer structures were controlled by monomers feed ratio, ECH and THF added. This polymers were functionalized from Chlorine group to Azide group using $S_N2$ reaction. Synthesized polymers were found to be as the prepolymer for polyurethane. Polyurethane was synthesized in the presence of N-100/IPDI mixture, a curing agent, and TPB(triphenyl bismuth)/MA(Maleic anhydride) mixture, a catalyst system. The curing behavior and mechanical properties of polyurethane after mixing with various prepolymer’s composition and the molecular weight were studied.

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Novel Polyurethane Binder for Propellant based on Hydroxyl-terminated Copolyether (폴리에테르 공중합체 디올(HTPE)을 사용한 새로운 추진제용 폴리우레탄 바인더)

  • Song Jong-Kwon;Pan Xiao;Lee Bum-Jae;Jeon Jun-Pyo;Hwang Gab-Sung
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2005.11a
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    • pp.417-421
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    • 2005
  • Novel two synthetic technics using cationic ring-opening copolymerization of tetrahydrofuran (THF) and ethylene oxide (EO), or just polymerized EO on Poly-THF, could lead to random hydroxyl-terminated poly(EO-ran-THF) or tri-block PEG-PTHF-PEC, respectively. These reactions were carried out using $BF_3O(C_2H_5)_2$ as catalyst, 1,4-butanediol or PTHF as diol initiator. Copolymer structures were controlled by monomer feed ratio, or initial PTHF and EO monomer added amount. The molecular weight of polymer was merely dependant on the ratio of [monomer]/[diol], but not on catalyst. Well-defined random and block hydroxyl-terminated copolyether was found to be as the prepolymer for the propellant binder from the experiment to polyurethane with them.

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Synthesis and Electrochemical Properties of Solid Polymer Electrolytes Using BF3LiMA as Monomer (BF3LiMA를 단량체로 하는 고체 고분자전해질 합성과 전기화학적 특성)

  • Kim, Kyung-Chan;Ryu, Sang-Woog
    • Journal of the Korean Electrochemical Society
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    • v.14 no.4
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    • pp.208-213
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    • 2011
  • Solid polymer electrolytes using $BF_3LiMA$ as monomer were synthesized by usual one step radical polymerization in THF solvent. The effect of $BF_3LiMA$ concentration on ionic conductivity and electrochemical stability was investigated by AC impedance measurement and linear sweep voltammetry. As a result, the highest ionic conductivity reached $7.71{\times}10^{-6}S\;cm^{-1}$ at $25^{\circ}C$ was obtained in 12.9 wt% of $BF_3LiMA$ content. Further increase or decrease of $BF_3LiMA$ content result to decrease the ionic conductivity due to the brittle matrix properties in former case and the insufficient number of charge carrier in the latter case. Furthermore, since the counter-anion was immobilized in the self-doped solid polymer electrolytes, high electrochemical stability up to 6.0 V was observed even in $60^{\circ}C$.

Hydroacylation of 1,5-Hexadiene through C-H Bond Activation (탄소-수소 결합 활성을 이용한 1,5-헥사디엔의 하이드로아실화반응 연구)

  • Jeon, Cheol Ho;Han, Jong Su;Kim, Seon Il
    • Journal of the Korean Chemical Society
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    • v.38 no.11
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    • pp.833-840
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    • 1994
  • 8-Quinolinecarboxaldehyde (1) reacted with 1,5-hexadiene (2) in THF under Wilkinson's catalyst(3) and $AgBF_4(8)$ to give a mixture of 8-quinolinyl 5-hexenyl ketone (4) and 8-quinolinyl 5-hexen-2-yl ketone (9) at initial reaction stage. The reason for the formation of the branched alkenyl ketone 9 is supposed to be that the vacant coordination site, generated from Wilkinson's catalyst and $AgBF_4(8)$, makes it possible to form the 5.5 membered ring metallacycle intermediate. The higher the concentration of $AgBF_4(8)$ was used, the greater the ratio of 9 to 4 was observed. Longer reaction time and high temperature induced isomerization of 9 and 4 to 10 and 5. Especially the high reaction temperature increased the possibility of cyclization of the 5-hexenyl metal intermediate to give 8-quinolinyl cyclopentylmethyl ketone (11).

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Comparison of Stereoselectivity in the Reactions of Crotylmetal Reagents with Dicobalt Hexacarbonyl-Complexed and Uncomplexed Propynals

  • 박상규;김석인;조인호
    • Bulletin of the Korean Chemical Society
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    • v.16 no.1
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    • pp.12-16
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    • 1995
  • The diastereoselectivity of addition reaction of crotylmetal reagents to cobalt-complexed acetylenic aldehydes and metal-free aldehydes was examined. The anti-diastereomer was the predominant product when the crotyl metallics were Cr, Sn, and Zr. In THF, the uncomplexed aldehydes normally gave higher anti-diastereoselectivity. However, the cobalt-complex of silicon-substituted propynals with three bulky substituents produced increased proportions of syn-diastereomer. In DMF, the selectivity shifted towards syn-isomer except in the case of dimethylphenylsilyl substituent. When tributylstannane was used in the presence of BF3 etherate, moderate syn- selectivity was observed with uncomplexed aldehydes, but only decomposed products from complexed aldehydes.