• Title/Summary/Keyword: cationic catalyst

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2-(Multimethoxyphenyl)-4-methylene-1,3-dioxolane: (III) Polymerization of 2-(2,4-Dimethoxyphenyl)-4-methylene-1,3-dioxolane with Various Cationic Catalysts

  • 장원철;배장순;공명선
    • Bulletin of the Korean Chemical Society
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    • v.20 no.12
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    • pp.1433-1436
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    • 1999
  • The 2-(2,4-dimethoxyphenyl)-4-MDO (2) underwent polymerization with ring opening as well as cyclization reaction in the presence of various cationic catalysts such as boron trifluoride, trifluoromethanesulfonic acid, p-toluenesulfonic acid, hydrochloric acid and trifluoroacetic acid. They afforded a mixture of the ring-opened poly(keto ether) and 3(2H)-dihydrofuranone derivative. Both the methylene group and oxygen atom of 1,3-dioxolane ring were participated in the reaction with cationic catalyst. The contents of the polymer and cyclization product were variable according to the acid strength of the cationic catalysts.

Living cationic polymerization of poly (isobutyl vinyl ether) and PVA derived therefrom

  • Mah, Soukil
    • Proceedings of the Korean Fiber Society Conference
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    • 2003.10a
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    • pp.1-2
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    • 2003
  • Some new synthetic routes for the preparation of poly (isobutyl vinyl ether) (P(IBVE)) having a controllable molar mass with narrow distribution via catalytic or photoinduced living cationic polymerization and their conversion to corresponding PVA have been developed. It was found that the combination of iodomethyl methyl ether (IMME)-zinc iodide is effective in the initiation of the catalytic and the various combinations of diphenyliodonium halides, well known photocationic initiators (DPIX) with zinc halides (ZnX$_2$) are also useful in photoinduced living cationic polymerization of isobutyl vinyl ether (IBVE). Polymerization both in the catalytic and photoinduced systems precede until the full consumption of the monomer and the rate of polymerization increases as the concentration of the catalyst or photoinitiator. The number average molar mass of the resulting polymer is proportional with % conversion, which is determined by the ratio of monomer consumed and the initial values of the catalyst or initiator. The living nature was also confirmed by subsequent monomer addition technique.

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2-(Multimethoxy)phenyl-4-methylene-1,3-dioxolane (Ⅰ): Preparation and Cationic Polymerization of 2-(Dimethoxy)phenyl-4-MDO Derivatives

  • 김종태;공명선
    • Bulletin of the Korean Chemical Society
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    • v.20 no.6
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    • pp.663-666
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    • 1999
  • The 4-methylene-1,3-dioxolane(4-MDO) derivatives with dimethoxyphenyl group on the 2-position of 1,3-dioxolane ring, 2-(x,y-dimethoxyphenyl)-4-MDO derivatives (x,y=2,3(1b), 2,4(2b), 2,5(3b) and 3,4(4b)) were prepared by acelalizationof the corresponding benzaldehyde with 3-chloro-1,2-propanediol, followed by dehydrochlorination. 2-(Dimethoxy)phenyl-4-MDO derivatives underwent polymerization wiht ring opening as will as cyclization reaction to afford a mixture of the ring-opened polymer and 3(2H)-dihydrofuranone derivative with boron trifluoride as a cationic catalyst. Both the methylene group and 1,3-dioxolane ring were participated in the reaction with cationic catalyst. The key intermediate of the polymerization is a benzyl cation generated by ring opening, and the cyclization reaction proceed via proton addition to oxygen atom of 1,3-dioxolane ring.

Cationic Cure of Epoxy Resin by an Optimum Concentration of N-benzylpyrazinium Hexafluoroantimonate

  • Lee, Jong-Keun;Park, Yusong;Jae-Rock lee;Park, Jaekyeung
    • Macromolecular Research
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    • v.10 no.1
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    • pp.34-39
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    • 2002
  • Cure behavior of an epoxy resin was investigated at different cure temperatures (110, 120, 130, 140, and 150 $^{\circ}C$) and cure times in the presence of 2 wt% of an N-benzylpyrazinium hexafluoroantimonate (BPH) cationic catalyst by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The glass transition temperature ( $T_{g}$) and chemical conversion (x) at the different temperatures were determined from DSC thermograms. The $T_{g}$ and x vs. In time data were superposed up to $T_{g}$ = 10$0^{\circ}C$ and x = 0.70 by shifting horizontally at a reference temperature of $T_{g}$ = 13$0^{\circ}C$. It is interesting that the $T_{g}$ and x of the superposed data increase rather slowly in the early stage of cure and rapidly thereafter. Therefore, the increase of the $T_{g}$ and x can be divided into two regions; $R_{I}$= -18.4(= $T_{go}$ ) ~5$^{\circ}C$ and $R_{II}$ = 5 ~ 10$0^{\circ}C$ in $T_{g}$, and $R_{I}$ : 0~0.24 and $R_{II}$ : 0.24~0.70 in x. The $R_{I}$ is closely related to the initiation reactions between BPH and epoxy and between hydroxy group and epoxy in this epoxy/catalyst system. From the kinetic analysis of the $T_{g}$-shift, activation energy was 12.5 kcal/mol. The relationship between $T_{g}$ and x was also considered. The gelation and vitrification times for different cure temperatures were obtained from DMA curves.urves. DMA curves.urves.

Polymerization of Tetrahydrofuran with New Transition Metal Catalyst and Its Mechanism: (p- Methylbenzyl)- o -cyanopyridinium Hexafluoroantimonate

  • 강준원;한양규
    • Bulletin of the Korean Chemical Society
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    • v.18 no.4
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    • pp.433-438
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    • 1997
  • (p-Methylbenzyl)-o-cyanopyridinium hexafluoroantimonate, a new catalyst, was synthesized by the reaction of o-cyanopyridine with α-bromo-p-xylene followed by exchange of counteranion with SbF6θ. We examined the effect of the catalyst on the bulk polymerization of tetrahydrofuran under various conditions. The catalytic activity was best in the presence of 1 : 1 of epichlorohydrin used as cocatalyst versus catalyst concentration. The resulting polymers had relatively low conversions in 1.0-40%. Their number average molecular weights were in the range of 800 to 5300. Propagation rate increased with increase in temperature according to an Arrhenius expression giving an activation energy of 62 KJ/mol. We also found catalyst proceeds via a cationic mechanism.

Selection of Suitable Micellar Catalyst for 1,10-Phenanthroline Promoted Chromic Acid Oxidation of Formic Acid in Aqueous Media at Room Temperature

  • Ghosh, Aniruddha;Saha, Rumpa;Ghosh, Sumanta K.;Mukherjee, Kakali;Saha, Bidyut
    • Journal of the Korean Chemical Society
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    • v.57 no.6
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    • pp.703-711
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    • 2013
  • In the present investigation, kinetic studies of oxidation of formic acid with and without catalyst and promoter in aqueous acid media were studied under the pseudo-first order conditions [formic acid]T ${\gg}[Cr(VI)]_T$ at room temperature. In the 1,10-phenanthroline (phen) promoted path, the cationic Cr(VI) phen complex is the main active oxidant species undergoes a nucleophilic attack by the substrate to form a ternary complex which subsequently experiences a redox decomposition through several steps leading to the products $CO_2$ and $H_2$ along with the Cr(III) phen complex. The anionic surfactant (i.e., sodium dodecyl sulfate, SDS) and neutral surfactant (i.e., Triton X-100, TX-100) act as catalyst and the reaction undergo simultaneously in both aqueous and micellar phase with an enhanced rate of oxidation in the micellar phase. Whereas the cationic surfactant (i.e., N-cetyl pyridinium chloride, CPC) acts as an inhibitor restricts the reaction to aqueous phase. The observed net enhancement of rate effects has been explained by considering the hydrophobic and electrostatic interaction between the surfactants and reactants. The neutral surfactant TX-100 has been observed as the suitable micellar catalyst for the phen promoted chromic acid oxidation of formic acid.

Thermal Properties and fracture Toughness of Difunctional Epoxy Resins Cured by Catalytic Initiators (촉매형 개시제로 경화된 이관능성 에폭시 수지의 열적 특성 및 파괴인성)

  • 박수진;허건영;이재락
    • Polymer(Korea)
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    • v.26 no.3
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    • pp.344-352
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    • 2002
  • In this work, two thermal cationic latent catalysts, i.e., triphenyl benzyl phosphonium hexafluoroantimonate (TBPH) and benzyl 2-methylpyrazinium hexafluoroantimonate (BMPH) were newly synthesized. And the thermal and mechanical properties of difunctional epoxy (diglycidylether of bisphenol h, DGEBA) resins initiated by 1 phr of either TBPH or BMPH catalyst were investigated. As experimental results, the epoxy/TBPH system showed higher curing temperature and critical stress intensity factor ($K_{IC}$) than those of epoxy/BMPH. This could be interpreted in terms of slow thermal diffusion rate and bulk structure of four phenyl groups in TBPH. However, the decomposed activation energy determined from Coats-Redfern method was lower in the case of epoxy/TBPH. This result was probably due to the fact that broken short chain structure was developed by steric hindrance of TBPH.

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

  • Yoo Ho-Joon;Song Jong-Kwon;Lee Bum-Jae;Hwang Gab-Sung
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2006.05a
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    • pp.229-232
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    • 2006
  • Two novel synthetic route proposed for Hydro-Terminated Poly(EO-ran-THF) and tri-block(PEC-PTHF-PEG) copolymer by cationic ring-opening polymerization of tetrahydrofuran(THF) and ethylene oxide(EO) and just by polymerization of EO on poly-THF, respectively. Polyurethane was synthesized from random and tri-block HTPE using N-100/IPDI mixture as curing agent, and TPB(Triphenylbismuth) as catalyst. The mechanical properties of resultant polyurethane after mixing with various ratio of isocyanate was also investigated. Finally, the post treatment process of HTPE based on amount of catalyst used in the synthesis was studied, to evaluate the optimum curing condition for the polyurethane propellant binder.

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