• 제목/요약/키워드: Ring-opening

검색결과 327건 처리시간 0.027초

Synthesis and Ring-Opening Polymerization of 1,2-Disubstituted Cyclobutanes

  • Lee, Ju-Yeon;Cho, I-Whan
    • Bulletin of the Korean Chemical Society
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    • 제7권3호
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    • pp.210-213
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    • 1986
  • 1,1-Dicyano-2-ethoxycyclobutane (1a) was prepared by [2 + 2] cycloaddition reaction of vinylidene cyanide with ethyl vinyl ether. 1,1-Dicyano-2-phenylcyclobutane (1b) was prepared by the reactions involving the reduction of cinnamyl alcohol, chlorination, cyanomethylation, bromination, and ring-closure reaction. Compound 1a was ring-opening polymerized with NaCN or n-butyllithium to give a low molecular weight polymer. The compound 1b however, failed to polymerize by either anionic or radical catalysts.

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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    • 제20권6호
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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.

Efficient and Regioselective Ring-Opening of Epoxides with Alcohols and Sodium Azide by using Catalytic Amounts of GaCl3/Polyvinylpyrrolidone

  • Pourali, Ali Reza;Ghayeni, Samaneh;Afghahi, Fatemeh
    • Bulletin of the Korean Chemical Society
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    • 제34권6호
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    • pp.1741-1744
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    • 2013
  • A new polymeric catalyst was prepared by supporting $GaCl_3$ on cross-linked polyvinylpyrrolidone ($GaCl_3$/PVP). This catalyst was employed for efficient and regioselective ring-opening reaction of epoxides by various alcohols under solvent-free conditions at room temperature. In our procedure, this heterogeneous catalyst was used at neutral and mild reaction conditions to afford high yields of ${\beta}$-alkoxy alcohols. Also, regioselective conversion of epoxides to ${\beta}$-azidohydrines was accomplished by sodium azide in MeOH in the presence of $GaCl_3$/PVP at room temperature. $GaCl_3$/PVP is a non-hygroscopic and recoverable catalyst and is easily separated from reaction mixture by a simple filtration and re-used repeatedly. Also, this catalyst has good handling and can be stored for long time without any reducing of its reactivity.

Uniform Grafting of Poly(1,5-dioxepan-2-one) by Surface-Initiated, Ring-Opening Polymerization

  • Yoon Kuk-Ro;Yoon Ok-Ja;Chi Young-Shik;Choi Insung-S.
    • Macromolecular Research
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    • 제14권2호
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    • pp.205-208
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    • 2006
  • A polymeric film of a biodegradable poly(1,5-dioxepan-2-one) (PDXO) was formed on a gold surface by a combination of the formation of self-assembled monolayers (SAMs) presenting hydroxyl groups and the surface-initiated, ring-opening polymerization (SI-ROP) of 1,5-dioxepan-2-one (DXO). The SI-ROP of DXO was achieved by heating a mixture of $Sn(Oct)_2$, DXO, and the SAM-coated substrate in anhydrous toluene at $55^{\circ}C$. The resulting PDXO film was quite uniform. The PDXO film was characterized by polarized infrared external reflectance spectroscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, atomic force microscopy, ellipsometry, and contact angle goniometry.

Efficient Bimodal Ring-opening Polymerization of ε-Caprolactone Catalyzed by Titanium Complexes with N-Alkoxy-β-ketoiminate Ligands

  • Cho, Min-Ho;Yoon, Jin-San;Lee, Ik-Mo
    • Bulletin of the Korean Chemical Society
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    • 제28권12호
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    • pp.2471-2476
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    • 2007
  • A series of titanium complexes containing terdentate β-ketoiminate ligands were found to be efficient for the ring-opening polymerization of ε-caprolactone (ε-CL), producing poly(ε-caprolactone) (PCL) with bimodal distribution. Steric factors imposed by methyl substituents on the back bone of the alkoxy group affected significantly the polymerization rate and physical properties of the resulting PCL. Intra- and intermolecular transesterifications rather than disproportional rearrangements were responsible for the bimodal behavior and for the change in the molecular weight (Mw). Dilution with toluene reduced yield, and lowered polydispersity (PDI) and Mw of PCL, while the catalytic activities of the dimeric complex, [Ti(Oi-Pr)2(N-alkoxy-β- ketoiminate)]2 and Ti(Oi-Pr)4 were not sensitive to the added solvent. The dimeric complex showed living character, while other catalysts suffered from chain termination reactions.

Synthesis of Norbornene Block Copolymers Containing Polyhedral Oligomeric Silsesquioxane by Sequential Ring-Opening Metathesis Polymerization

  • Kwon Young-Hwan;Kim Kyung-Hoe
    • Macromolecular Research
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    • 제14권4호
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    • pp.424-429
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    • 2006
  • The synthesis of a series of poly(POSS-NBE-b-MTD) copolymers was successfully accomplished, taking advantage of sequential, ring-opening, metathesis block copolymerization using $RuCl_2(=CHPh)(PCy_3)_2$ catalyst. By using cyclopentyl-POSS-norbornene (POSS-NBE) monomer as the first block in the block copolymer, living poly(POSS-NBE) with controlled molecular weight and narrow molecular weight distribution was produced. Then, poly(POSS-NBE-b-MTD) copolymers were successfully prepared, in which sequential monomer addition of methyltetracyclododecene (MTD) to the living poly(POSS-NBE) chain ends was utilized to achieve quantitative crossover efficiency. Characterization by $^1H$ NMR spectroscopy and GPC confirmed the high definition and structural integrity of the poly(PO$S-NBE-b-MTD) copolymers. Thermal properties-and morphologies of the POSS-containing block copolymer nanocomposites were also investigated by using thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and wide-angle X-ray scattering (WAXS).

Study on the Optimization of Cationic Ring Opening Polymerization of Silicone-Based Epoxy Monomers for Holographic Photopolymers

  • Kim, Dae-Heum;Chung, Dae-Won
    • Macromolecular Research
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    • 제17권9호
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    • pp.651-657
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    • 2009
  • This study examined the optimum compositions of binder, photo-acid generator (PAG) and sensitizer for the cationic ring opening polymerization of 1,3-bis[2-(3-{7-oxabicyclo-[4.1.0]heptyl})]-tetramethyldisiloxane in the presence of polydimethylsiloxane with four epoxide moieties as a co-monomer. When diffractive efficiency (DE) values were compared quantitatively to analyze the effect of the binder on holographic photopolymerization, DE was affected by the viscosity of the binders and miscibility with the monomer mixture. Extremely low DE values were observed when the immiscible dimethyl silicone was used as a binder. Therefore, methylphenyl silicone, which is miscible with the monomer mixture, was used as the binder for further studies. The optimal conditions were a binder viscosity between 250 to 390 cP, and contents of the binder, PAG, and sensitizer were 75-125 wt%, > 6 wt% and 0.05 wt% to the total monomer mixture, respectively.

고분자 고리 열림 반응을 이용한 Poly(ferrocenylsilane) 의 합성과 특성 (Synthesis and Characterization of Poly(ferrocenylsilane) via Ring-Opening Polymerization(ROP))

  • 정경선;김성기
    • 통합자연과학논문집
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    • 제2권2호
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    • pp.78-81
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    • 2009
  • In recent years, organometallic polymer containing silane and silole unit has been a topic of interest because of the wide range of optical, electrical and luminescent properties. In previous work, we synthesized functionalsilanebridged[1]ferrocenophane from the reaction of dimethyldichlorosilane[Me2SiCl2] and diphenyldichlorosilane[Ph2SiCl2] and dichloromethylvinylsilane[C3H6SiCl2] with ferrocene$[Fe({\eta}-C5H4)2]$ and n-BuLi. In this work, we have synthesized Poly(ferrocenylsilane) via the Thermal Ring-Opening Polymerization(ROP). characteristics of the poly(ferrocenylsilane) were investigated by gel permeation chromatography(GPC), 1H- and 13C-NMR spectroscopy.

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InCl3-Catalyzed Regioselective Ring-Opening Reactions of Epoxides to β-Hydroxy Ethers

  • Kim, Byeong-Hyo;Piao, Fengyu;Lee, Eun-Joo;Kim, Ji-Sook;Jun, Young-Moo;Lee, Byung-Min
    • Bulletin of the Korean Chemical Society
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    • 제25권6호
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    • pp.881-888
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    • 2004
  • By applying a catalytic amount of indium trichloride, regioselective ring-opening of epoxides to ${\beta}$-hydroxy ethers was established. While the alcoholysis of styrene oxides produed $S_N1$-type product, the alcoholysis of ${\alpha}$-heteroatom-substituted epoxides predominantly produced $S_N2$-type product.