• Title/Summary/Keyword: ring opening polymerization

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Photo-Induced Cationic Ring-Opening Polymerization of 4-Methylene-2-styryl-1,3-dioxolane by Benzylsulfonium Salt

  • Park, Jaekyeung
    • Macromolecular Research
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    • v.9 no.4
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    • pp.206-209
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    • 2001
  • One of the approaches to obtain functional polymer is polymerization of a monomer having two functional groups. Although polymerization of a monomer having two different types of functional group is general, the author has been interested in the polymerization of a monomer having two similar types of functional group. This work shows the preparation and selective polymerization of 4-methylene-2-styryl-1,3-dioxolane having two similar reactive double bonds via cationic polymerization at ambient temperature. Cationic ring-opening polymerization of 4-methylene-2-styryl-1,3-dioxolane using benzylsulfonium salt as a photo-initiator quantitatively afforded high molecular weight of poly(keto-ether).

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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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    • v.28 no.12
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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.

Ring Opening and Polymerization of Alpha-Lipoic Acid (알파 리포산의 개환 및 중합)

  • Park Chul-Ho;Kim Ae-Ran;Yun Hye-Lee;Lee Jong-Hwi
    • Polymer(Korea)
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    • v.30 no.4
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    • pp.357-361
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    • 2006
  • Alpha-lipoic acid (ALA) synthesized in the body has virtues such as anti-oxidation, blood sugar regulation, appetite suppression, and anti-obesity, etc. ALA, which is also used as a drug, has a five-membered ring including disulfide and so easily losses bioavailability due to ring opening and subsequent polymerization by heat or ultraviolet. This report studies various conditions for ring opening polymerization. The ring opening starts above the melting point of ALA, but there was no temperature dependence above it. At $70^{\circ}C$, the degree of ring opening was proportional to reaction time and inversely proportional concentration. The degree of ring opening in acetic acid with UV for 1 hour reached the maximum conversion (70%). Most cleaved ALA changed into disulfide polymers, and the molecular weight of the polymers increased as the amount of ring opening increased.

Synthesis of Polystyrene-b-Poly(ethylene oxide)-b-Polylactide Copolymers via Sequential Anionic and Ring-Opening Polymerizations (순차적 음이온 및 개환중합반응을 통한 폴리스티렌-폴리에틸렌옥사이드-폴리락티드 블록공증합체의 합성)

  • Song, Jie;Cho, Byoung-Ki
    • Polymer(Korea)
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    • v.33 no.5
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    • pp.458-462
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    • 2009
  • We have synthesized ABC linear triblock copolymers, i.e., polystyrene-b-poly(ethylene oxide)-b-polylactide, via sequential anionic and ring-opening polymerizations. In the first anionic polymerization step, styrene was polymerized in cyclohexane using sec-butyllithium as the initiator. Poly (styryl) lithium was hydroxylated by the addition of ethylene oxide, and the subsequent protonation with methanolic HCl. In the second anionic polymerization step, potassium naphthalenide was used to deprotonate the hydroxyl group of the PS to generate the macroinitiator of PS-$O^-K^+$. Polymerization of ethylene oxide was performed in THF and terminated with methanolic HCl. In the ring-opening polymerization step, the PS-b-PEO-$AlEt_2$ macroinitiator was prepared from an $AlEt_3$/pyridine system in THF, and the polymerization of lactide was performed at $90^{\circ}C$. The resulting block copolymers showed well-defined molecular weights and narrow molecular weight distributions as revealed by $^1H$- NMR spectroscopy and gel permeation chromatography (GPC).

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.

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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    • v.14 no.2
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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.

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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    • v.17 no.9
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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.

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

  • Jung, Kyoungsun;Kim, Sung Gi
    • Journal of Integrative Natural Science
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    • v.2 no.2
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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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Ring-Opening Polymerization of ʟ-Lactide with Polydimethylsiloxane Based Stabilizers in Supercritical Carbon Dioxide (폴리디메틸실록산계 안정화제를 이용한 초임계 이산화탄소에서의 ʟ-Lactide의 개환중합)

  • Hwang, Ha Soo;Lim, Kwon Taek
    • Clean Technology
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    • v.12 no.2
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    • pp.62-66
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    • 2006
  • Poly($\small{L}$-Lactide)(PLLA) was prepared by a ring-opening polymerization of $\small{L}$-Lactide with various polydimethylsiloxane(PDMS) based copolymers as a stabilizer in supercritical carbon dioxide($scCO_2$). The block copolymeric stabilizers were synthesized by group transfer polymerization (GTP) by using PDMS macroinitiator. PLLA was found to be produced with fairly low molecular weight distribution as confirmed by gel permeation chromatography(GPC) analysis. Scanning electron microscopy (SEM) results showed that sub-micron size Poly($\small{L}$-lactide)(PLLA) particles were formed by suspension polymerization.

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Effect of Interface on the Properties of Polyamide 6/Carbon Nanotube Nanocomposites Prepared by In-situ Anionic Ring-opening Polymerization

  • Min, Jin Hong;Huh, Mongyoung;Yun, Seok Il
    • Composites Research
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    • v.32 no.6
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    • pp.375-381
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    • 2019
  • Multiwalled carbon nanotubes (MWCNTs) are covalently functionalized with isocyanates by directly reacting commercial hydroxyl functionalized MWCNTs with excess 4,4'-methylenebis (phenyl isocyanate) (MDI) and hexamethylene diiosocyanate (HDI). HDI-modified MWCNTs results in a higher surface isocyanate density than MDI-modified MWCNTs. Anionic ring-opening polymerization of ε-caprolactam is conducted using a sodium caprolactam initiator in combination with a di-functional hexamethylene-1,6-dicarbamoylcaprolactam activator in the presence of isocyanate functionalized MWCNTs. This polymerization proceeds in a highly efficient manner at relatively low reaction temperature (150℃) and short reaction times (10 min). During the polymerization, the isocyanate functionalized MWCNTs act not only as reinforcing fillers but also as second activators. Nanocomposites with HDI modified MWCNTs exhibit higher reinforcement and faster isothermal crystallization than MDI modified MWCNTs. The results show that PA6 chains grow more effectively from HDI modified MWCNT surface than from MDI modified MWCNT surface, resulting in stronger interaction between PA6 and MWCNTs.