• Title/Summary/Keyword: Anionic polymerization

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Anionic Polymerization of Hexafluoropropylene Oxide Using Hexafluoropropylene Oligomer (헥사플루오르프로필렌 올리고머를 사용한 헥사플루오르프로필렌 옥사이드의 음이온 중합)

  • Lee, Sang Goo;Ha, Jong-Wook;Park, In Jun;Lee, Soo-Bok;Lee, Jong Dae
    • Polymer(Korea)
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    • v.37 no.1
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    • pp.80-85
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    • 2013
  • Anionic polymerization of hexafluoropropylene oxide (HFPO) was investigated under various reaction conditions such as various hexafluoropropylene (HFP) oligomers composed of dimer and trimer, reaction temperatures, and feeding rates of hexafluoropropylene oxide monomer. HFP oligomer was synthesized from cesium fluoride (CsF) and HFP in tetraethyleneglycol dimethylether (TG). Under 5 g of CsF, 200 g of HFP, 10 g of TG, and reaction temperature $30^{\circ}C$, HFP dimer content in oligomer was relatively increased. HFPO oligomer with a high molecular weight ($M_w$ 3600) was synthesized in conditions of reaction temperature $0^{\circ}C$, HFP oligomer with 35.1% of dimer, and 1.85 g/min of HFPO feeding rate. Otherwise, chain transfer was increased under unoptimized reaction conditions. Consequently, it was found that reaction conditions impact chain propagation and chain transfer in the anionic polymerization of HFPO.

Precise Synthesis of Dendron-Like Hyperbranched Polymers and Block Copolymers by an Iterative Approach Involving Living Anionic Polymerization, Coupling Reaction, and Transformation Reaction

  • Hirao Akira;Tsunoda Yuji;Matsuo Akira;Sugiyama Kenji;Watanabe Takumi
    • Macromolecular Research
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    • v.14 no.3
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    • pp.272-286
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    • 2006
  • Dendritic hyperbranched poly(methyl methacrylate)s (PMMA)s, whose branched architectures resemble the 'dendron' part(s) of dendrimer, were synthesized by an iterative methodology consisting of two reactions in each iteration process: (a) a coupling reaction of u-functionalized, living, anionic PMMA having two tert-butyldimethylsilyloxymethylphenyl(SMP) groups with benzyl bromide(BnBr)-chain-end-functionalized PMMA, and (b) a transformation reaction of the introduced SMP groups into BnBr functionalities. These two reactions, (a) and (b), were repeated three times to afford a series of dendron-like, hyperbranched (PMMA)s up to third generation. Three dendron-like, hyperbranched (PMMA)s different in branched architecture were also synthesized by the same iterative methodology using a low molecular weight, functionalized 1,1-diphenylalkyl anion prepared from sec-BuLi and 1,1-bis(3-tert-butyldime-thylsilyloxymethylphenyl)ethylene in the reaction step (b) in each iterative process. Furthermore, structurally similar, dendron-like, hyperbranched block copolymers could be successfully synthesized by the iterative methodology using $\alpha$-functionalized, living, anionic poly(2-(perfluorobutyl) ethyl methacrylate) (PRfMA) in addition to $\alpha$-functionalized, living PMMA. Accordingly, the resulting block copolymers were comprised of both PMMA and PRfMA segments with different sequential orders. After the block copolymers were cast into films and annealed, their surface structures were characterized by angle-dependent XPS and contact angle measurements. All three samples showed significant segregation and enrichment of PRfMA segments at the surfaces.

Dispersion Stability of Pigments in Aqueous Solution of Anionic Oligo-Type Surfactants(IV);Dispersiveness of ${\alpha}-sulfo$ fatty acid vinyl ester oligomers (올리고머형 음이온성계면활성제 수용액에서 안료의 분산안정성(제4보);알파 술폰 지방산 비닐에스테르 올리고머의 분산성)

  • Lee, H.W.;Park, S.Y.;Nam, K.D.
    • Journal of the Korean Applied Science and Technology
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    • v.15 no.3
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    • pp.55-60
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    • 1998
  • The sodium ${\alpha}-sulfo$ fatty acid vinyl ester oligomers, which are oligomer type surfactants were prepared by polymerization with fatty acid vinyl acetate. The ${\alpha}-sulfonation$ of fatty acid vinyl ester oligomers were carried by direct addition of sulfur trioxide. The dispersing performance of oligomer type anionic surfactants and sodium dodecyl sulfate(SDS) in the aqueous suspension of iron oxide and titanium dioxide particles was evaluated by particle size distribution and zeta-potential measurement. As results, the particles of iron oxide and titanium dioxide were flocculated by addition of small amount of oligomer type anionic surfactants and sodium dodecyl sulfate(SDS), then the flocks redispersed by more addition of oligomer type anionic surfactants and SDS. The flocculation, redispersion process was observed in lower concentration range of oligomer type anionic surfactants than SDS. Especially, the dispersing action of sodium ${\alpha}-sulfo$ palmitic acid vinyl ester oligomer was better than sodium ${\alpha}-sulfo$ lauric acid vinyl ester oligomer.

Synthesis of Sodium ${\alpha}$-Sulfo Fatty Acid Allyl Ester Oligomer and Didpersion Stability of Pigments in Aqueous Solution ((${\alpha}$-술폰 지방산 알릴에스테르 올리고머의 합성 및 안료 분산성)

  • Lee, Hyang-Woo;Kwon, Soon-Il;Nam, Ki-Dae
    • Journal of the Korean Applied Science and Technology
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    • v.18 no.1
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    • pp.60-66
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    • 2001
  • Allylaliphatic carboxylate oligomers were prepared from polymerization giving allyl aliphatic carboxylates in the presence of potassium persulfate in methanol and the ${\alpha}-sulfonation$ of these allyl aliphatic carboxylates oligomers were carried by direct addition of dry sulfur trioxide. The dispersing performance of oligomer type anionic surfactants and SDS in the aqueous suspension of $Fe_{2}O_{3}$ and $Tio_{2}$ particles were evaluated by particle size distribution and ${\zeta}-potential$ measurement. As results, the particles of $Fe_{2}O_{3}$ and $Tio_{2}$ were flocculated by addition of small amount of oligomer type anionic surfactants and SDS, then the flocks redispersed by more addition oligomer type anionic surfactants and SDS. The dispersion and flocculation were observed in lower concentration range of oligomer type anionic surfactants than SDS.

Control of Block Copolymer Microdomain: In-Situ and Real-Time SANS Studies of Polymerization-Induced Self-assembly of Block Copolymer Microdomain Structure

  • Koizumi, Satoshi;Yamauchi, Kazuhiro;Hasegawa, Hirokazu;Tanaka, Hirokazu;Motokawa, Ryuhei;Hashimoto, Takeji
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.71-72
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    • 2006
  • We investigated a simultaneous living anionic polymerization process of isoprene (I) and 4styrene-d_8$ (S) in $benzene-d_6$ as a solvent with sec-buthyllithium as an initiator into polyisoprene(PI)-block-poly($styrene-d_8$)(PS) and the polymerization-induced molecular self-assembling process. This process was observed in-situ by time-resolved small-angle neutron scattering (SANS) experiment. The SANS profiles measured exhibited three time regions, where (i) the selective growth of PI chains occurs; (ii) the living chain ends switch from isoprenyllithium to styryllithium, and (iii) the SANS exhibited the polymerization induced disorder-to-order transition and order-to-order transition.

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Preparation and Physical Properties of Poly(Styrene/Acrylate) Core-Shell Latex Particles (Poly(Styrene/Acrylate) Core-Shell 라텍스 입자의 제조와 물성에 관한 연구)

  • Lee, Kyoung-Goo;Park, Keun-Ho
    • Journal of the Korean Applied Science and Technology
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    • v.20 no.1
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    • pp.27-32
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    • 2003
  • The core-shell latex particles were prepared by sequential emulsion polymerization of alkyl methacrylate and styrene(ST) by using an water-soluble initiator(APS) after preparing monomer pre-emulsion in the presence of an anionic surfactant(SDBS). In organic/organic core-shell polymerization, the pre-emulsion method, which minimized required quantity of sulfactant, has been used to increase the conversion rate and the stability of core-shell latex particles as well as to reduce the formation of secondary particle that cause problems of soap-free emulsion during shell polymerization. We used several methods to observe the core-shell structure. The core-shell structure was studied by measuring pH change during hydrolysis by NaOH, glass transition temperature($T_g$) by differential scanning calorimeter(DSC), morphology of latex by transmission electron microscope(TEM) and change of particle size and distribution by a particle analyzer.

Preparation and Application Characteristics of Carboxylated Styrene Butadiene Latex for Latex Modified Concrete (라텍스 개질 콘크리트용 Carboxylated Styrene Butadiene 라텍스의 제조와 적용 특성)

  • Lee, Bong-Kyu;Ju, Chang-Sik
    • Korean Chemical Engineering Research
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    • v.50 no.6
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    • pp.1076-1081
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    • 2012
  • For the purpose of development of the latex suitable for latex modified concrete, experimental researches on the preparation of carboxylated styrene butadiene latex by the method of the two-step emulsion polymerization and application to concrete were performed. Sodium dodecylbenzene sulfonate and sodium salt of lauryl sulfonate were selected as anionic emulsifiers, and nonylphenoxy poly(ethyleneoxy) ethanols (n=10, 20, 40) as latex stabilizer. Potassium persulfate and sodium bisulfite were used as redox initiator, besides $Na_2HPO_4$ and $K_2CO_3$ as electrolytes. Polymerization recipe of latex suitable for latex modified concrete were suggested from the experimental researches on the effects of anionic emulsifiers and their concentration on the polymerization stability, and the effect of electrolytes concentration on the particle size of latex. Physical properties, such as slump, air contents, compressive and flexural strength, of latex prepared by suggested polymerization recipe were examined. The experimental results showed that latex modified concrete satisfied the quality standards in slump and air contents. Furthermore, it was turned out that the compressive and the flexural strength of latex modified concrete with 28 days curing time showed appreciably improvements.

The Synthesis and Characterization of (TBMA)Macromer Grafted Anionic Acrylic Copolymer ((TBMA)Macromer를 그라프트시킨 음이온성 아크릴 공중합체의 합성과 물성)

  • Kim, Hyoung-Ook;Noh, Si-Tae;Kang, Shin-Chun
    • Applied Chemistry for Engineering
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    • v.4 no.3
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    • pp.627-636
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    • 1993
  • Anionic acrylic resin utilizing macromer(TBMA-g-MMA) copolymer was synthesized by preparing (TBMA) macromer using anionic living polymerization, followed by graft copolymerization with MMA macromer. To control the anionic site content in graft copolymer, the relative composition((TBMA) macromer/MMA ratio) of the graft copolymer was controlled at 7/3, 10/90, 15/85, 20/80, 30/70, 40/60, 50/50 in weight content. In the course of anionic living polymerization of(TBMA) macromer, broad molecular weight distribution (1.4~1.5) was obtained by using n-butyllithium-diphenyethylene initiatior system at $-78^{\circ}C$. To introduce the double bond at the end of chain in termination step, methacryloyl chloride was reacted after insertion of benzaldehyde as capping material. Moreover, TBMA parts in graft copolymer were hydrolyzed in the presence of p-toluenesulfonic acid catalyst, and neutralization of graft copolymer with triethylamine was granted acrylic resin to anionic site. Molecular weight and molecular weight distribution of(TBMA) macromer were determined by GPC, and the hydrolysis of TBMA with neutralization of acrylic resin were determined by IR and NMR. From water dispersion and stability point of view, stable dispersion state appeared at low molecular weight(TBMA) macromer with a small TBMA content as a result of scrutiny about the relation to TBMA content and branch length for(TBMA) macromer molecular weight in graft copolymer.

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