• Title/Summary/Keyword: radical polymerization

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Synthesis of a Triblock Copolymer Containing a Diacetylene Group and Its Use for Preparation of Carbon Nanodots

  • Kim, Beom-Jin;Oh, Dong-Kung;Chang, Ji-Young
    • Macromolecular Research
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    • v.16 no.2
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    • pp.103-107
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    • 2008
  • Carbon nanodots were prepared by the pyrolysis of a triblock copolymer. The triblock copolymer, poly(methyl methacrylate)-b-polystyrene-b-poly(methyl methacrylate) was synthesized by atom transfer radical polymerization using an initiator containing a diacetylene group. A polymer thin film on a mica substrate was prepared by spin-casting at 2,000 rpm from a 0.5 wt% toluene solution of the triblock copolymer. After drying, the cast film was vacuum-annealed for 48 h at $160^{\circ}C$. The annealed film formed a spherical morphology of polystyrene domains with a diameter of approximately 30 nm. The film was exposed to UV irradiation to induce a cross-linking reaction between diacetylene groups. In the subsequent pyrolysis at $800^{\circ}C$, the cross-linked polystyrene spheres were carbonized and the poly(methyl methacrylate) matrix was eliminated, resulting in carbon nanodots deposited on a substrate with a diameter of approximately 5 mn.

Synthesis of New pH-Sensitive Amphiphilic Block Copolymers and Study for the Micellization Using a Fluorescence Probe

  • Kim, Kyung-Min;Choi, Song-Yee;Jeon, Hee-Jeong;Lee, Jae-Yeol;Choo, Dong-Joon;Kim, Jung-Ahn;Kang, Yong-Soo;Yoo, Hyun-Oh
    • Macromolecular Research
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    • v.16 no.2
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    • pp.169-177
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    • 2008
  • This paper reports a facile synthesis of new water-soluble poly(ethylene oxide) (PEO)-based amphiphilic block copolymers showing pH sensitive phase transition behaviors. The copolymers were prepared by atom transfer radical polymerization (ATRP) of methacrylamide type of monomers carrying a sulfonamide group using a PEO-based macroinitiator and a Cu(I)Br/$Me_6TREN$ catalytic system in aqueous media. The resulting polymers were characterized by a combination of $^1H$-NMR, size exclusion chromatography, and UV/Visible spectrophotometeric analysis. The micellization of the block copolymers as a drug-loading mechanism in aqueous media using fluorescein salt was examined as a function of pH. The stable micelle formation and its loading efficacy suggest that the block copolymers can be used as precursors for drug-nanocontainers.

Preparation of poly(methyl methacrylate)/clay nanocomposites by microwaveassisted in-situ radical polymerization

  • Jeong, Ji-Won;Kim, Dong-Hyun;Jang, Jae-Ho;Lee, Jung-Taek;Yoo, Kyung-Hyeon;Yoon, Seog-Young
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.29 no.1
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    • pp.19-23
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    • 2019
  • The PMMA (polymethyl methacrylate)/clay nanocomposites were synthesized by in situ radical polymerizations with different clay contents (3 and 7 wt%) using microwave heating. The nanostructure, optical, and thermal properties of the synthesized PMMA/clay nanocomposites were measured by XRD, TEM, AFM, UV-vis, and TGA. It was found that the intercalated- or exfoliated structure of PMMA/clay nanocomposites was strongly dependent on the content of clay. Thus, the imposition of microwave-assisted polymerization facilitated a delamination process of layered silicates to achieve exfoliation state of interlayer distance. The PMMA/3 wt% C10A nanocomposite with well-dispersed and exfoliated clay nano-layers showed the good optical transparency similar to pure PMMA in this study. The thermal decomposition rates of the PMMA/clay nanocomposites become to be lower compared to that of the pure PMMA, indicating the intercalated- or exfoliated inorganic silicate has high thermal stability. A possible reason is that the thermally segmental motion of PMMA polymer into inorganic silicate interlayer spacing has increased the thermal stability of the PMMA/clay nanocomposites.

A Novel Synthetic Route to Highly Cross-Linked Poly(vinyl ethers): Ⅲ. Synthesis and Free Radical Polymerization of Aryloxyethyl Vinyl Ethers Having an Electron Acceptor in ortho- or meta-Position

  • 이주연;김무용;안광덕
    • Bulletin of the Korean Chemical Society
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    • v.18 no.3
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    • pp.318-323
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    • 1997
  • ο-(2-Vinyloxyethoxy)benzylidenemalononitrile (3a) and methyl ο-(2-vinyloxyethoxy)-benzylidenecyanoacetate (3b), m-(2-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl m-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b) were prepared by the condensation of ο-(2-vinyloxyethoxy)benzaldehyde (1) and m-(2-vinyloxyethoxy)benzaldehyde (2) with malononitrile or methyl cyanoacetate, respectively. Bifunctional vinyl ether monomers 3a and 3b polymerized quantitatively with radical initiators in γ-butyrolactone solution at 65 ℃, while meta-isomers 4a and 4b gave lower yields of polymers under the same conditions. The polymers 5-6 obtained from the monomers 3-4 were insoluble in common solvents due to cross-linking. Under the same polymerization conditions ethyl vinyl ether polymerized well with model compounds ο-methoxybenzylidenemalononitrile 7a, methyl ο-methoxybenzylidenecyanoacetate 7b, m-methoxybenzylidenemalononitrile 8a, and methyl m-methoxybenzylidenecyanoacetate 8b, respectively, to give 1:1 alternating copolymers 9-10 in high yields. Cross-linked polymers 5-6 showed a thermal stability up to 300 ℃, and showed a double phase degradation pattern in their TGA thermograms. Polymers 5-6 showed broad endothermic bands around 75-110 ℃ without any characteristic Tg peaks in DSC thermograms. Alternating copolymers 9-10, except copolymer 9b were soluble in common organic solvents. The inherent viscosities of polymer 9-10 were in the range of 0.35-0.62 dL/g. Polymer films cast from acetone solution were cloudy and tough and Tg values obtained from DSC thermograms were in the range of 118-165 ℃.

Polymerization of Polystyrene Latex using Ultrasound Energy Effect (초음파 에너지를 이용한 Polystyrene Latex의 중합 특성)

  • Kim, Hyung Jin;Kim, Won II;Lee, Seung Bum;Hong, In Kwon
    • Applied Chemistry for Engineering
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    • v.8 no.6
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    • pp.886-892
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    • 1997
  • There are many methods to synthesize polystyrene latex. Emulsion polymerization technique is commonly used commercially, but it requires a new technology to replace a traditional polymerization method because of the disadvantage of chemical initiator for environmental pollution. Since free radicals can be produced by ultrasound energy effect, polystyrene latex was synthesized using ultrasound energy instead of chemical initiator. As the ultrasonic irradiation time was increased, average molecular weight was increased and polydispersity was decreased. The degree of polymerization was increased with the concentration of SDS and maximum degree of polymerization was shown at 2wt.% SDS concentration and the reaction temperature of $40^{\circ}C$. During the course of polymerization, molecular weight was repeatedly fluctuated because of occurrence of depolymerization. Narrow molecular weight distribution polystyrene latex having controlled molecular weight was synthesized by controlling ultrasonic irradiation time and the concentration of SDS.

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Interactions and Ionic Conductivities of Poly(epichlorohydrin) Graft Copolymer Electrolyte Membranes (Poly(epichlorohydrin) 가지형 공중합체 전해질막의 상호작용 및 이온 전도도)

  • Koh, Joo-Hwan;Lee, Kyung-Ju;Park, Jung-Tae;Ahn, Sung-Hoon;Kim, Jong-Hak
    • Membrane Journal
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    • v.20 no.3
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    • pp.203-209
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    • 2010
  • Amphiphilic graft copolymers based on poly(epichlorohydrine) (PECH) were synthesized using atom transfer radical polymerization (ATRP). Successful graft polymerization of poly(methyl methacrylate)(PMMA) and poly(butyl methacrylate) (PBMA) from PECH was confirmed by nuclear magnetic resonance ($^1H$ NMR) and FT-IR spectroscopy. Upon the introduction of KI or LiI to the graft copolymers, the ether stretching bands were shifted to a lower wavenumber due to coordinative interactions. Ionic conductivities of PECH-g-PBMA complexes were always higher than those of PECH-g-PMMA complexes, resulting from higher mobility of rubbery PBMA chains. The maximum ionic conductivity of $2.7{\times}10^{-5}\;S/cm$ was obtained at 10 wt% of KI for PECH-g-PBMA electrolytes.

Orientational Control of Nano Structures from Block Copolymer Using Homo-Polymer Nano Interface (단일 성분 고분자 나노 계면의 도입을 통한 블락 고분자 박막의 나노 구조 배향 조절)

  • In, Insik
    • Journal of Adhesion and Interface
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    • v.9 no.4
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    • pp.30-33
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    • 2008
  • Two polymeric interfaces with single component homo-polymers were prepared to control the orientation of block copolymer thin-film nanostructures. Poly(4-acetoxy styrene) (OH-PAS) and poly(4-methoxy styrene) (OH-PMS) which have the average chemical composition of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) were precisely synthesized through nitroxide-mediated radical polymerization. After dehydration reactions between above polymers and SiOx layers of silicon wafers, the polymer-modified interface induced partial (30%) vertical orientation of PS-b-PMMA thin film in the case of OH-PMS and wholly parallel orientation in the case of OH-PAS. Chemical compositions of polymeric interface layers are regarded as the key parameter to control the orientation of nanostructures of block copolymer thin film.

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Preparation and Properties of Polyolefin Graft Polymer available as a Primer for Polyurethane Adhesive (I) Synthesis of polyolefins with cyclic acid anhydride by free radical graft polymerization

  • Ryu, Ki Jung;Kim, Min Jung;Min, Seong Kee;Lee, Won Kee;Park, Chan Young
    • Elastomers and Composites
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    • v.50 no.2
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    • pp.119-125
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    • 2015
  • Because of their low surface free energy and absence of polar groups at the surface, polyolefins are substrates whose wetting and adhesion are very difficult. Free radical grafting of monomers to backbone polymer is one of the most attractive ways for the chemical modification of polymers. Synthesis of graft copolymer through graft polymerizations of PE and/or PP with phthalic anhydride (PhAn) was made and FTIR spectra of the graft polymer were the examined. And also the effects of phthalic anhydride content on the grafting ratio, thermal properties and contact angle of the graft polymer were examined.

Steric Hindrance in the Free Radical Polymerization of Aryloxyethyl Vinyl Ethers Containing Electron-Deficient Olefin Groups$^{\dag}$

  • Lee, Ju Yeon;Jin, Mi Gyeong
    • Bulletin of the Korean Chemical Society
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    • v.21 no.6
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    • pp.613-617
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    • 2000
  • p-(2-Vinyloxyethoxy)benzylidenemalononitrile (4a), methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b), 3,5-dimethoxy-4-(2'-vinyloxyethoxy)benzylidenemalononitrile (5a), methyl 3,5-dimethoxy-4-(2'-vinyloxy-ethoxy) benzylidenecyanoacetate (5 b), o-(2 -vinyloxyethoxy)benzylidenemalononitrile (6a), methyl o-(2-viny-Ioxyethoxy) benzylidenecyanoacetate (6b), 1,3-di-(2',2'-dicyanovinyl)-5-methyl-2-(2'-vinyloxyetioxy)benzene (7a), l,3-di-(2'-carbomethoxy-2'-cyanovinyl)-5-methyl-2-(2'-vinyloxyethoxy)benzene (7b), 2,3,4-tri-(2'-viny-Ioxyethoxy) benzylidenemalononitrile (8a), methyl 2,3,4-tri-(2'-vinyloxyethoxy)benzylidenecyanoacetate (8b), 2,4,6-tri-(2'-vinyloxyethoxy)benzylidenemalononitrile (9a), and methyl 2,4,6-tri-(2'-vinyloxyethoxy)benzyl-idenecyanoacetate(9b) were prepared by the condensation of the corresponding benzaldehyde 1-3 with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 4, 6, and 8 polymerized readily with radical initiators to yield crosslinked polymers 10, 12, and 14. However, compounds 5, 7, and 9 were inert to radical initiators due to the steric hindrance. The resulting polymers 10, 12, and 14 were not soluble in common solvents showing a thermal stability up to $300^{\circ}C$.

Encapsulation of Nanomaterials within Intermediary Layer Cross-linked Micelles Using a Photo-Cross-linking Agent

  • Kim, Jin-Sook;Youk, Ji-Ho
    • Macromolecular Research
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    • v.17 no.11
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    • pp.926-930
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    • 2009
  • A new method for encapsulating nanomaterials within intermediary layer cross-linked (ILCL) polymeric micelles using a bifunctional photo-cross-linking agent was developed. For ILCL polymeric micelles, an amphiphilic triblock copolymer of poly(ethylene glycol)-b-poly(2-hydroxyethyl methacrylate)-b-poly(methyl methacrylate) (PEG-PHEMA-PMMA) was synthesized via consecutive atom transfer radical polymerization (ATRP), Di(4-hydroxyl benzophenone) dodecanedioate (BPD) was used as a bifunctional photo-cross-linking agent. The PMMA-tethered Au nanoparticles and BPD, or pyrene and BPD were encapsulated in the PEG-PHEMA-PMMA micelles, and their intermediary layers were photo-cross-linked by UV irradiation for 1 h. The HEMA units donated labile hydrogens to the excited-state benzophenone groups in BPD, and they were subsequently cross-linked by BPD through radical-radical combination. The spherical structures of the PEG-PHEMA-PMMA micelles containing the Au nanoparticles or pyrene were unaffected by the photo-cross-linking process.