• Title/Summary/Keyword: Free radical polymerization

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Reaction Kinetics and Morphological Changes at Polymer-polymer Interface measured by Rheological Properties (유변학적 성질 측정으로 측정한 고분자 계면에서의 반응 kinetics와 morphology 변화)

  • Kim, Hwang-Yong;Unyong Jeong;Kim, Jin-Kon
    • Proceedings of the Korean Society of Rheology Conference
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    • 2002.05a
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    • pp.25-27
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    • 2002
  • In this study we investigated the reaction kinetics by a convenient but useful method-rheology to characterize the interface between two immiscible blends with a Reactive compatibilizer. Also, we made an attempt to correlate changes of interface roughness with rheological properties. The blend systems employed in this study was mono-carboxylated polystyrene (PS-mCOOH) and an poly(methyl methacrylate-ran-glycidylmethacrylate) (PMMA-GMA). PS-mCOOH was synthesized by an anionic polymerization and PMMA-GMA by a free radical polymerization. We prepared two plates of each polymer using compression molding with a smooth surface molder, then put one upon another. As soon as these two plates welds together inside a rheometer under nitrogen environment, the torque and moduli were obtained with reaction time at different temperatures. Through the analysis of this modulus change with reaction time, we estimated interfacial reaction and roughening. The increment of modulus in initial state can be correlated to the extent of reaction. We obtained the reaction kinetic constant by fitting appropriate kinetic equation into experimental data. We also showed that increment of modulus in later state was due to by roughened interface.

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Copolymerization of N-Vinylurea and Vinyl Acetate (Ⅱ). Solvent Effects in Radical Copolymerization (N-비닐尿素와 醋酸비닐의 混成重合 (第2報). 라디칼混成重合에서의 溶媒效果)

  • Woo Sik Kim;Hak-ki Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.80-85
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    • 1980
  • The free radical copolymeriaztion of N-vinylurea(VU) with vinyl acetate (VAc) was carried out at $60^{\circ}C$ in three solvents. VU-vinyl alcohol(VA) copolymers were prepared by the methanolysis of the VU-VAc copolymers. From the nitrogen content measurements of VU-VA copolymers, the monomer reactivity ratios for the VU-VAc copolymerization and the values of Alfrey-Price's Q and e for VU were determined. These Q and $\varrho$ values obtained in the cases of using methanol and methanol-dioxane as the polymerization solvents are comparable with those found for other monomers which have > NCO-pendent groups. The $\varrho$ value indicates that the urea group of VU is a electron-donating group. The copolymerization parameter of VU shows a strong effect of the solvents. These results are interpreted to be that VU is in equilibrium with its tautomer at the polymerization temperature.

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Optimization of Preparing Poly(AM-DMDAAC)/MMT Superabsorbent Nanocomposite by Orthogonal Experiment (Orthogonal 방법을 통한 Poly(AM-DMDAAC)/MMT 고흡수성 나노복합체 제조 연구)

  • Zhou, Ming;Yang, Shuangqiao;Zhou, Yongguo;Qin, Nan;He, Songtao;Lai, Dong;Xie, Zhongqiang;Yuan, Jundong
    • Polymer(Korea)
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    • v.38 no.1
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    • pp.16-23
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    • 2014
  • A novel poly(AM-DMDAAC)/MMT superabsorbent nanocomposites are prepared by radical polymerization using ammonium persulfate (APS) and anhydrous sodium sulfite as a free radical initiator and N,N-methylene bisacrylamide (MBA) as a crosslinker. In this paper, an optimization study on the synthesis of superabsorbent nanocomposites is carried out. Orthogonal array experiment indicates that the optimized conditions is acrylamide (AM) content 23 wt%, diallyl dimethyl ammonium chloride (DMDAAAC) content 6 wt%, montmorillonite (MMT) content 4 wt%, initiator content 0.2 wt% and crosslinker content 0.02 wt%. Under the optimization syntheses conditions concluded, the maximum water absorbency in distilled water is $659.53g{\cdot}g^{-1}$ and in 2 wt% sodium chloride solution is $116.25g{\cdot}g^{-1}$. Compared with the range values of different factors ($R_j$), the order of significance factors in distilled water is C (MMT) > B (DMDAAC) > A (AM) > D (crosslinker) > E (initiator). MMT is intercalated during polymerization reaction and a nanocomposite structure is formed as shown by TEM analysis and XRD analysis.

SFRP Synthesis of Acenaphthylene Oligomers and Block Copolymers. Potential Light Harvesting Structures

  • Ali, Dildar;Ahmed, Zaheer;Dust, Julian M.;Kazmaier, Peter M.;Buncel, Erwin
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2377-2384
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    • 2011
  • Azo-acenaphthylene oligomers with repeating acenaphthylene units "n" up to 4, 5, 7, 17 and 19 have been prepared successfully using nitroxide mediated Stable Free Radical Polymerization (SFRP). Azo-acenaphthylene oligomers, reversibly end-capped by the stable nitroxide 2,2,6,6-tetramethyl-1-piperidinoxyl (TEMPO), were further reacted via radical addition to 4-(naphthalenemethoxy)styrene monomer for diblock co-polymer formation. Characterization of the oligomers and diblock co-polymers was accomplished using MALDI-MS supported by GPC (Gel Permeation Chromatography) and $^1H$ NMR spectrometry. MALDI-MS afforded definitive results by providing an inter-peak interval of 152 (m/z), corresponding to acenaphthylene monomer, and inter-peak interval of 260 (m/z) for the naphthalenemethoxystyrene monomer unit in block copolymers. Our study opens the way to control the number of repeat units in the oligomers. Further these oligomers can be tailored with various monomers for the formation of block copolymers.

Copolymerization and Contact Lens Application of HEMA-Substituted Polyphosphazene (HEMA가 치환된 Polyphosphazene의 공중합 및 콘택트렌즈 응용)

  • Kim, Tae-Hum;Seong, A-Young
    • Journal of the Korean Chemical Society
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    • v.53 no.3
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    • pp.340-344
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    • 2009
  • HEMA/vinyl-substituted polyphosphazene was prepared by the ring-opening polymerization of phosphonitrillic chroride trimer at $200{\sim}300\;{^{\circ}C}$, followed by Grignard reaction with vinyl magnesium bromide and then by the reaction with HEMA(2-hydroxyethyl methacrylate). HEMA/vinyl-substituted polyphosphazene was copolymerized with EGDMA(ethylene glycol dimethacrylate; used as a cross-linker for the free-radical copolymerization), NVP (N-vinyl-pyrrolidone) in the presence of AIBN (azobisisobutyronitrile) as a radical initiator. The oxygen transmissibility, water content and visible-ray transmissibility of the resulting copolymer were measured to be Dk/t 88, 30.89% and 87%, respectively, indicating that the copolymer can be used as a good contact lens material.

A Study on the Antimicrobial Activity of Allylamine Polymers(II) (Allylamine계 항균제의 합성 및 그 항균성에 관한 연구(II))

  • 심재윤;조예경;윤남식;박태수
    • Textile Coloration and Finishing
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    • v.11 no.6
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    • pp.36-42
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    • 1999
  • The antimicrobial activities of the copolymer of N,N'-dimethyl- N,N'-diallyl ammonium chloride(DMDAAC) and diallyl amino(DA) were investigated. The copolymer of DMDAAC and DA was prepared by free radical Polymerization through an intra-intermolecular propagation mechanism ie, cyclopolymerization. The copolymer was, then, reacted with cyanuric chloride for reactivity with hydroxyl group of cellulose. Cotton fabrics were finished by synthesized polymer, and their antimicrobial activities and fastness to launderings were tested. Dichlorotriazinyl DMDAAC-DA copolymer has MIC value of 1ppm against S. aureus and 10ppm against K pneumoniae. The antimicrobial fastness of the finished cotton to launderings were good enough to show colony reduction above 70% against S. aureus and K pneumoniae after 50 repeated laundering in anionic commercial detergent. Optimum treatment concentrations of the polymer were 0.5% in cold pad-batch method, and 0.1% in pad-dry method.

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Controlled Drug Release from Polyacrylic Acid-Polyethylene Glycol Interpenetrating Networks (폴리아크릴산-폴리에칠렌글리콜 IPN공중합체 마트릭스의 팽윤 및 약물방출)

  • Kim, Youn-Jung;Kim, Kil-Soo;Lee, Seung-Jin
    • Journal of Pharmaceutical Investigation
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    • v.24 no.4
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    • pp.257-263
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    • 1994
  • The interpenetrating polymer networks (IPNs) of polyacrylic acid (PAA)-polyethylene glycol (PEG) were synthesized via crosslinking of PEG and simultaneous free radical polymerization of PAA. The equilibrium swelling of the IPNs matrices, ranged from 40% to 95%, was varied to a great extent as compared with PAA homopolymer due to the interpolymer interaction between PAA and PEG. The drug release kinetics of drug loaded matrices was significantly affected by the charge of drugs as well as interpolymer complexation.

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Synthesis of an Ordered Porous SiCN Ceramic Film by Self-Assembly of Inorganic-Organic Diblock Copolymer

  • Nghiem Quoc Dat;Kim Dong-Pyo
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.296-296
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    • 2006
  • Highly temperature stable mesoporous materials have excellent properties and potential applications. Here we show a novel poly(vinyl)silazane-block-polystyrene diblock copolymer, which was synthesized by controlled/living free radical polymerization with reversible addition fragmentation chain transfer (RAFT) route. The obtained diblock copolymer occurs the phaseseparation on the nanoscale to form ordered nanostructure, which is converted to mesoprorous ceramic after heating at 800oC. This route demonstrates the preparation of highly temperature stable mesoporous silicon carbon nitrides (SiCN) ceramic film directed from highly cross-linking poly(vinyl)silazane blocks with high ceramic yield, which is different from previous pathway.

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Copolymers of p-acryloyloxyacetophenone (AcAP) with MMA: Synthesis, Characterization and their Antifouling (AF) Efficiency

  • Elango, S.;Sidharthan, M.;Viswanadh, G.S.;Cho, Ji-Young;Park, N.S.;Shin, H.W.
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.381-381
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    • 2006
  • AcDP and AcAP were prepared by the reaction of acryloyl chloride (Ac) with 2,4,4' -trichloro-2' -hydroxydiphenyl ether (DP) and p-hydroxyacetophenone respectively in presence of triethylamine (TEA) in MEK at $0^{\circ}C$. The reaction was monitored by TLC and the prepared monomer was characterized by UV, IR, $1^H-NMR$ and GC-MS. Further, copolymers poly (AcDP-MMA-AcAP) were prepared in different feed ratio of monomers by free radical polymerization at $70^{\circ}C$, in which BPO as initiator and their molecular weight was determined by GPC. The AF activity of prepared polymers was investigated against representatives of marine microfoulers, shipfouling bacteria (B. macroides & P. aeruginosa) and microalgae (A.coffeaeformis & N. incerta). The antibacterial activity and diatom attachment assays showed significant AF potential of these polymers.

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Synthesis of High-Performance Polycarboxylate(PC)-Type Superplasticizer, and Its Fluidity and Hydration Behavior in Cement Based-System (폴리카복실레이트계 고성능 유동화제의 합성과 시멘트계 내의 유동 및 수화 반응 거동)

  • Shin, Jin-Yong;Chae, Eun-Jin;Hong, Ji-Sook;Suh, Jeong-Kwon;Hwang, Eui-Hwan
    • Proceedings of the Korea Concrete Institute Conference
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    • 2006.05b
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    • pp.77-80
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    • 2006
  • Graft copolymerized polycarboxylate(PC)-type superplasticizers(PCs) which have carboxylic acid with $\pi$ bond among the molecular structure and polyethyleneglycol methyl ether methacrylate(PMEM) were synthesized by free radical reaction and investigated the chemical structure, polymerization condition, and physical and chemical properties. Also, the effects of PCs in the dispersion, adsorption and hydration of cement were evaluated. As the molecular weight of graft chain decreases, the adsorption amount on cement particles increased. It was advantageous for the flow to reduce molar ratio, the lower the side bone molecular weight, and increase the molar ratio, the larger the side bone molecular weight. The hydration reaction speed was highly delayed at day 1, due to increase in molar ratio and reduction in side bone molecular weight, but it was recovered in the days after.

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