• Title/Summary/Keyword: solid state polymerization

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Molecular Weight Distribution of Liquid Phase AN and Solid Phase Polymer in Precipitation Polymerization of AN By Changing Solution Composition and Temperature

  • Liu, Weiwei;Zhang, Shuangkun;Wang, Jing;Ryu, Seung Kon;Jin, Ri-Guang
    • Carbon letters
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    • v.13 no.3
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    • pp.133-138
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    • 2012
  • According to kinetic mechanisms, liquid phase polymerization and solid phase polymerization are different in acrylonitrile (AN) polymerization, and so the relationship between the contribution ratio and molecular weight distribution (MWD) was obtained through theoretic analysis. The precipitation homopolymerization of AN was carried out in a mixture solution of dimethyl sulfoxide (DMSO) and water at $50{\sim}65^{\circ}C$ using ${\alpha}$,${\alpha}^{\prime}$-azobisisobutyronitrile as an initiator. The contribution ratio decreased and approached 0; the MWD also decreased and approached 2 with the increase of the $H_2O$/DMSO ratio from 10/90 to 90/10. The experimental data were found to coincide well with the theoretical equation derived from the mechanisms.

Influence of "Historical Effects" on the Rheological Properties of a Polyacrylonitrile Copolymer Solution

  • Cheng, Yumin;Zhang, Huibo;Zhang, Shuangkun;Liu, Weiwei;Wang, Jing;Cheng, Run;Ryu, SeungKon;Jin, Riguang
    • Carbon letters
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    • v.14 no.1
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    • pp.45-50
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    • 2013
  • Polyacrylonitrile (PAN) copolymers of different molecular weights were synthesized by a suspension polymerization and precipitation polymerization method. The rheology behaviors of the synthesized PAN copolymers were investigated in relation to their molecular weight, solid content and melting temperature. The influence of "historical effects" on the spinning solution of PAN was studied by analyzing the laws of viscosity considering the diversification time and temperature. The viscosity disciplines of each spinning solution conformed well to the rheological universal laws in a comparison of the suspension polymerization product with that of precipitation polymerization. Viscosity changes in the swelling process of dissolution were gentler in the suspension polymerization product; a small amount of water will quickly debase the solution viscosity, and high-speed mixing can greatly shorten the time required by the spinning solution to reach the final viscosity.

Improving Power Conversion Efficiency and Long-term Stability Using a Multifunctional Network Polymer Membrane Electrolyte; A Novel Quasi-solid State Dye-sensitized Solar Cell

  • Gang, Gyeong-Ho;Gwon, Yeong-Su;Song, In-Yeong;Park, Seong-Hae;Park, Tae-Ho
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.484.2-484.2
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    • 2014
  • There are many efforts to improving the power conversion efficiencies (PCEs) of dye-sensitized solar cells (DSCs). Although DSCs have a low production cost, their low PCE and low thermal stability have limited commercial applications. This study describes the preparation of a novel multifunctional polymer gel electrolyte in which a cross-linking polymerization reaction is used to encapsulate $TiO_2$ nanoparticles toward improving the power conversion efficiency and long-term stability of a quasi-solid state DSC. A series of liquid junction dye-sensitized solar cells (DSCs) was fabricated based on polymer membrane encapsulated dye-sensitized $TiO_2$ nanoparticles, prepared using a surface-induced cross-linking polymerization reaction, to investigate the dependence of the solar cell performance on the encapsulating membrane layer thickness. The ion conductivity decreased as the membrane thickness increased; however, the long term-stability of the devices improved with increasing membrane thickness. Nanoparticles encapsulated in a thick membrane (ca. 37 nm), obtained using a 90 min polymerization time, exhibited excellent pore filling among $TiO_2$ particles. This nanoparticle layer was used to fabricate a thin-layered, quasi-solid state DSC. The thick membrane prevented short-circuit paths from forming between the counter and the $TiO_2$ electrode, thereby reducing the minimum necessary electrode separation distance. The quasi-solid state DSC yielded a high power conversion efficiency (7.6/8.1%) and excellent stability during heating at $65^{\circ}C$ over 30 days. These performance characteristics were superior to those obtained from a conventional DSC (7.5/3.5%) prepared using a $TiO_2$ active layer with the same thickness. The reduced electrode separation distance shortened the charge transport pathways, which compensated for the reduced ion conductivity in the polymer gel electrolyte. Excellent pore filling on the $TiO_2$ particles minimized the exposure of the dye to the liquid and reduced dye detachment.

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New Polymerization using Microwave Radiation

  • Lee, Jae-Heung;Kim, Yong-Seok;Hong, Young-Taik;Jung, Hyun-Min;Oh, Hyoung-Suk
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.213-213
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    • 2006
  • High molecular weight of polycarbonate(PC) and well dispersed PC/MMT nanocomposites were successfully prepared through the novel technology, microwave solid-state polymerization. In our studies, the microwave irradiation is more effective than conventional oil-bath heating on achieving the high molecular weight and uniform nanocomposites. Using the polycarbonate prepolymer made it possible to intercalate the short chains into the galleries of MMT more easily. And it was observed that prepared nanocomposites by microwave solid-state polymerization have more uniform dispersion of silicate of MMT into the polymer matrix than by oil heating.

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Scale-Up of Polymerization Process of Biodegradable Polymer Poly(lactic acid) Synthesis Using Direct Polycondensation Method

  • Pivsa-Art, Sommai;Niamlang, Sumonman;Pivsa-Art, Weraporn;Santipatee, Nutchapon;Wongborh, Tossamon;Pavasupree, Sorapong;Ishimoto, Kiyoaki;Ohara, Hitomi
    • International Journal of Advanced Culture Technology
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    • v.3 no.2
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    • pp.100-109
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    • 2015
  • Environmental problems from petroleum-based plastic wastes have been rapidly increasing in recent years. The alternative solution is focus on the development of environmental friendly plastic derived from renewable resource. Poly(lactic acid) (PLA) is a biodegradable polymer synthesized from biomass having potential to replace the petroleum-based non-degradable polymers utilizations. PLA can be synthesized by two methods: (1) ring-opening of lactide intermediate and (2) direct polycondensation of lactic acid processes. The latter process has advantages on high yields and high purity of polymer products, materials handling and ease of process treatments. The polymerization process of PLA synthesis has been widely studied in a laboratory scale. However, the mass scale production using direct polycondensation of lactic acid has not been reported. We have investigated the kinetics and scale-up process of direct polycondensation method to produce PLA in a pilot scale. The order of reaction is 2 and activation energy of lactic acid to lactic acid oligomers is 61.58 kJ/mol. The pre-polymer was further polymerized in a solid state polymerization (SSP) process. The synthesized PLA from both the laboratory and pilot scales show the comparable properties such as melting temperature and molecular weight. The appearance of synthesized PLA is yellow-white solid powder.

Disposable Solid-State pH Sensor Using Nanoporous Platinum and Copolyelectrolytic Junction

  • Noh, Jong-Min;Park, Se-Jin;Kim, Hee-Chan;Chung, Taek-Dong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.11
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    • pp.3128-3132
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    • 2010
  • A disposable solid-state pH sensor was realized by utilizing two nanoporous Pt (npPt) electrodes and a copolyelectrolytic junction. One nanoporous Pt electrode was to measure the pH as an indicating electrode (pH-IE) and the other assembled with copolyelectrolytic junction was to maintain constant open circuit potential ($E_{oc}$) as a solid-state reference electrode (SSRE). The copolyelectrolytic junction was composed of cationic and anionic polymers immobilized by photo-polymerization of N,N'-methylenebisacrylamide, making buffered electrolytic environment on the SSRE. It was expected to make. The nanoporous Pt surrounded by a constant pH excellently worked as a solid state reference electrode so as to stabilize the system within 30 s and retain the electrochemical environment regardless of unknown sample solutions. Combination between the SSRE and the pH-IE commonly based on nanoporous Pt yielded a complete solid-state pH sensor that requires no internal filling solution. The solid state pH sensing chip is simple and easy to fabricate so that it could be practically used for disposable purposes. Moreover, the solid-state pH sensor successfully functions in calibration-free mode in a variety of buffers and surfactant samples.

Surface Polarity Dependent Solid-state Molecular Biological Manipulation with Immobilized DNA on a Gold Surface

  • Lee, Jiyoung;Kim, Jeong Hee
    • International Journal of Oral Biology
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    • v.37 no.4
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    • pp.181-188
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    • 2012
  • As the demand for large-scale analysis of gene expression using DNA arrays increases, the importance of the surface characterization of DNA arrays has emerged. We compared the efficiency of molecular biological applications on solid-phases with different surface polarities to identify the most optimal conditions. We employed thiol-gold reactions for DNA immobilization on solid surfaces. The surface polarity was controlled by creating a self-assembled monolayer (SAM) of mercaptohexanol or hepthanethiol, which create hydrophilic or hydrophobic surface properties, respectively. A hydrophilic environment was found to be much more favorable to solid-phase molecular biological manipulations. A SAM of mercaptoethanol had the highest affinity to DNA molecules in our experimetns and it showed greater efficiency in terms of DNA hybridization and polymerization. The optimal DNA concentration for immobilization was found to be 0.5 ${\mu}M$. The optimal reaction time for both thiolated DNA and matrix molecules was 10 min and for the polymerase reaction time was 150 min. Under these optimized conditions, molecular biology techniques including DNA hybridization, ligation, polymerization, PCR and multiplex PCR were shown to be feasible in solid-state conditions. We demonstrated from our present analysis the importance of surface polarity in solid-phase molecular biological applications. A hydrophilic SAM generated a far more favorable environment than hydrophobic SAM for solid-state molecular techniques. Our findings suggest that the conditions and methods identified here could be used for DNA-DNA hybridization applications such as DNA chips and for the further development of solid-phase genetic engineering applications that involve DNA-enzyme interactions.

Afterpolymerization and Depolymerization of Poly-${\varepsilon}$-caproamide in Solid State (고체상태에서 Poly-${\varepsilon}$-caproamide의 후중합 및 해중합에 관한 연구)

  • Jung-Ji Moon;Dong-ho Lee;Tae-oan Ahn
    • Journal of the Korean Chemical Society
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    • v.17 no.6
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    • pp.450-454
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    • 1973
  • The afterpolymerization and depolymerization of poly-${\varepsilon}$-caproamide in solid state have been studied under two different reaction conditions, nitrogen flow and sealed state. The degree of polymerization ($\bar{P}$) of nylon 6 increased with the increase in reaction time and temperature, and then reacted finally an equilibrium. In the presence of oxygen, $\bar{P}$ decreased by increasing the reaction time due to the oxidation reaction. Under certain reaction condition, the change of $\bar{P}$ for different initial degree of polymerization ($\bar{P}_0$) tendered toward unity in equilibrium.

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Multinuclear Solid-state NMR Investigation of Nanoporous Silica Prepared by Sol-gel Polymerization Using Sodium Silicate

  • Kim, Sun-Ha;Han, Oc-Hee;Kim, Jong-Kil;Lee, Kwang-Ho
    • Bulletin of the Korean Chemical Society
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    • v.32 no.10
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    • pp.3644-3649
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    • 2011
  • Multinuclear solid-state nuclear magnetic resonance (NMR) experiments were performed to investigate the local structure changes of nanoporous silica during hydrothermal treatment and surface modification with 3-aminopropyltriethoxysilane (3-APTES). The nanoporous silica was prepared by sol-gel polymerization using inexpensive sodium silicate as a silica precursor. Using $^1H$ magic angle spinning (MAS) NMR spectra, the hydroxyl groups, which play an important role in surface reactions, were probed. Various silicon sites such as $Q^2$, $Q^3$, $Q^4$, $T^2$, and $T^3$ were identified with $^{29}Si$ cross polarization (CP) MAS NMR spectra and quantified with $^{29}Si$ MAS NMR spectra. The results indicated that about 25% of the silica surface was modified. $^1H$ and $^{29}Si$ NMR data proved that the hydrothermal treatment induced dehydration and dehyroxylation. The $^{13}C$ CP MAS and $^1H$ MAS NMR spectra of 3-APTES attached on the surface of nanoporous silica revealed that the amines of the 3-aminopropyl groups were in the chemical state of ${NH_3}^+$ rather than $NH_2$.