• Title/Summary/Keyword: solution polymerization

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A Novel Synthetic Route to Highly Cross-Linked Poly(alkylvinylether)s. Synthesis and Free Radical Polymerization of a Vinyl Ether Monomer Containing Electron Acceptors in Side Chain

  • 이주연;이현주;김무용
    • Bulletin of the Korean Chemical Society
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    • v.17 no.3
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    • pp.257-262
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    • 1996
  • p-(2-Vinyloxyethoxy)benzylidenemalononitrile 2 and methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate 3 was prepared by the condensation of p-(2-vinyloxyethoxy)benzaldehyde 1 with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2 and 3 polymerized quantitatively with radical initiators in γ-butyrolactone solution at 65 ℃. The trisubstituted terminal double bond participated in the vinyl polymerization and radical polymerization of 2 and 3 led to swelling polymers 4 and 5 that were not soluble in common solvents due to cross-linking. Under the same polymerization conditions ethylvinyl ether polymerized well with model compounds of p-methoxybenzylidenemalononitrile 6 and methyl p-methoxybenzylidenecyanoacetate 7, respectively, to give 1:1 alternating copolymers 8 and 9 in high yields. Polymers 4 and 5 showed a thermal stability up to 300 ℃ without any characteristic Tg peaks in DSC thermograms. Alternating copolymers 8 and 9 were soluble in common solvents such as acetone and DMSO, and the inherent viscosities of the polymers were in the range of 0.36-0.74 dL/g. Films cast from acetone solution were cloudy and tough and Tg values obtained from DSC thermograms were in the range of 59-60 ℃.

수처리 목적의 대기압플라즈마를 이용한 유사 폴리도파민 필름 증착

  • Mun, Mu-Gyeom;Yeom, Geun-Yeong
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2018.06a
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    • pp.124-124
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    • 2018
  • Polydopamine은 수중 접착력, 친환경 접착제, nanoparticle absorption 등 다양한 특성으로 많이 연구되고 있는 소재이다. 본 연구에서는 dopamine을 이용하여 수중 금속을 흡착시키는 thin film을 제작하였다. 종래의 Polydopamine coating 방법으로 wet coating 이 사용되고 있다. 하지만 wet 방식의 경우 시간이 오래 걸릴 뿐만 아니라 in-line, roll to roll 방식을 적용하는 것이 어렵기 때문에 생산적이지 않다. 이에 본 연구에서는 Atmospheric Pressure Plasma(APP)를 이용 하여 Polydopamine-like film을 coating 하였다. APP의 경우 vacuum system, solution tank가 필요 없고 in-line, roll to roll 방식을 적용 할 수 있기 때문에 더 경제적이고 생산적인 공정이다. 또한 기존의 Plasma polymerization 방법은 Plasma energy가 높기 때문에 source의 분자구조가 바뀌거나 atom 단위로 분해된다. source의 분자구조가 바뀌는 "Atomic polymerization", Neiswender-Rosskamp Mechanism이 적용되면 wet 방식 coating한 film과는 다른 특성을 갖게 된다. 하지만 APP polymerization은 Plasma energy가 vacuum plasma 보다 매우 낮기 때문에 stile polymerization mechanism을 구현 하는데 적합 하다. stile polymerization mechanism은 Plasma 내부에서 polymer source를 분해 성장 시켜서 Polymer film 얻는 것이 아닌 source의 분자구조가 깨지지 않으면서 polymer growing 시키는 방법이다. dopamine source의 분자구조를 최대한 유지하려고 하는 이유는 metal absorption과 같은 특성이 dopamine chemical structure에 영향을 받기 때문이다. 많은 논문들에서 dopamine의 catechol group이 metal absorption, adhesion force에 영향을 주는 주요 인자라고 주장하고 있기 때문이다. 그래서 본 논문에서는 Dopamine source의 형태를 보존하면서 Polymerization 하는 방법으로 APP process를 사용 하여 낮은 전압에서 Polydopamine-like film을 제작 하였다. APP system 의 Plasma 방전부 에 Dopamine source를 유입하기 위하여 본 논문에서는 Piezo Spray 방식을 사용 하였다. Dopamine을 evaporator 하는 것이 어렵고 chemical composition이 유사한 monomer를 사용해서 Plasma Polymerization으로 Dopamine 분자 구조를 재현하는 것도 어렵다. 그래서 본 연구에서는 Dopamine을 water에 immerse 하고 Dopamine solution을 mist 상태로 만들어서 Plasma discharge area에 유입하였다. 이러한 방법으로 만들어진 film은 Polydopamine film은 아니지만 Polydopamine film과 유사한 Chemical composition, chemical structure, metal absorption을 갖는 것을 FT-IR, SEM, XPS을 이용 하여 확인 하였다. Dopamine source의 보존에 대하여 명확하게 확인하기 위하여 FT-IR을 측정 하였다. 전압에 따른 Benzene ring, hydroxyl group의 비율을 확인 하였다. 낮은 전압으로 coating 된 Polydopamine-like film 일수록 hydroxyl group peak($3400{\sim}3000cm^{-1}$)과 비교하여 Benzene ring peak($1600{\sim}1580cm^{-1}$ and $1510{\sim}500cm^{-1}$)이 흡수를 더 많이 하는 것을 확인 할 수 있다. 이것은 Benzene ring이 파괴되지 않고 보존되는 것을 보여준다. Dopamine에서 Benzene ring은 absorption main factor인 catechol에 있는 chemical structure이다. 즉 Benzene ring peak이 높을수록 Catechol이 잘 보존 되었다는 의미 이다. Catechol의 보존은 absorption main factor가 보존 된다는 의미 이다. 이러한 Polydopamine-like film으로 As, Cr, Mg, Cu 200ppm solution에 대한 filtration 능력을 확인 하였다. As, Cr, Cu, Mg 의 제거율이 각각 약25%, 35%, 45%, 65%인 것을 확인 하였다. 이 수치는 시중에 판매되는 제품들과 비교했을 때 300%~500% 향상된 수치 이다.

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Characteristic of Sintering of Mullite-Cordierite Composite by a Solution-Polymerization Route Employing PVA (PVA를 이용한 Solution-Polymerization 합성법에 의하여 제조된 Mullite-Cordierite 복합체의 소결특성)

  • Lee, Yong-Seok;Lee, Byung-Ha
    • Journal of the Korean Ceramic Society
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    • v.42 no.3 s.274
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    • pp.155-164
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    • 2005
  • The characteristics of sintering for Mullite-Cordierite (MC) composites and the effect of $TiO_2$ addition were studied. The MC composites were manufactured by a solution-polymerization method using PVA as a polymer carrier, and $TiO_2$ was used as a sintering agent. They were calcined at $1300^{\circ}C$, planetary milled for 4 h and sintered at $1450^{\circ}C$. As cordierite content increased, relative density of materials was increased up to $98\%$ and sinterability was improved. In case of $50\;wt\%$ mullite/$5\;wt\%$ cordierite composition sintered for 16 h, the flexural strength and thermal expansion coefficient were 190 MPa and $3.07{\times}0^{-6}/^{\circ}C$, respectively. However, mechanical properties were decreased with the cordierite contents higher than $50\;wt\%$ because of the excess liquid-phase amount. As the addition of $TiO_2$ is increased, columnar crystal of mullite and liquid-phase contents were increased. In particular, the flexural strength and thermal expansion coefficient decreased in case of $5\;wt\%\;TiO_2$ addition.

Multiwalled Carbon Nanotubes Functionalized with PS via Emulsion Polymerization

  • Park, In-Cheol;Park, Min;Kim, Jun-Kyung;Lee, Hyun-Jung;Lee, Moo-Sung
    • Macromolecular Research
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    • v.15 no.6
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    • pp.498-505
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    • 2007
  • This study demonstrated the in-situ functionalization with polymers of multi-walled carbon nanotubes (MWNTs) via emulsion polymerization. Polystyrene-functionalized MWNTs were prepared in an aqueous solution containing styrene monomer, non-ionic surfactant and a cationic coupling agent ([2-(methacryloyloxy)ethyl]trime-thylammonium chloride (MATMAC)). This process produced an interesting morphology in which the MWNTs, consisting of bead-string shapes or MWNTs embedded in the beads, when polymer beads were sufficiently large, produced nanohybrid material. This morphology was attributed to the interaction between the cationic coupling agent and the nanotube surface which induced polymerization within the hemimicellar or hemicylindrical structures of surfactant micelles on the surface of the nanotubes. In a solution containing MATMAC alone without surfactant, carbon nanotubes (CNTs) were not well-dispersed, and in a solution containing only surfactant without MATMAC, polymeric beads were synthesized in isolation from CNTs and continued to exist separately. The incorporation of MATMAC and surfactant together enabled large amounts of CNTs (> 0.05 wt%) to be well-dispersed in water and very effectively encapsulated by polymer chains. This method could be applied to other well-dispersed CNT solutions containing amphiphilic molecules, regardless of the type (i.e., anionic, cationic or nonionic). In this way, the solubility and dispersion of nanotubes could be increased in a solvent or polymer matrix. By enhancing the interfacial adhesion, this method might also contribute to the improved dispersion of nanotubes in a polymer matrix and thus the creation of superior polymer nanocomposites.

Preparation of Monodisperse Poly(Methacrylic acid) with a Water-Soluble Initiator by Solution Polymerization in the Aqueous Phase (수용액 내에서 수용성개시제를 이용한 단분산성 폴리메타크릴산의 용액중합)

  • Moon, Jiyeon;Chung, Kyungho;Park, Moonsoo
    • Elastomers and Composites
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    • v.48 no.4
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    • pp.294-299
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    • 2013
  • Solution polymerization was conducted with water-soluble methacrylic acid (MAA) as a monomer and potassium persulfate (KPS) as an initiator at a selected temperature between $70^{\circ}C$ and $90^{\circ}C$. When the ratio between MAA and water was reduced or initiator concentration increased, molecular weights decreased. Molecular weights of poly(methacrylic acid) (PMAA) showed nearly no dependence on reaction temperature. The Weissenberg effect was observed in most polymerization reactions, while its effect weakened at $90^{\circ}C$. The polydispersity index was less than 1.5 in most of the reactions. An increase in the stirring speed produced PMAAs with increasing molecular weights. When the stirring speed reached 800 rpm, we retrieved a monodisperse PMAA with both the number and weight average molecular weights of 791,000 g/mol. The glass transition temperature was found to be $162^{\circ}C$.

Cyclopolymerization of 1,6-Heptadiyne by Molybdenum and Tungsten-Based Catalysts

  • Gal, Yeong-Soon;Lee, Won-Chul;Gui, Tae-Long;Jin, Sung-Ho;Kwangnak Koh;Kim, Sung-Hoon;Kim, Dong-Won;Ko, Jang-Myoun;Chun, Jong-Han
    • Macromolecular Research
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    • v.9 no.4
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    • pp.220-227
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    • 2001
  • The polymerization of 1,6-heptadiyne was carried out by molybdenum and tungsten-based transition metal catalysts. This polymerization by MoCl$\_$5/ alone proceeded well to give a quantitative yield of polymer. The effect of monomer to catalyst mole ratio (M/C), initial monomer concentration ([M]$\_$0/), and the polymerization temperature for the cyclopolymerization of 1,6-heptadiyne was studied and discussed. The polymerization solution exhibited red color even after 30 min of polymerization time. The resulting polymers were mostly brown powders and mostly insoluble in any organic solvents although the polymerization proceeded in homogeneous manner in some cases. The polymer structure was characterized by various instrumental methods to have the conjugated polymer backbone structure carrying cyclic recurring unit. The thermal and morphological properties of the resulting poly(1,6-heptadiyne) were also discussed.

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Reactive Extrusion of Starch-g-Polyacrylonitrile in the Preparation of Absorbent Materials

  • Yoon, Kee-Jong;Carr, M.E.;Bagley, E.B.
    • Proceedings of the Korean Fiber Society Conference
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    • 1990.06b
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    • pp.8-8
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    • 1990
  • A new method for the graft polymerization of acrylonitrile onto starch is presented. Graft polymerization of acrylonitrile onto starch and the subsequent hydrolysis in sodium hydroxide solution to prepare absorbents is well known. This process has been utilized to produce the commercial product, Super Slurper. In a typical batch process, ~5% starch in water mixture is gelatinized at $95^{\circ}C$ under stirring for 1 hour then cooled to room temperature. The graft polymerization itself is carried out for approximately 2 hours at $25~30^{\circ}C$ on the gelatinized starch by eerie ion initiation. In this study, graft polymerization of acrylonitrile onto starch via a reactive extrusion process which is a continuous, efficient process is described. Initial concentration of starch in water is 35% and the reaction temperatures are between $50~80^{\circ}C$. However, the most significant difference in the reactive extrusion process is the short time in which the graft polymerization takes place. Preliminary results on the properties of graft polymerization products obtained from the reactive extrusion process are compared to those obtained from the batch process as well as the absorbency of the hydrolyzed samples. Absorbent material has also been prepared by sequential grafting and saponification in the extruder followed by a 2 hour heat treatment of the extrudate in an air circulated oven at $100^{\circ}C$.

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Characterization of Chemically Stabilized $\beta$-cristobalite Synthesized by Solution-Polymerization Route

  • Lee, Sang-Jin
    • The Korean Journal of Ceramics
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    • v.3 no.2
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    • pp.116-123
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    • 1997
  • A chemically stabilized $\beta$-cristobalite, which is stabilized by stuffing cations of $Ca^{2+}$ and $Al^{3+}$, was prepared by a solution-polymerization route employing Pechini resin or PVA solution as a polymeric carrier. The polymeric carrier affected the crystallization temperature, morphology of calicined powder, and particle size distribution. In case of the polyvinyl alcohol (PVA) solution process, a fine $\beta$-cristobalite powder with a narrow particle size distribution (average particle size : 0.3$\mu\textrm{m}$) and a BET specific surface area of 72 $\m^2$/g was prepared by an attrition-milling for 1 h after calcination at 110$0^{\circ}C$ for 1h. Wider particle size distribution and higher specific surface area were observed for the $\beta$-cristobalite powder derived from Pechini resin. The cubie(P1-to-tetraganalb) phase transformation in polynystalline $\beta$-cristobalite was induced at approximately 18$0^{\circ}C$. Like other materials showing transformation toughening, a critical size effect controlled the $\beta$-to-$\alpha$ transformation. Densifed cristobalite sample had some cracks in its internal texture after annealing. The cracks, occurred spontaneoulsy on cooling, were observed in the sample with an average grain sizes of 4.0 $\mu\textrm{m}$ or above. In case of the sintered cristobalite having a composition of CaO.$2Al_2O_3$.40SiO$_2$, small amount of amorphous phase and slow grain growth during annealing were observed. Shear stress-induced transformation was also observed in ground specimen. Cristobalite having a composition of CaO.2Al2O3.80SiO2 showed a more sensitive response to shear stress than the CaO.$2Al_2O_3$.40SiO$_2$ type cristobalite. Shear-induced transformation resulted in an increase of volume about 13% in $\alpha$-cristobalite phase on annealing for above 10 h in the case of the former composition.

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Development of Multi-layer Pressure Sensor using PEDOT Vapor Phase Polymerization (PEDOT 기상중합 원단을 이용한 멀티 레이어 압력 센서 개발)

  • Lim, Seung Ju;Bae, Jong Hyuk;Jang, Seong Jin;Lim, Jee Young;Park, Keun Hae;Ko, Jae Hoon
    • Journal of Sensor Science and Technology
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    • v.27 no.3
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    • pp.186-191
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    • 2018
  • Smart textile industries have been precipitously developed and extended to electronic textiles and wearable devices in recent years. In particular, owing to an increasingly aging society, the elderly healthcare field has been highlighted in the smart device industries, and pressure sensors can be utilized in various elderly healthcare products such as flooring, mattress, and vital-sign measuring devices. Furthermore, elderly healthcare products need to be more lightweight and flexible. To fulfill those needs, textile-based pressure sensors is considered to be an attractive solution. In this research, to apply a textile to the second layer using a pressure sensing device, a novel type of conductive textile was fabricated using vapor phase polymerization of poly(3,4-ethylenedioxythiophene) (PEDOT). Vapor phase polymerization is suitable for preparing the conductive textile because the reaction can be controlled simply under various conditions and does not need high-temperature processing. The morphology of the obtained PEDOT-conductive textile was observed through the Field Emission Scanning Electron Microscope (FESEM). Moreover, the resistance was measured using an ohmmeter and was confirmed to be adjustable to various resistance ranges depending on the concentration of the oxidant solution and polymerization conditions. A 3-layer 81-point multi-pressure sensor was fabricated using the PEDOT-conductive textile prepared herein. A 3D-viewer program was developed to evaluate the sensitivity and multi-pressure recognition of the textile-based multi-pressure sensor. Finally, we confirmed the possibility that PEDOT-conductive textiles could be utilized by pressure sensors.