• Title/Summary/Keyword: in situ polymerization.

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Synthesis and Properties of Ionic Polyacetylene Composite from the In-situ Quaternization Polymerization of 2-Ethynylpyridine Using Iron (III) Chloride (염화 철(III)을 이용한 2-에티닐피리딘의 in-situ4차염화중합을 통한 이온형 폴리아세틸렌 복합체의 합성과 특성)

  • Taehyoung Kim;Sung-Ho Jin;Jongwook Park;Yeong-Soon Gal
    • Applied Chemistry for Engineering
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    • v.35 no.4
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    • pp.296-302
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    • 2024
  • An ionic conjugated polymer-iron (III) chloride composite was prepared via in-situ quaternization polymerization of 2-ethynylpyridine (2EP) using iron (III) chloride. Various instrumental methods revealed that the chemical structure of the resulting conjugated polymer (P2EP)-iron (III) chloride composite has the conjugated backbone system having the designed pyridinium ferric chloride complexes. The polymerization mechanism was assumed to be that the activated triple bond of 2-ethynylpyridinium salt, formed at the first reaction step, is easily susceptible to the step-wise polymerization, followed by the same propagation step that contains the propagating macroanion and monomeric 2-ethynylpyridinium salts. The electro-optical and electrochemical properties of the P2EP-FeCl3 composite were studied. In the UV-visible spectra of P2EP-FeCl3 composite, the absorption maximum values were 480 nm and 533 nm, and the PL maximum value was 598 nm. The cyclic voltammograms of the P2EP-FeCl3 composite exhibited irreversible electrochemical behavior between the oxidation and reduction peaks. The kinetics of the redox process of composites were found to be very close to a diffusion-controlled process from the plot of the oxidation current density versus the scan rate.

Study on the Oxidative Polymerization of EDOT Induced by Graphene Oxide (산화 그래핀에 의한 EDOT의 산화중합에 관한 연구)

  • Kim, Min Chae;Park, Min Ui;Park, No Il;Lee, Seul Bi;Lee, Seong Min;Yang, So Yeon;Choi, Jong Hyuk;Chung, Dae-won
    • Applied Chemistry for Engineering
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    • v.27 no.1
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    • pp.45-49
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    • 2016
  • In the presence of poly(4-styrene sulfonate) (PSS) and excess amount of graphene oxide (GO), we conducted in-situ polymerization of 3,4-ethylenedioxythiophene (EDOT) without an oxidant. XPS and IR spectroscopies of the product (GO-P) showed that PEDOT/PSS was successfully synthesized by oxidative polymerization of EDOT and hybridized with GO. GO-P displayed a stable aqueous suspension, however, the high content (42%) of GO in GO-P diminished electrical conductivity down to $15S{\cdot}m^{-1}$. Annealing of GO-P films at $200^{\circ}C$ for 8 hr induced partial reduction of GO and finally enhanced electrical conductivity up to $212S{\cdot}m^{-1}$.

Effect of Interface on the Properties of Polyamide 6/Carbon Nanotube Nanocomposites Prepared by In-situ Anionic Ring-opening Polymerization

  • Min, Jin Hong;Huh, Mongyoung;Yun, Seok Il
    • Composites Research
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    • v.32 no.6
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    • pp.375-381
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    • 2019
  • Multiwalled carbon nanotubes (MWCNTs) are covalently functionalized with isocyanates by directly reacting commercial hydroxyl functionalized MWCNTs with excess 4,4'-methylenebis (phenyl isocyanate) (MDI) and hexamethylene diiosocyanate (HDI). HDI-modified MWCNTs results in a higher surface isocyanate density than MDI-modified MWCNTs. Anionic ring-opening polymerization of ε-caprolactam is conducted using a sodium caprolactam initiator in combination with a di-functional hexamethylene-1,6-dicarbamoylcaprolactam activator in the presence of isocyanate functionalized MWCNTs. This polymerization proceeds in a highly efficient manner at relatively low reaction temperature (150℃) and short reaction times (10 min). During the polymerization, the isocyanate functionalized MWCNTs act not only as reinforcing fillers but also as second activators. Nanocomposites with HDI modified MWCNTs exhibit higher reinforcement and faster isothermal crystallization than MDI modified MWCNTs. The results show that PA6 chains grow more effectively from HDI modified MWCNT surface than from MDI modified MWCNT surface, resulting in stronger interaction between PA6 and MWCNTs.

Preparation of Honeycomb-patterned Polyaniline-MWCNT/Polystyrene Composite Film and Studies on DC Conductivity

  • Kim, Won-Jung;Huh, Do-Sung
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2345-2351
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    • 2012
  • Conductive honeycomb-patterned polystyrene (PS) thin films were prepared by the formation of a polyaniline (PANI) thin layer on the surface of the patterned PS thin films using simple one-step chemical oxidative polymerization of aniline. The in situ chemical oxidation polymerization of aniline hydrochloride solution on the patterned structure of the PS films was conducted in the presence of multiwalled carbon nanotubes (MWCNT) to prepare the PANI-MWCNT/PS composite film. The concentration (wt %) of MWCNT was varied in the range of 1%-3% by weight. The dependence of surface morphology of the PANI/PS and PANI-MWCNT/PS composite film to the polymerization time was observed by scanning electron microscopy. The room temperature DC conductivity was obtained by the four-probe technique. The conductivity of the PANI-MWCNT/PS composite film was affected both by the MWCNT concentration and polymerization time. In addition, DC electrical field was loaded during the oxidative polymerization to affect the distribution of the MWCNT included in the composite film, varying the loading voltage in the range of 0.1-3.0 V. The conductivity of the PANI-MWCNT/PS composite film was increased as loading voltage rose. However, this increase stops at a voltage higher than the critical value.

Photo-induced Living Cationic Polymerization of Isobutyl Vinyl Ether in the Presence of Various Combinations of Halides of Diphenyliodonium and Zinc Salts in Methylene Chloride

  • Kwon Soonhon;Chun Hyunjeong;Mah Soukil
    • Fibers and Polymers
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    • v.5 no.4
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    • pp.253-258
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    • 2004
  • Living nature of photoinduced cationic polymerization of isobutyl vinyl ether (IBVE) in the presence of various combinations of diphenyliodonium halide (DPIX), a photocationic initiator and zinc halide $(ZnX_2)$ in methylene chloride has been investigated. Attainment of $100\%$ conversion and a linear relationship between $\%$conversion and number average molar mass of the resulting polymer, strongly suggests the living nature of this system. Livingness of the polymerization system was observed irrespective to the type of halide anion of the initiator and zinc salts unless the reaction temperature is not higher than $-30^{\circ}C$. The rate of polymerization decreases in the order of iodide > bromide > chloride when halide salt of DPIX and $ZnX_2$ are used. It is postulated that the cationic initiation is started by the insertion of weakly basic monomer in to the activated C-X terminal of the monomer adduct which is a reaction product of monomer and HX, a photolytic product of DPIX, formed in situ during the photo-irradiation process. It was concluded that polymerization is initiated by the insertion of weakly basic monomer into activated C- X terminal of monomer adduct due to the pulling action of$ZnX_2$, which successively producing a new polarized C-X terminal for the propagation in cationic nature. This led us to a conclusion that the living nature of this cationic polymerization is ascribable to the polarized C-X growing terminal, which is stable enough to depress the processes of chain transfer or termination process.

Isospecific Propylene Polymerization Behavior of Lewis Base Functionalized Unbridged Zirconocences under Bulk Conditions

  • Yoon, Seung Woong;Kim, Hwa Kyu;Kim, Seong Kyun;Kim, Taewon;Lee, Min Hyung;Do, Youngkyu
    • Bulletin of the Korean Chemical Society
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    • v.35 no.1
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    • pp.236-242
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    • 2014
  • Isospecific propylene polymerization behavior of meta- and para-Lewis base (E) functionalized unbridged zirconocenes ($[1-(E_n-Ph)-3,4-Me_2C_5H_2]_2ZrCl_2$, E = $NMe_2$, OMe; n = 1 or 2) was investigated under bulk conditions. Catalytic activity of the zirconocenes, and molecular weight and isotacticity of polypropylenes are found to be dependent on the position and number of the Lewis base functional groups in the zirconocenes. All the crude polypropylenes possess a broad molecular weight distribution and multi-melting transitions, indicating an involvement of multi-catalytic active species in the polymerization. The highest [mmmm] value of an isotactic portion of the polypropylenes reached 89%, which is higher than that (85%) from the well-known $C_2$-symmetric EBIZr (rac-$Et(Ind)_2ZrCl_2$) catalyst. These results support that the in situ generated, rigid rac-like cation-anion pair through the Lewis acid-base interactions between the functional groups of zirconocenes and methylaluminoxane anion is effective in the formation of isotactic polypropylene under bulk propylene polymerization conditions.

Preparation of Poly(methyl methacrylate)/Na-MMT Nanocomposites via in-Situ Polymerization with Macroazoinitiator

  • Jeong Han Mo;Ahn Young Tae
    • Macromolecular Research
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    • v.13 no.2
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    • pp.102-106
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    • 2005
  • Poly(methyl methacrylate) (PMMA)/sodium montmorillonite (Na-MMT) nanocomposites were prepared with a novel method utilizing a macroazoinitiator (MAI). To induce the intergallery polymerization of methyl methacrylate (MMA), the MAI containing a po1y(ethylene glycol) (PEG) segment was intercalated between the lamellae of Na-MMT and swelled with water to enhance the diffusion of MMA into the gallery. The structure of the nanocomposite was examined using X-ray diffraction and transmission electron microscopy, and the thermal properties were examined using differential scanning calorimetry and thermogravimetry. The PMMA/Na-MMT nanocomposite prepared by intergallery polymerization showed a distinct enhancement of its thermal properties; an approximately $30^{\circ}C$ increase in its glass transition temperature and an $80\sim100^{\circ}C$ increase in its thermal decomposition temperature for a $10\%$ weight loss.

Preparation of Ag/PVP Nanocomposites as a Solid Precursor for Silver Nanocolloids Solution

  • Hong, Hyun-Ki;Park, Chan-Kyo;Gong, Myoung-Seon
    • Bulletin of the Korean Chemical Society
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    • v.31 no.5
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    • pp.1252-1256
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    • 2010
  • A polyvinylpyrrolidone (PVP)/Ag nanocomposites was prepared by the simultaneous thermal reduction and radical polymerization route. The in situ synthesis of the Ag/PVP nanocomposites is based on the finding that the silver n-propylcarbamate (Ag-PCB) complex can be directly dissolved in the NVP monomer, and decomposed by only heat treatment in the range of 110 to $130^{\circ}C$ to form silver metal. Silver nanoparticles with a narrow size distribution (5 - 40 nm) were obtained, which were well dispersed in the PVP matrix. A successful synthesis of Ag/PVP nanocomposites then proceeded upon heat treatment as low as $110^{\circ}C$. Moreover, important advantages of the in situ synthesis of Ag/PVP composites include that no additives (e.g. solvent, surface-active agent, or reductant of metallic ions) are used, and that the stable silver nanocolloid solution can be directly prepared in high concentration simply by dissolving the Ag/PVP nanocomposites in water or organic solvent.

Synthesis and characterization of polybenzoxazole/graphene oxide composites via in situ polymerization

  • Lim, Jun;Kim, Min-Cheol;Goh, Munju;Yeo, Hyeounk;Shin, Dong Geun;Ku, Bon-Cheol;You, Nam-Ho
    • Carbon letters
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    • v.14 no.4
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    • pp.251-254
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    • 2013
  • In this study, poly(amic acid) was prepared via a polycondensation reaction of 3,3'-dihydroxybenzidine and pyromellitic dianhydride in an N-methyl-2-pyrrolidone solution; reduced graphene oxide/polybenzoxazole (r-GO/PBO) composite films, which significantly increased the electrical conductivity, were successfully fabricated. GO was prepared from graphite using Brodie's method. The GO was used as nanofillers for the preparation of r-GO/PBO composites through an in situ polymerization. The addition of 50 wt% GO led to a significant increase in the electrical conductivity of the composite films by more than sixteen orders of magnitude compared with that of pure PBO films as a result of the electrical percolation networks in the r-GO during the thermal treatment at various temperatures within the films.