• Title/Summary/Keyword: Free radical polymerization

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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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Synthesis and Performance Evaluation of Linear Polycarboxylate Dispersant of Glacial Acrylic Acid - Maleic Acid- Sodium Methallyl Disulfonate for Ceramics

  • Kommanapalli, Kiran Kumar;Lyot, Pierre;Sunkara, Jhansi Rani;Checule, Pierrick
    • Journal of the Korean Ceramic Society
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    • v.55 no.2
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    • pp.126-134
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    • 2018
  • Using aqueous solution free radical polymerization with glacial acrylic acid (GAA), maleic anhydride (MA) and sodium methallyl disulfonate (SMADS), a novel linear polycarboxylate dispersant was synthesized for ceramics. Dispersant linear structural characterization was done by FTIR, $^1H$ NMR, HPLC and GPC, and the ratio of monomers was determined using an orthogonal experiment. This research is focused on the effects of polymerization temperature, monomer mole ratios and dosage of initiator on ceramic slurry viscosity with linear polycarboxylate dispersant for ceramic dosage rate of 0.30% (based on dry slurry), all of which were investigated by single factor test. The best polymerization conditions for linear GAA-MA-SMADS are when n(AA) : n(MA) : n(SMADS) equals 3.0 : 1.0 : 0.5, the molecular weight of the polymer is 4600 daltons, the initiator sodium persulfate accounts for 7% of the total mass of polymerized monomers, the polymerization temperature is $90^{\circ}C$ and the reaction time is 2 h. The ceramic body slurry viscosity drops from $820mPa{\cdot}s$ to $46mPa{\cdot}s$ when the concentration of the polycarboxylate dispersant is 0.30%.

Preparation and Application of Polysilane Derivatives (Polysilane 유도체의 합성과 그 응용)

  • Kang, Doo-Whan
    • Applied Chemistry for Engineering
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    • v.1 no.1
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    • pp.1-10
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    • 1990
  • Polysilane derivatives are attracting considerable attention as a new class of material since 1980. The preparation methods of low molecular weight, cyclic, and high molecular weight polysilane derivatives are described, and also photochemistry characteristics for silicon-silicon single bond and for the nature of the substituent on silicon backbone are discussed. Polysilanes may be used as a precursors to silicon carbide fiber, as photoresist in microelectronics, as photoconductor, and as photoinitatior for free radical polymerization.

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Synthesis of Highly Crosslinked Temperature-resistant Poly(vinyl ethers) by Free Radical Polymerization

  • 이주연;김지향
    • Bulletin of the Korean Chemical Society
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    • v.19 no.8
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    • pp.851-856
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    • 1998
  • 2,4-Di-(2-vinyloxyethoxy)benzylidenemalononitrile (2a), methyl 2,4-di-(2-vinyloxyethoxy)benzylidenecyanoacetate (2b), 3,4-di-(2-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl 3,4-di-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b), 2,5-di-(2-vinyloxyethoxy)benzylidenemalononitrile (6a), and methyl 2,5-di-(2-vinyloxyethoxy)benzylidenecyanoacetate (6b) were prepared by the condensation of 2,4-di-(2-vinyloxyethoxy)benzaldehyde (1), 3,4-di-(2-vinyloxyethoxy)benzaldehyde (3), and 2,5-di-(2-vinyloxyethoxy)benzaldehyde (5) with malononitrile or methyl cyanoacetate, respectively. Trifunctional divinyl ether monomers 2, 4 and 6 were polymerized readily by free radical initiators to give optically transparent swelling poly(vinyl ethers) 7-9. Polymers 7-9 were not soluble in common organic solvents such as acetone and DMSO due to crosslinking. Polymer 7-9 showed a thermal stability up to 300 ℃ in TGA thennograms.

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 $300^{\circ}C$.

Synthesis and Thermal Property of Poly(styrene-g-caprolactone) with Well-defined Structure (분자구조가 제어된 Poly(styrene-g-caprolactone)의 합성 및 그라프트 공중합체의 열적 성질)

  • 오병석;안성국;조창기
    • Polymer(Korea)
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    • v.24 no.3
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    • pp.306-313
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    • 2000
  • Polycaprolactone (PCL) macromer containing terminal methacrylate group was synthesized by ring-opening polymerization. The number average molecular weight of PCL macromer was 11600 g/mole and polydispersity index was 1.09. The synthesized PCL macromer was copolymerized with styrene by stable free radical polymerization using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), benzoyl peroxide, and well-defined poly(styrene-g-caprolactone)s were synthesized. The synthesized copolymers was characterized by $^1$H-NMR and gel permeation chromatography equipped with multiangle laser light scattering detector. Thermal properties of graft copolymers were investigated by DSC.

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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 ℃.

Morphology of the Conducting Poly-N-vinylcarbazole-coated Silica Gel Nanocomposites

  • Basavaraja, C.;Kim, Na-Ri;Jo, Eun-Ae;Revanasiddappa, M.;Huh, Do-Sung
    • Bulletin of the Korean Chemical Society
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    • v.31 no.2
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    • pp.298-302
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    • 2010
  • We report the effect of surface morphology on the conductivity of the poly-N-vinylcarbazole (PVK)/silica gel ($SiO_2$) nanocomposites as a function of $SiO_2$ weight percentage (%).The polymerization of PVK was initiated by a free-radical polymerization. The surface morphology of the prepared composite shows the incorporation of $SiO_2$ in the prepared PVK-$SiO_2$ (PS) nanocomposites. The conductivity increased from $9.2{\times}10^{-5}S\;cm^{-1}$ to $9.6{\times}10^{-4}S\;cm^{-1}$ with the increase in the percentage of silica gel from 5 to 30%. The nanocomposites show a percolation behavior having a threshold value between 15 and 20%.

Synthesis of Star like Random Copolymers from Resorcinarene-based Alkoxyamine Initiator via Nitroxide Mediated Free Radical Polymerization

  • Abraham, Sinoj;Choi, Jae-Ho;Ha, Chang-Sik;Kim, Il
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.337-337
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    • 2006
  • The synthesis of an octafunctional resorcinarene based initiator for nitroxide mediated polymerization and its ability to yield random star copolymers of styrene and methyl methacrylate is studied. The effect of the initiator conformations towards its activity and the conditions that permit the formation of well-defined star block copolymers is also investigated in detail. The characterization of the initiator and the polymers were carried out by various spectro-analytical techniques. Well-defined random copolymers were obtained with controlled molecular weight and low PDI depending on the monomer feed.

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Strategy for molecular weight distribution control in a batch polymerization reactor system (회분식 중합 반응기에서의 분자량 분포제어 전략)

  • 김인선;유기윤;이현구
    • 제어로봇시스템학회:학술대회논문집
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    • 1993.10a
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    • pp.766-771
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    • 1993
  • A mathematical model is developed to represent the batch reactor for free radical polymerization of PMMA The model is validated by comparing the simulation result with the experimental data. A computational scheme is proposed to determine the trajectory of the reactor temperature that will produce polymer product having the desired molecular weight distribution. For this instantaneous number average chain length and polydispersity are introduced to calculate the reactor temperature. The former is assumed to be a second order polynomial of the sum of the living and dead polymer concentrations. Various reactor temperature, trajectories are observed depending on the reactor conditions and prescribed molecular weight distributions. Fuzzy and PID control algorithms are applied to trace the reactor temperature trajectory. While the PID control gives rise to an overshoot when the trajectory changes its direction, the fuzzy controller yields a more satisfactory performance because it secures information on the trajectory pattern.

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