• Title/Summary/Keyword: radical condensation

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Radical Ring-Crossover Polymerization of Macrocycles with Radically Exchangeable Dynamic Covalent Bonds

  • Otsuka, Hideyuki;Yamaguchi, Go;Takahara, Atsushi
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.320-320
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    • 2006
  • The authors report the synthesis and radical ring-crossover polymerization of macrocycles with radically exchangeable dynamic covalent bonds. The macrocyclic compounds with alkoxyamine units were designed and synthesized by condensation from alkoxyamine-based diol and the corresponding acid chlorides in the presence of pyridine under high-dilution condition. The macrocycles can thermally polymerize by intermolecular radical crossover reaction. Furthermore, the poly(alkoxyamine)s depolymerized to the monomers principally by the intramolecular radical exchange process under high-dilution conditions.

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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 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.

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 ℃.

Inhibitory Effects of Epigallocatechin Gallate on Apoptosis in Human Vascular Endothelial Cells (혈관내피세포의 세포사멸작용에 대한 (-)Epigallocatechin Gallate의 억제효과)

  • Choi, Yean-Jung;Choi, Jung-Suk;Lee, Se-Hee;Lee, Yong-Jin;Kang, Jung-Sook;Kang, Young-Hee
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.31 no.4
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    • pp.672-678
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    • 2002
  • Oxidative stress contributes to cellular injury following clinical and experimental ischemia/reperfusion scenarios. Oxidative injury can induce cellular and nuclear damages that result in apoptotic cell death. We tested the hypothesis that the catechin flavonoid of (-)epigallocatechin gallate, a green tea polyphenol, inhibits hydrogen peroxide ($H_2O$$_2$)-induced apoptosis in human umbilical vein endothelial cells. The effect of apigenin, a flavone found in citrus fruits, on apoptosis parameters was also examined. A 30 min pulse treatment with 0.25 mM $H_2O$$_2$ decreased endothelial cell viability within 24 hrs by > 30% ; this was associated with nuclear condensation and biochemical DNA damage consistent with programmed cell death. In the 0.25 mM $H_2O$$_2$apoptosis model, 50${\mu}{\textrm}{m}$ (-)epigallocatechin gallate markedly increased cell viability with a reduction in the nuclear condensation and DNA fragmentation. In contrast, equimicromolar apigenin increased cell loss with intense DNA laddering, positive nick-end labeling and Hoechst 33258 staining. Thus, polyphenolic (-)epigallocatechin gallate, but not apigenin flavone, qualify as an antioxidant in apoptosis models caused by oxidative stress. Further work is necessary for elucidating the anti-apoptotic mechanisms of polyphenolic catechins.

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 ℃.

The $SO_2$ effect on NOx removal by Corona Shower System (코로나 샤워 시스템을 이용한 NOx제거에서 $SO_2$의 영향)

  • Park, Jae-Yoon;Kim, Ick-Kewn;Lee, Jae-Dong;Kim, Jong-Dal;Lee, Duck-Chool;Chang, J.S.
    • Proceedings of the KIEE Conference
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    • 1998.07e
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    • pp.1794-1796
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    • 1998
  • In this study, the $SO_2$ addition effect on NOx removal has been conducted from a combustion flue gases by the do corona discharge-activated radical shower systems. The simulated flue gases were consisted of NO-O_2-$N_2$, NO-$CO_2-N_2-O_2$ and $NO-SO_2-CO_2-Na-O_2$([NO]o:200ppm and $[SO_2]o$:800ppm). The injection gases used as radical source gases were $NH_3$-Ar-air. $SO_2$ and NOx removal efficiency and the other by-products were measured by Fourier Transform Infrared(FTIR) as well as $SO_2$. NOx and $NO_2$ gas detectors. By-product aerosol particles were also observed by Condensation Nucleation Particle Counter(CNPC) and SEM images after sampling. The results showed that asignificant aerosol Particle formation was observed during a removal operation in corona radical shower systems. The NOx removal efficiency significantly increased with increasing applied voltage and $NH_3$ molecule ratio. The $SO_2$ removal efficiency was not significantly effected by applied voltage and slightly increased with increasing $NH_3$ molecule ratio. The NOx removal efficiency for NO-$SO_2-CO_2-N_2-O_2$ was better than that for NO-$CO_2-N_2-O_2$.

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Variable surface coatings composed of organic-inorganic hybrid polymers

  • Kessler, Daniel;Bahnmuller, Stefan;Theato, Patrick
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.315-315
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    • 2006
  • A variable surface coating with the potential to fulfill the requirements of industry will be presented. Via controlled radical polymerization methods from a functionalized Polymethylsilsesquioxane delivers an inorganic-organic block copolymer, which can be easily modified and tuned for different applications. Spin coated or dip coated on various substrates show promising results. By using different block copolymers the contact angle on a silicon wafer can be varied in a range of $90^{\circ}\;up\;to\;145^{\circ}$ After curing and complete condensation a perfect adhesion on glasses, plastics and metals is achieved.

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Preparation of isotropic pitch precursor for pitch-based carbon fiber through the co-carbonization of ethylene bottom oil and polyvinyl chloride

  • Liu, Jinchang;Shimanoe, Hiroki;Nakabayashi, Koji;Miyawaki, Jin;Ko, Seunghyun;Jeon, Young-Pyo;Yoon, Seong-Ho
    • Journal of Industrial and Engineering Chemistry
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    • v.67
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    • pp.276-283
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    • 2018
  • For the first time, polyvinyl chloride (PVC) was used as an easily-handled chlorine source for preparation of isotropic pitch-based carbon fiber (IPCF) incorporating ethylene bottom oil (EO) as a raw material. Pitch precursors were prepared by the chlorination-dehydrochlorination triggered by chlorine radicals originated from PVC; aromatization and poly-condensation reactions occurred by polyene-type radicals from PVC. Radical production and co-carbonization were facilitated by pretreatments of EO through vacuum distillation, bromination, and additional heat treatment. Pitches were prepared by the co-carbonization of pretreated EO and EO containing 20 wt% PVC, and had higher yields and better spinnability than those by simple distillation.

Cytotoxic Effect of Free Radical on Rat Primary Astrocytes (자유라디칼이 백서의 뇌별아교세포에 미치는 독성작용)

  • Jang, Hyuk;Kim, Myung-Sunny;Park, Hyun-Young;Kim, Yo-Sik;Cho, Kwang-Ho;Chung, Hun-Taeg;Park, Rae-Kil
    • Toxicological Research
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    • v.16 no.1
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    • pp.1-8
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    • 2000
  • Astrocytes generate free radicals including nitric oxide (NO) and reactive oxygen intermediates(ROI) which in turn play roles in the pathogenesis of degenerative diseases and sclerotic changes of the brain. This study was designed to evaluate the mechanism that free radicals contribute to the cytotoxicty of rat neonatal primary astrocytes. Treatment with NO donors alone including soldium nitroprusside(SNP), S-nitrosoglucathinoe (GSNO), and S-nitroso-n-acetylpenicillamine (SNAP) showed a little effect on the death of rat neonatal primary astrocytes, whereas SNP markedly induced the death of RAW 264.7 cells. ROI inculding H2O2 and O2 donor also slightly induced the death of rat primary astrocytes. However, 3-morpholinosydnonimine(SIN-1), a donor of peroxynitrite (ONOO), which is a reactive compound of NO with superoxide, significantly decreased the viability of rat primary astrocytes in a dose-dependent manner. Cells were retarded in outgrowth of viability of cellular processes with cell shrinkage and detachment from culture dishes. Hoechst staining demonstrated that SIN-1-induced cell death might be due to an apoptosis which was characterized by nuclear condensation and fragmentation. SIN-1-induced apoptosis was prevented by the pretreatment with superoxide dismutase (SOD) and catalase in rat primary astorocytes. Furthermore, prevention of the generation of reduced glutathione (GSH) by DL-buthionine-[S, R]-sulfoximine (BSO) aggravated the cytotoxic effects of SNP, benzene triol, and SIN-1 in rat primary astrocytes. Taken together, it is suggested that peroxynitrite may be a major effector of apoptosis and cellular antioxidant system is important for cell survival in rat prima교 astrocytes.

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