• Title/Summary/Keyword: equilibrium polymerization

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Electrical Properties of Silicone Rubber Filled with Surface Treated Alumina Trihydrate

  • Jung, Se-Young;Kim, Byung-Kyu
    • Transactions on Electrical and Electronic Materials
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    • v.7 no.3
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    • pp.134-140
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    • 2006
  • The effect of surface treatment of fillers on the mechanical, electrical properties, and tracking performance of silicone rubber insulators have been investigated. For base polymer, $\alpha,\;\omega$) vinyl poly(dimethyl-methylphenyl) siloxane(VPMPS) containing dimethyl siloxane and methylphenyl siloxane was prepared by the equilibrium polymerization. High voltage silicone rubber composites(HVSRC) were prepared from VPMPS, nano-silica, and alumina trihydrate (ATH) modified by various coupling agents. Bound rubber of uncured silicone rubber, cross-linking density of the vulcanizate as well as the mechanical, electrical properties, and tracking performance were measured.

Studies on Polymerization of Metal Anion (III). The Temperature Effect on Polymolybdate Ions Equilibrium in 1 M $NaCIO_4$ Solution (Metal Anion Polymerization에 관한 연구 (제3보). The Temperature Effect on Polymolybdate Ions Equilibrium in 1 M $NaClO_4$Solution)

  • Sang Woon Ahn;Eui Suh Park
    • Journal of the Korean Chemical Society
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    • v.17 no.3
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    • pp.145-153
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    • 1973
  • The temperature effects on the equilibria between polymolybdatd anions in 1M sodium perchlorate solution has been investigated in the temperature range of 20~50$^{\circ}$C. The polymolybdate anions formed are heptamolybdate ($Mo_7O_{24}^{6-}$) ions and the protonized forms of heptamolybdate ions ($H_LMo_7O_{24}^{(6-L)-}$). The equilibrium constants for the formation of heptamolybdate ions calculated by Sillen's method are as follow;$8H^{+}+7MoO_4^{2-}=Mo_7O_{24}^{6-}+4H_2O$, $k_{7.8}=2.77{\times}10^{53}:20^{\circ}C= 9.29{\times}10^{51}:40^{\circ}C$,$k_{7.8}= 4.22{\times}10^{52}:30^{\circ}C = 9.29{\times}10^{51}:50^{\circ}C$ The enthalpy change for calculated for the above reaction is 31.51 kcal/mole. A method of calculation of the equilibrium constants for the formation of protonized heptamolybdate ions from heptamolybdate ions and hydrogen ions has been derived. The equilibrium constants calculated for the formation of protonized heptamolybdate ions are as follow; $ LH^++ Mo_7O_{24}^{-6} = H_LMo_7O_{24}^{(6-L)-} : L = 1\;or\;2$, $k_1 = 2.31{\times}10^4=2.53{\times}10^4=2.76{\times}10^4= 3.10{\times}10^4$, $k_2 = 6.19{\times}10^7\;20^{\circ}C = 7.80{\times}10^7\;30^{\circ}C = 1.22{\times}10^8\;40^{\circ}C = 2.03{\times}10^8\;50^{\circ}C$The enthalpy change for the following step reactions are as follow;$H^{+}+Mo_7O_{24}^{6-}= HMo_7O_{24}^{5-}\;{\Delta}H^{\circ}=1.90 kcal/mole$, $2H^{+}+Mo_7O_{24}^{6-}=H_2Mo_7O_{24}^{4-}\;{\Delta}H^{\circ}=7.50kcal/mole$

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Preparation and Characteristics of Liquid Silicone Rubber Using Polyorganosiloxane Modified with Dimethylacrylamide (디메틸아크릴아마이드 변성 폴리오가노실록산을 이용한 액상 실리콘 고무의 제조와 그 특성)

  • 강두환;이병철
    • Polymer(Korea)
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    • v.28 no.2
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    • pp.143-148
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    • 2004
  • ${\alpha}$,$\omega$-Hydrogen polyorganosiloxane(HPMDMS) prepolymer was prepared from equilibrium polymerization ofoctamethylcyclotetrasiloxane, 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethyl-cyclotetrasiloxane, and 1,1,3,3-tetramethyl disiloxane as an end-blocker in the presence of tetramethylammonium siloxanolate as a catalyst. Polyorganosiloxane modified with dimethylacrylamide(APMDMS) was prepared by hydrosilylation of HPMDMS with dimethylacrylamide in the presence of Pt catalyst, and followed by coordination of metal oxide (APMDMS-MO), such as NiO and FeO, to the amide moieties of the resulting polymer. The chemical structures of HPMDMS and APMDMS were confirmed by FT-IR and $^1$H-NMR analysis. Liquid silicone rubber containing metal oxide composite (LSRMO) was prepared by compounding APMDMS-MO, ${\alpha}$,$\omega$-vinylpolydimethylsiloxane, and a catalyst in a high speed dissolver. The thermal conductivity of LSRMO composite was determined to be 0.29 W/mK, and the volume resistivity exhibited a lower value than that of LSR composite. The mechanical and thermal properties of LSRMO and LSR composite were measured by UTM and TGA.

Copolymerization of N-Vinylurea and Vinyl Acetate (Ⅱ). Solvent Effects in Radical Copolymerization (N-비닐尿素와 醋酸비닐의 混成重合 (第2報). 라디칼混成重合에서의 溶媒效果)

  • Woo Sik Kim;Hak-ki Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.80-85
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    • 1980
  • The free radical copolymeriaztion of N-vinylurea(VU) with vinyl acetate (VAc) was carried out at $60^{\circ}C$ in three solvents. VU-vinyl alcohol(VA) copolymers were prepared by the methanolysis of the VU-VAc copolymers. From the nitrogen content measurements of VU-VA copolymers, the monomer reactivity ratios for the VU-VAc copolymerization and the values of Alfrey-Price's Q and e for VU were determined. These Q and $\varrho$ values obtained in the cases of using methanol and methanol-dioxane as the polymerization solvents are comparable with those found for other monomers which have > NCO-pendent groups. The $\varrho$ value indicates that the urea group of VU is a electron-donating group. The copolymerization parameter of VU shows a strong effect of the solvents. These results are interpreted to be that VU is in equilibrium with its tautomer at the polymerization temperature.

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Theoretical Studies on the Cationic Polymerization Mechanism of Oxetanes(II) ($BF_3$촉매하의 옥세탄 공중합에 관한 분자 궤도론적 연구)

  • Park, Jeong Hwan;Cho, Sung Dong;Park, Seong Kyu;Cheun, Young Gu
    • Journal of the Korean Chemical Society
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    • v.40 no.1
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    • pp.11-19
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    • 1996
  • The cationic polymerization of energetic substituted oxetanes which have pendant energetic group such as azido and nitrato are investigated theoretically, using semiempirical HF/3-21G, MINDO/3, MNDO and AM1 method. The stereo- and electronic structure of binary molecular complex composed of energetic substituted oxetane and boron trifluoride can be explain by molecular orbital theory. The reactivity of propagation in the copolymerization of oxetanes can be presented by the positive charge on carbon(C2) atom of oxetane and energy level of the lowest unoccupied molecular orbital(LUMO) of propagating species of oxetanes. The reactivity ratios for copolymerization of oxetanes are a random copolymer-zation which is agree with MO calculated and experimental results. The relative equlibrium concentration of cyclic oxonium and open carbenium ions is found to be a major determinant of mechanism, owing to the rapid equilibrium of these cation forms and the expectation based on calculation that in the prepolymer propagation step, SN1 mechanism will be at least as fast as that for SN2 mechanism.

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Theoretical Studies on the Cationic Polymerization Mechanism of Oxiranes (산촉매하의 옥시란 공중합에 관한 분자궤도론적 연구)

  • Young-Gu Cheun
    • Journal of the Korean Chemical Society
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    • v.35 no.5
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    • pp.461-468
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    • 1991
  • The cationic polymerizations of substituted oxiranes which have pendant energetic groups such as azido, and nitrato, are investigated theoretically using the semiempirical MNDO, and $AM_1$ methods. The nucleophilicity and basicity of substituted oxiranes can be explained by the negative charge on oxygen atom of oxiranes. The reactivity of propagation in the polymerization of oxiranes can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxiranes. Ring opening of the complexed cyclic oxonium ion to the open chain carbenium ion is expected computational stability of the oxonium and carbenium ion by 30∼40 kcal/mol favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium and open carbenium ions will be a major determinant of mechanism. The chain growth $SN_1$, mechanism will be at least as fast as that for $SN_2$ mechanism.

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Synthesis of Surface Crosslinked Poly(sodium acrylate) for Delayed Absorption in Cement Solution (시멘트 수용액에서 흡수 지연을 위한 Crosslinked Poly(sodium acrylate)의 표면 가교)

  • Hwang, Ki-Seob;Jang, Seok-Soo;Jung, Yong-Wook;Lee, Seung-Han;Ha, Ki-Ryong
    • Polymer(Korea)
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    • v.35 no.4
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    • pp.363-369
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    • 2011
  • To study the effect of incorporation of a surface crosslinking layer on a crosslinked poly (sodium acrylate) (cPSA) absorbent with ethylene glycol dimethacrylate CEGDMA), we synthesized several surface crosslinked cPSAs with EGDMA by an inverse emulsion polymerization method to delay the absorption of excess water in concrete, Liquid paraffin was used as a continuous phase. cPSA was synthesized with acrylic acid (AA) neutralized with aqueous 8 M sodium hydroxide solution as a monomer, N,N-methylene bisacrylamide (MBA) as crosslinking agent and ammonium persulfate (APS) and sodium metabisulfite (SMBS) as a redox initiator system by inverse emulsion polymerization. FTIR spectroscopy was used to characterize $Ca^{2+}$ ion interaction with cPSA and cPSA-EGDMAs. The swelling ratios of synthesized absorbents were evaluated from the absorption in deionized water, cement saturated aqueous solution and aqueous solution of calcium hydroxide (pH 12). Equilibrium swelling times for cPSA and surface crosslinked cPSA with EGDMA were 2 and 3 hrs, respectively. We also observed an increase in setting time of the cement and an increase in the compressive strength of mortar by addition of the synthesized cPSA-EGDMA.

Preparation and Swelling Properties of Poly(potassium acrylate-co-acrylamide) Superabsorbent Particles (폴리(아크릴산 포타슘-co-아크릴아마이드) 고흡수성 입자의 제조 및 팽윤 특성)

  • 손오건;심상준;이동현;이영관;김지홍;김덕준
    • Polymer(Korea)
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    • v.28 no.1
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    • pp.18-23
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    • 2004
  • Superabsorbent poly(potassium acrylate-co-acrylamide)s were synthesized in particle form using inverse suspension polymerization technique. Mean diameter of the prepared polymer particles decreased from 300 to 50 $\mu\textrm{m}$ with increasing surfactant concentration. The dynamic and equilibrium swelling behaviors during water absorption and drying process were investigated by weight measurement. The swelling ratio of polymer particles in water changed according to not only polymer crosslinking density, but particle size, saline concentration of aqueous medium, and copolymer compositions. Water sorption amount was increased with decreasing particle size, crosslinking agent concentration, and ion concentration in bulk solution. Being different from the water sorption process, the drying process was not significantly affected by particle size, polymer composition, or crosslinking amount.

Drug Release Control of Poloxamer-Poly(acrylic acid) Interpenetrating Polymer Networks (폴록사머-폴리아크릴산 IPNs의 약물 조절 방출)

  • Byun, Eun-Jung;Park, Joo-Ae;Lee, Seung-Jin;Kim, Kil-Soo
    • YAKHAK HOEJI
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    • v.41 no.1
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    • pp.22-29
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    • 1997
  • Poloxamer-poly (acrylic acid) (PAA) interpenetrating polymer networks (IPNs) were prepared via matrix polymerization of acrylic acid with poloxamer prepolymer. The equilibrium s welling of poloxamer/PAA IPNs was determined in various pH medium. The swelling of poloxamer/PAA IPNs was more affected by pH difference compared with the swelling of homo PAA gel due to protonation and deprotonation of the PAA network, followed by reversible formation and dissociation of the interpolymer complex due to hydrogen bonding between acidic hydrogens and ether oxygens. Nonionic/anionic/cationic drugs were incorporated into IPN matriceds as a model drug and their release behavior was studied. Nonionic, drug revealed release patterns depending solely on pH dependent swelling kinetics. In contrast, the release of ionic drugs was significantly affected by ionic drug-polymer interaction as well as the swelling kinetics.

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Stimuli-Sensitive Poly(NIPA-co-APA) Hydrogels for the Controlled Release of Keterolac Tromethamine

  • Kim, Yonghyun;Babu, V. Ramesh;Rao, K.S.V. Krishna;Lim, Jae-Min;Thangadurai, T. Daniel;Lee, Yong-Ill
    • Journal of the Korean Chemical Society
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    • v.58 no.1
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    • pp.92-99
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    • 2014
  • The pH sensitive hydrogels composed of N-isopropylacrylamide (NIPA) and acryloyl phenylalanine (APA) were prepared by redox polymerization using N,N'-methylenebisacrylamide (MBA) as a crosslinker. Anti-inflammatory and analgesic agent, Keterolac Tromethamine (KT), was loaded successfully into poly(NIPA-co-APA) copolymeric hydrogels by swelling equilibrium method. To understand the nature of drug in the polymeric matrix, the newly synthesized drug loaded poly(NIPA-co-APA) copolymeric hydrogels were characterized by using differential scanning calorimetry (DSC) and X-ray diffraction (XRD) techniques. The scanning electron microscopy (SEM) technique result indicates the spherical smooth surface of the hydrogels. The drug (KT) releasing nature of the poly(NIPA-co-APA) hydrogels was studied in pH 1.2 and 7.4. Effects of drug loading, crosslinking agent, pH and the ionic strength of the external medium on swelling of hydrogels were also investigated.