• Title/Summary/Keyword: Cationic Polymerization

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Synthesis and Characterization of Water Repellent Materials Containing 2-(Perfluorooctyl) Ethyl Acrylate and m-Isopropenyl-α, α-Dimethylbenzyl Isocyanate (2-(Perfluorooctyl) Ethyl Acrylate (PFOEA) 및 m-Isopropenyl-α, α-Dimethylbenzyl Isocyanate (TMI)가 함유된 발수체 합성 및 특성연구)

  • Kang, Young Taec;Kwak, Eun Mi;Chung, Ildoo
    • Journal of Adhesion and Interface
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    • v.15 no.4
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    • pp.151-160
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    • 2014
  • A series of terpolymers based on stearyl methacrylate (SMA), n-methyol acrylamide (n-MAM), and 2-(perfluorooctyl) ethyl acrylate (PFOEA) were synthesized by changing PFOEA contents up to 8 wt% in order to obtain optimal water-repellent properties. In addition, various contents of m-isopropenyl-${\alpha}$,${\alpha}^{\prime}$-dimethylbenzyl isocyanate (TMI) from 1 to 4 wt% were added to the above terpolymers with 4 wt% of PFOEA content. The emulsion polymerization was carried out using tridecyl alcohol (EO)7 (TDA-7) as a nonionic surfactant, alkyl dimethyl amine derivatives (ADAD) as a cationic surfactant, and 2,2'-azobis(2-amidinopropane dihydrochoride) (AAPDL) as an initiator. The synthesized copolymers were characterized by FT-IR spectroscopies, contact angle, surface energy, and water-repellency. Surface and thermal properties were analyzed by SEM, TGA, and DSC. It was found that water repellency increased with increasing the contents of PFOEA and TMI.

Synthesis of Mid-range Vinylidene Content Polyisobutylene by Using BF3/Alcohol Catalyst (삼불화붕소 착물촉매를 사용한 중반응성 폴리부텐의 합성)

  • Park, Min-Sup;Kim, Yeong-Joon
    • Applied Chemistry for Engineering
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    • v.29 no.3
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    • pp.307-311
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    • 2018
  • Mid-range vinylidene content polyisobutylenes were prepared by using a Lewis acid catalyst. The best results were obtained when a complex catalyst composed of n-propanol as a cocatalyst and $BF_3$ as a main catalyst was used at the reaction temperature of -8 to $5^{\circ}C$ under a pressure of $2.5kg/cm^2$. The number average molecular weight ($M_n$) and viscosity of the polyisobutylenes were 500~1,000 g/mol and 20~210 cSt (at $100^{\circ}C$), respectively. The vinylidene content was 40~70% and easily varied by adjusting the reaction temperature.

Synthesis and Characterization of Biocompatible Block Copoly (L-Lactde-$\gamma$-Benzyl-L-Glutamate) (생체적합성 공중합체의 합성과 물성에 관한 연구 -Block Copoly (L-Lactde-$\gamma$-Benzyl-L-Glutamate)-)

  • Sung, Yong-Kiel;Kim, Hoon;Song, Dae-Kyung;Kim, Young-Soon;Paek, U-Hyun
    • Journal of Biomedical Engineering Research
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    • v.9 no.2
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    • pp.215-224
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    • 1988
  • Block copoly(L-lactide-${\gamma}$-benzyl-L-glutamate)was synthesized from L-lactide by cationic ring opening polymerization and ${\gamma}$-benzyl-L-glutamate N-carboxy anhydride by introducing amino group terminated poly(L-lactide). L-lactide was polymerized in the presence of stannous octate at $110^{\circ}C$ and ${\gamma}$-benzyl- L-glutamate was polymerized in the presence of NaH at room temperature. The synthesized monomers and copolymers were identified by IR and NMR. The Itermal properties of the copolymers were characterized by differential scanning calorimetry and thermogravimetry. The thermal stability and melting temperature(Tm) of the block copolymers were measured and discussed. The activation energies of thermal decomposition for the block copoly(L-lactide-${\gamma}$ benzyl-L-glutamate) were evaluated from the thermogravimetric data by Freeman and Carroll method.

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Synthesis of the Polysaccharide, (1 $\longrightarrow$ 5)-$\alpha$-D-Ribofuranan and Its Catalytic Activities for the Hydrolysis of Phosphates and the Cleavage of Nucleic Acids

  • Han, Man-Jung;Yoo, Kyung-Soo;Kim, Young-Heui;Kim, Hong-Youb;Shin, Hyun-Joon;Chang, Ji-Young
    • Macromolecular Research
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    • v.12 no.4
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    • pp.359-366
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    • 2004
  • The polysaccharide, (1\longrightarrow5)-$\alpha$-D-ribofuranan, was synthesized by a cationic ring-opening polymerization of 1,4-anhydro-2,3-di-O-benzyl-$\alpha$-D-ribopyranose with the aid of boron trifluoride etherate and subsequent debenzylation. This polysaccharide catalyzed the hydrolysis of ethyl p-nitrophenyl phosphate, uridylyl(3'\longrightarrow5')uridine ammonium salt, and 4-tert-butylcatechol cyclic phosphate N-methyl pyridinium. The polymer also catalyzed the cleavage of nucleic acids (DNA and RNA). The hydrolysis of ethyl p-nitrophenyl phosphate in the presence of the polymer was accelerated by 1.5 ${\times}$ 10$^3$ times relative to the uncatalyzed reaction. The catalytic activity was attributable to the vic-cis-diols of the riboses being located inside the active center that is formed by polymer chain folding; these diols form hydrogen bonds with two phosphoryl oxygen atoms of the phosphates so as to activate the phosphorus atoms to be attacked by nucleophile ($H_2O$).

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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Disposable Solid-State pH Sensor Using Nanoporous Platinum and Copolyelectrolytic Junction

  • Noh, Jong-Min;Park, Se-Jin;Kim, Hee-Chan;Chung, Taek-Dong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.11
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    • pp.3128-3132
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    • 2010
  • A disposable solid-state pH sensor was realized by utilizing two nanoporous Pt (npPt) electrodes and a copolyelectrolytic junction. One nanoporous Pt electrode was to measure the pH as an indicating electrode (pH-IE) and the other assembled with copolyelectrolytic junction was to maintain constant open circuit potential ($E_{oc}$) as a solid-state reference electrode (SSRE). The copolyelectrolytic junction was composed of cationic and anionic polymers immobilized by photo-polymerization of N,N'-methylenebisacrylamide, making buffered electrolytic environment on the SSRE. It was expected to make. The nanoporous Pt surrounded by a constant pH excellently worked as a solid state reference electrode so as to stabilize the system within 30 s and retain the electrochemical environment regardless of unknown sample solutions. Combination between the SSRE and the pH-IE commonly based on nanoporous Pt yielded a complete solid-state pH sensor that requires no internal filling solution. The solid state pH sensing chip is simple and easy to fabricate so that it could be practically used for disposable purposes. Moreover, the solid-state pH sensor successfully functions in calibration-free mode in a variety of buffers and surfactant samples.

Synthesis of Polyurethane-polyacrylate Hybrid Emulsions (폴리우레탄-폴리아크릴레이트 하이브리드 에멀젼의 제조)

  • Kang, Sang Yong;Kim, Hyung Joong
    • Journal of Adhesion and Interface
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    • v.9 no.1
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    • pp.16-21
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    • 2008
  • Hybrid emulsions consisting of polyurethane and acrylic polymer were prepared by emulsion polymerization of acrylic monomers and polyurethane water dispersions (PUD) as an emulsifier. At first, cationic type of PUD was synthesized with IPDI, PTMG1000, MDEA, and acetic acid. Then, acrylic monomers, such as MMA and n-BA, were copolymerized with the PUD without adding further surfactant. The tensile properties and water resistance increased with increasing acrylic monomer ratio. The hybrid emulsions showed better properties than the emulsions simply blended with the PUD and the acrylic emulsions.

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Syntheses of Alternating Head-to-Head Copolymers of Vinyl Ketones and Vinyl Ethers, and Their Properties. Ring-Opening Polymerization of 2,3,6-Trisubstituted-3,4-dihydro-2H-pyrans

  • Lee, Ju-Yeon;Cho, I-Whan
    • Bulletin of the Korean Chemical Society
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    • v.8 no.2
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    • pp.102-105
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    • 1987
  • 2-Methoxy-6-methyl-3,4-dihydro-2H-pyran ($1_a$), 2-ethoxy-3,6-dimethyl-3,4-dihydro-2H-pyran ($1_b$), and 2-ethoxy-3-methyl-6-ethyl-3,4-dihydro-2H-pyran ($1_c$) were prepared by (4 + 2) cycloaddition reaction from the corresponding vinyl ketones and alkyl vinyl ethers. Compounds $1_{a-c}$ were ring-open polymerized by cationic catalyst to obtain alternating head-to-head (H-H) copolymers. For comparison, copolymer of head-to-tail (H-T) was also prepared by free radical copolymerization of the mixture of the corresponding monomers. The H-H copolymer exhibited some differences in its $^1H$ NMR and IR spectra. However, significant differences were showed between the H-H and H-T copolymers in the $^{13}C$ NMR spectra. Also noteworthy was that$T_g$ value of H-H copolymer was higher than that of the corresponding H-T structure. Decomposition temperature of the H-H copolymer was lower than that of the H-T copolymer. All the H-H and H-T copolymers were soluble in common solvents.

Preparation of MWCNTs/Poly(methyl methacrylate) Composite Particles via the Emulsion Polymerization of Methyl Methacrylate Using MWCNTs Modified by Silanization Reaction and Their Morphological Characteristics (실란화 반응으로 표면 개질된 다중벽 탄소나노튜브(MWCNTs)와 Methyl Methacrylate의 유화중합을 통한 MWCNTs/Poly(methyl methacrylate) 복합 입자 제조 및 그 형태학적 특성)

  • Kwon, Jaebeom;Park, Seonghwan;Kim, Sunghoon;Jo, Jieun;Han, Changwoo;Ha, KiRyong
    • Polymer(Korea)
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    • v.39 no.2
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    • pp.329-337
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    • 2015
  • In this study, multi-walled carbon nanotubes (MWCNTs) were oxidized with a mixture of nitric acid and sulfuric acid. After oxidation, oxidized MWCNTs were treated with thionyl chloride ($SOCl_2$) and 1,4-butanediol (BD) in sequence at room temperature to introduce hydroxyl groups on the surface of MWCNTs. The prepared MWCNT-OH was silanized with 3-methacryloxypropyltrimethoxylsilane (MPTMS) to make MWCNT-MPTMS. The MWCNT-MPTMS was used as fillers in emulsion polymerization to make MWCNT-MPTMS/PMMA composite particles with 3 kinds of emulsifiers, hexadecyltrimethylammoniumbromide (CTAB) as a cationic, sodium dodecylbenzene sulfonate (SDBS) as an anionic and polyethylene glycol tert-octylphenyl ether (Triton X-114) as a nonionic emulsifier. Morphologies of composite emulsions were confirmed by a particle size analyzer (PSA) and a scanning electron microscope (SEM). Morphologies of emulsion polymerized MWCNT-MPTMS/PMMA with SDBS showed more uniform particle size distribution compared to those of other two emulsifiers used emulsions. MWCNT-MPTMS/PMMA showed $3.4^{\circ}C$ higher $T_g$ compared to pristine MWCNT/PMMA due to covalent bond formation at interface of MWCNT-MPTMS and PMMA.

Copolymerization of Ethylene and 1-Hexene via Polymethylene Bridged Cationic Dinuclear Constrained Geometry Catalysts (폴리메틸렌 다리로 연결된 양이온 이핵 CGC를 이용한 에틸렌과 1-헥센의 공중합)

  • Bian, Feng Ling;Que, Dang Hoang Dan;Lyoo, Won-Seok;Lee, Dong-Ho;Noh, Seok-Kyun;Kim, Yong-Man
    • Polymer(Korea)
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    • v.31 no.6
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    • pp.497-504
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    • 2007
  • We have prepared the dinuclear half-sandwich CGC(constrained geometry catalyst) with polymethylene bridge $[Zr(({\eta}^5\;:\;{\eta}^1-C_9H_5SiMe_2NCMe_3)Me_2)_2\;[(CH_2)_n]$ [n=6(4), 9(5), 12(6)] by treating 2 equivalents of MeLi with the corresponding dichlorides compounds. To study the catalytic behavior of the dinuclear catalysts we conducted copolymerization of ethylene and 1-hexene in the presence of three kinds of boron cocatalysts, $Ph_3C^+[B(C_6F_5)_4]^-\;(B_1),\;B(C_6F_5)_3\;(B_3)$, and $Ph_3C^+[(C_6F_5)_3B-C_6F_4-B(C_6F_5)_3]^{2-}\;(B_2)$. It turned out that all active species formed by the combination of three dinuclear CGCs with three cocatalyst were very efficient catalysts for the polymerization of olefins. The activities increase as the bridge length of the dinuclear CGCs increases. At the same time the dinuclear cocatalyst exhibited the lowest activity among three cocatalysts. The prime observation is that the dinuclear cocatalyst gave rise to the formation of the copolymers with the least branches on the polyethylene backbone.