• Title/Summary/Keyword: Copolymers

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SYNTHESIS OF BLOCK COPOLYMERS CONTAINING POLYPEPTIDE AND ITS BIOMEDICAL APPLICATION

  • Cho, Chong-Su
    • Proceedings of the Korean Society of Sericultural Science Conference
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    • 1997.06a
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    • pp.159-169
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    • 1997
  • ABA-type(or AB) block copolymers composed of poly(${\gamma}$-alkyl L-glutamate) (PALG)[or poly(L-leucine)] as the A component and polyether[or poly (N-isopropy1 acrylamide) as the B component were synthesized by polymerization of (${\gamma}$-alkyl L-glutamate N-carboxyanhydride initiated by primary amined located at both(or one) ends of the polymer chains. Structural studies of the block copolymers were performed in the solution and solid state. Also, artificial skin, drug delivery system of the block copolymers and cell attachment onto the copolymer were carried out for biomedical applications.

Polymerization and Thermal Characteristics of Acrylonitrile/Dicyclohexylammonium 2-Cyanoacrylate Copolymers for Carbon Fiber Precursors

  • Kim, Ki-Young;Park, Woo-Lee;Chung, Yong-Sik;Shin, Dong-Geun;Han, Jin-Wook
    • Carbon letters
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    • v.12 no.1
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    • pp.31-38
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    • 2011
  • This study experimentally investigated dicyclohexylammonium 2-cyanoacrylate (CA) as a potential comonomer for polyacrylonitrile (PAN) based carbon fiber precursors. The P(AN-CA) copolymers with different CA contents (0.19-0.78 mol% in the feed) were polymerized using solution polymerization with 2,2-azobis(isobutyronitrile) as an initiator. The chemical structure and composition of P(AN-CA) copolymers were determined by proton nuclear magnetic resonance and elemental analysis, and the copolymer composition was similar to the feeding ratio of the monomers. The effects of CA comonomer on the thermal properties of its copolymers were characterized differential scanning calorimetry (DSC) in nitrogen and air atmospheres. The DSC curves of P(AN-CA) under nitrogen atmosphere indicated that the initiation temperature for cyclization of nitrile groups was reduced to around $235^{\circ}C$. The heat release and the activation energy for cyclization reactions were decreased in comparison with those of PAN homopolymers. On the other hand, under air atmosphere, the P(AN-CA) with 0.78 mol% CA content showed that the initiation temperature of cyclization was significantly lowered to $160.1^{\circ}C$. The activation energy value showed 116 kJ/mol, that was smaller than that of the copolymers with 0.82 mol% of itaconic acids. The thermal stability of P(AN-CA), evidenced by thermogravimetric analyses in air atmosphere, was found higher than PAN homopolymer and similar to P(AN-IA) copolymers. Therefore, this study successfully demonstrated the great potential of P(AN-CA) copolymers as carbon fiber precursors, taking advantages of the temperature-lowering effects of CA comonomers and higher thermal stability of the CA copolymers for the stabilizing processes.

Synthesis and Characterization of Low Molecular Weight Poly(maleic anhydride-co-vinyl acetate) Copolymers

  • Yoon, Kee-Jong;Woo, Jong-Hyung;Seo, Young-Sam
    • Proceedings of the Korean Fiber Society Conference
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    • 2003.10a
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    • pp.63-64
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    • 2003
  • As a part of a research on the development of polymeric textile finishing agents, polymerization of low molecular weight copolymers containing maleic anhydride residues have been studied. In order to obtain low molecular weight poly(maleic anhydride-co-vinyl acetate) copolymers, the feed ratio of the two monomers and the concentrations of initiator and chain transfer agent were varied in the copolymerization. The copolymers were characterized using GPC, NMR, FTIR, DSC, and TGA. Copolymers with molecular weights in the range 2,150 to 6,630 have been prepared and characterized. The hydrolysis of the anhydride groups of the copolymer in water is also discussed.

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Thermally Stable and Processible Norbornene Copolymers

  • Yoo Dong-Woo;Yang Seung-Jae;Lee Jin-Kyu;Park Joohyeon;Char Kookheon
    • Macromolecular Research
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    • v.14 no.1
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    • pp.107-113
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    • 2006
  • Processible norbornene copolymers were realized by judiciously designing norbomene comonomers, which were themselves prepared by the Diels-Alder reaction of cyclopentadiene and benzoquinone followed by the isomerization and alkylation of alcohols. The norbornene copolymers containing these derivatized comonomers, prepared by [Pd($x_{2}CH-{3} $)$_{4}$][$SbF_{6}$]$_{2}$ catalyst, exhibited excellent solubility in many organic solvents as well as good thermal stability, as evidenced by their high glass transition ($T_{g}$) and decomposition ($\∼$350$^{circ}C$) temperatures. In addition, fairly strong adhesion to substrates such as glasses and silicon wafers was also achieved with these copolymers to overcome the limitations experienced by polynorbornene homopolymers and to make them attractive for many important industrial applications.

Sequence Distribution and Thermal Property of PEN/PBN Copolymers

  • Park, Sang-Soon;Hwang, Jeong-Jun;Jun, Ho-Wook;Im, Seung-Soon
    • Bulletin of the Korean Chemical Society
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    • v.18 no.1
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    • pp.38-43
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    • 1997
  • Poly(ethylene 2, 6-naphthalate-co-tetramethylene 2, 6-naphthalate) (PEN/PBN) copolymers were synthesized and studied by 13C NMR spectroscopy, DSC analysis and X-ray diffraction. A minimum in the melting point vs. composition curve was found at approximately 60 mol% tetramethylene 2, 6-naphthalate. The PEN/PBN copolymers were shown to be statistically random throughout the range of 1, 4-butanediol compositions. The melting point depression behavior of annealed PEN/PBN copolymers depended upon the sequence propagation probability, PS, which is suggested by indivisual crystal formation of two pure comonomers; that is, ethylene-naphthalate-ethylene, EE, and tetramethylene-naphthalate-tetramethylene, BB. However, it can be seen from the X-ray curve that the peaks of PEN/PBN copolymers appear from a crystal lattice which is governed only by the rich component between two different aliphatic units in the copolymer composition.

Paeparation and Properties of Epoxy Copolymers Containing Oxime-urethane Groups as Photobase Generators

  • Chae, Gyu Ho;Song, Hye Bong;Seon, Ho Yong;Jang, Ji Yeong
    • Bulletin of the Korean Chemical Society
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    • v.21 no.7
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    • pp.690-696
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    • 2000
  • Epoxy copolymers containing oxime urethane groups were prepared by the polymerization of glycidyl methacrylate and N-[5-(benzophenoneoximinocarbonylamino)pentanyl]maleimide (BOPM). Their physical properties were characterized by GPC, DSC and TGA analyses. Photochemical changes of the copolymers were studied by UV, IR spectroscopy, and contact angle measurements. A photoinduced cross-linking reaction in copolymer films was observed by measuring the insoluble fraction. Irradiation of the copolymers at 254 nm UV light leads to the formation of pendant amino groups by photodissociation of the oxime-urethane groups. Treatment of the amino groups with HCl resulted in the formation of ammonium salts, which changed the polymer surface to be hydrophilic. An insoluble fraction of the copolymers increased with irradiation time, heating time, and heating temperature. Cross-linking of the epoxy resin effectively catalyzed by the photogenerated pendant amines upon heating.

Stimuli-Responsive Micelles of Amphiphilic and Bis-hydrophilic Block and Graft Copolymers

  • Muller Axel H. E.
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.101-101
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    • 2006
  • We have studied the micellisation of poly(n-butyl acrylate)-block-poly(acrylic acid) and poly(n-butyl acrylate)-graft-poly(acrylic acid) in aqueous solution. The size and structure of the formed micelles was elucidated by scattering and imaging techniques. The micelle structure depends on pH, composition, and topology: graft copolymers form much smaller micelles that block copolymers of similar composition. We have also synthesized block copolymers of acrylic acid and N-isopropylacrylamide (NIPAAm) or N,N-diethylacrylamide (DEAAm). Due to the LCST of polyNIPAAm and polyDEAAm, these block copolymers spontaneously form micelles upon heating and they form inverse micelles upon decreasing pH below 4. If the LCST block is much longer than the PAA one, this presents a very convenient way to prepare crew-cut micelles. The polymers have been successfully used as stabilizers in emulsion polymerization. They also have been conjugated to streptavidin. The conjugates reversibly form mesoscopic particles on heating.

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Chemical Compositional Distribution of Ethylene-1-Butene Copolymer Prepared with Heterogeneous Ziegler-Natta Catalyst: TREF and Crystaf Analysis

  • Ko, Young-Soo;Jeon, Jong-Ki;Yim, Jin-Heong;Park, Young-Kwon
    • Macromolecular Research
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    • v.17 no.5
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    • pp.296-300
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    • 2009
  • Ethylene-1-butene copolymers were prepared with $SiO_2$-supported $TiCl_4$ catalyst by changing of 1-butene/ethylene molar ratio in feed, and the resulting copolymers were analyzed using temperature rising elution fractionation (TREF) and crystallization fractionation (Crystaf) methods to investigated the influence of $C_4/C_2$ molar ratio in feed on chemical compositional distribution and other parameters such as molecular weight and its distribution. TREF analysis showed that the copolymers had a broad and bimodal chemical compositional distribution (CCD) regardless of the content of 1-butene in the copolymer. The chemical composition was in the range of 5 to 55 branches per 1,000 carbons for all copolymers prepared in the study. Furthermore, the broader CCD was revealed for the copolymers having the higher content of 1-butene. Crystaf analysis did not showed a bimodal CCD for the copolymers having the 1-butene content of less than 5.1 wt%. The lower crytalline part having 1-butene content in Crystaf analysis was less than of TREF analysis.

Copolymerization of N-Vinyl Pyrrolidone with Functionalized Vinyl Monomers: Synthesis, Characterization and Reactivity Relationships

  • Vijaykumar, S.;Prasannkumar, S.;Sherigara, B.S.;Shelke, N.B.;Aminabhavi, Tejraj M.;Reddy, B.S.R.
    • Macromolecular Research
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    • v.17 no.12
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    • pp.1003-1009
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    • 2009
  • Copolymers of N-vinylpyrrolidone (NVP) comonomer with styrene (St), hydroxypropyl methacrylate (HPMA) and carboxyphenyl maleimide (CPMI) were synthesized by free radical polymerization using 2,2'-azobisisobutyronitrile (AIBN) initiator in 1,4-dioxane solvent. The copolymers formed were characterized by FTIR, $^1H$ NMR and $^{13}C$ NMR techniques and their thermal properties were studied by DSC and TGA. Copolymer composition was determined by $^1H$ NMR and/or by elemental analysis and monomer reactivity ratios (MRR) were estimated by the linear methods of Kelen-Tudos (K-T) and extended Kelen-Tudos (EK-T) and the non-linear approach. Copolymers of St and HPMA with NVP formed blocks of one of the monomer units, whereas alternating copolymers were obtained in CPMI-NVP, depending upon the side chain substitution. The MRR values are discussed in terms of monomer structural properties such as electronegativity and electron delocalization. The sequence distribution of monomers in the copolymers was studied by statistical method based on the average reactivity ratios obtained by EK-T method.

A Molecular Dynamics Simulation on the Self-assembly of ABC Triblock Copolymers.3. Effects of Block Composition in Asymmetric Triblock Copolymers

  • Ko, Min-Jae;Kim, Seung-Hyun;Jo, Won-Ho
    • Fibers and Polymers
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    • v.4 no.1
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    • pp.15-19
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    • 2003
  • The self-assembly of asymmetric ABC triblock copolymers in the ordered structure is investigated using an isothermal-isobaric molecular dynamics simulation. Unlike symmetric A BC triblock copolymers, more fascinating mophologies are observed in asymmetric ones because of a larger difference of incompatibility between the components. Various modes of self-assembly in assymmetric ABC triblock copolymers are also observed depending on the block composition. When the composition of block A Is changed from 0.125: to 0.25 at the same $f_B$ : 0.25, the morphological transition from the “cylinder in cylinder” to “cylinders at cylinder” structure is observed in the simulation. In the case of ABC triblocks with $f_B$=0.5, a lamellar-type structure is changed to a cylinder-type structure with increasing the length of block A. When the midblock length increases further to $f_B$=0.625, the “spheres on cylinder” structure is observed in both the $A_{10}$$B_{50}$$C_{20}$ and $A_{20}$$B_{50}$$C_{10}$ triblocks. From these results, the phase diagram of ABC triblock copolymers can be constructed.