• Title/Summary/Keyword: syndiotactic

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Polymerization of Methyl Methacrylate with Nickel $\alpha$-Diimine Catalysts: Effect of the Methyl Position in the Ligand

  • Kim, Il;Kim, Jae-Sung;Han, Byeong-Heui;Ha, Chang-Sik
    • Macromolecular Research
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    • v.11 no.6
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    • pp.514-517
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    • 2003
  • In the solution polymerizations of methyl methacrylate with (${\alpha}$-diimine)nickel(II)/methylaluminoxane (MAO), we observed effects of the position of two methyl substituents in the ligand on both the activities of the catalysts and the polymer microstructure. ${\alpha}$-Diimine nickel(II) catalysts gave syndiotactic-rich poly(methyl methacrylate) with high molecular weight and narrow molecular weight distribution.

Molecular Modeling for the Crystal Structure of Stereoregular Poly(vinyl Alcohol) (I) - New Crystal Dimension of Syndiotactic Poly(vinyl Alcohol) -

  • Lyoo, Won-Seok;Sergei Chvalun;John Blackwell
    • Proceedings of the Korean Fiber Society Conference
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    • 1998.04a
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    • pp.135-139
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    • 1998
  • Poly(vinyl acetate) (PVAc) from which atactic poly(vinyl alcohol) (PVA) is derived, is always noncrystalline. This was attributed to the irregular steric arrangement of the acetyl groups in PVAc. However, the X-ray diffraction patterns of atactic PVA, a derivative of PVAc, were found to show distinct crystallinity, and to give an identity period of 2,52 ${\AA}$ along the fiber axis, despite the expectation of an irregular arrangement of the hydroxyl groups in atactic PVA, in the same manner as that of the acetyl groups in PVAc.(omitted)

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Rheological Properties of High Molecular Weight (HMW) Syndiotactic poly(vinyl alcohol) (PVA)/HMW Atactic PVA Blend Solutions (고분자량 교대배열 폴리비닐알코올/고분자량 혼성배열 폴리비닐알코올 블렌드 용액의 유변학적 특성)

  • Yeum, Jeong-Hyun;Ji, Byung-Chul;Lyoo, Won-Seok
    • Proceedings of the Korean Fiber Society Conference
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    • 2003.10b
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    • pp.74-75
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    • 2003
  • Recently, people are gradually concerned about environmental issue, bionics, environmental-friendly or biocompatible materials. Poly(vinyl alcohol) (PVA) is suitable for these materials, because it is typically water-soluble polymer that have linear-flexible chains, a material of no toxicity for human, and biodegradable polymer[1]. One of the most effective factors that dominate the properties of PVAs is tacticity. (omitted)

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Molecular Conformation and Application of Stereoregular PMMA Langmuir-Blodgett Films

  • Kim, Jang-Joo;Jung, Sang-Don;Hwang, Wol-Yon
    • ETRI Journal
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    • v.18 no.3
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    • pp.195-206
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    • 1996
  • Molecular conformations of stereoregular poly(methyl methacrylate) (PMMA) monolayers have been investigated by scanning probe microscopes. Isotactic and syndiotactic PMMAs were found to have right and left hand helical structures, respectively. On the contrary atactic PMMA showed rather random arrangement of the chains. It has been demonstrated that the PMMA Langmuir-Blodgett (LB) films can be utilized to form nanoscale patterns down to 50 nm and to forma geodesic lens. It has also been manifested that the quantum efficiency of a polymer electroluminescent device can be significantly enhanced by inserting the PMMA LB films between the emitting layer and the cathode. All the applications utilize the unique characteristics of the LB films to form thin and uniform films in the molecular level.

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Polymerizations of Propylene with Unsymmetrical ($\alpha$-Diimine)nickel(II) Catalysts

  • Jeon Man-Seong;Han Chul-Jong;Kim Sang-Youl
    • Macromolecular Research
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    • v.14 no.3
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    • pp.306-311
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    • 2006
  • New unsymmetrical ($\alpha$-Diimine)nickel(II) catalysts having different pendent groups at the ortho positions on aromatic rings were synthesized and subjected to propylene polymerizations with MAO (methylaluminoxane). Structural analyses of the resulting polypropylenes by $^1H\;and\;^{13}C\;NMR$ showed that the ortho substituents on aromatic rings of ($\alpha$-diimine)nickel(II) catalyst affected significantly the polypropylene microstructure. While $C_s$ symmetric catalyst afforded a syndiotactic polypropylene (rr triad content=66%) due to the syndiospecific chain end control, $C_1$ symmetric catalysts produced much less stereoregular polypropylenes (rr triads content <50%), presumably because of collision of the isospecific site control with the syndiospecific chain end control.

Some Model Solute Affinity for a Tactic p-HEMA Membranes by K$_D$ Measurement

  • Lee, Eun-Hee;Jeon, Sang-Il;Jhon, Mu-Shik
    • Bulletin of the Korean Chemical Society
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    • v.5 no.5
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    • pp.175-178
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    • 1984
  • Two series of membranes have been prepared by postcrosslinking highly syndiotactic and isotactic poly (2-hydroxyethyl methacrylate), P(HEMA). The crosslinker used was hexamethylene diisocyante (HMDIC). The distribution coefficients (K$_{D2}$) of the model solutes such as urea (and thiourea), their derivatives, homologous alcohol series and amide sreies in water-swollen tactic P(HEMA) membranes at $25^{\circ}C$ were mesaured. In addition, the concentration effects of acetamide and butyramid were also measured. On the basis of hydrophobic interaction and the structural factors of tactic P(HEMA) membranes, the hydrophobic adsorption of the solutes in the polymer matrix were discussed. The results showed that the more hydrphobic the solute is, the higher the $K_{D2}$ value is. And the polymer conformation also affects the distribution of solvents.

Drug Adsorption Behavior of Polyolefin Infusion Tube Compared to PVC and PU (Non-PVC(폴리올레핀) 수액용 튜브 내면에서의 약물흡착 거동 - PVC 및 PU 수액튜브와의 비교)

  • Park, Kang Hoon;Park, Chang Kyu;Park, Jong;Jeon, Seungho;Bang, Sa-Ik;Kim, Ji-Heung;Chung, Dong June
    • Polymer(Korea)
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    • v.38 no.3
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    • pp.333-337
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    • 2014
  • PVC (polyvinyl chloride) intravenous fluid bags and tubes that contain DEHP (diethylhexyl phthalate) as a plasticizer have several associated disadvantages for intravenous injections. We investigated the drug absorption behaviors on the inner surface of an infusion tube that consisted of commercialized PVC/PU (polyurethane). We developed a non-PVC (polyolefin) tube in order to improve the efficacy of this drug administration method. We prepared four types of non-PVC (polyolefin) infusion tubes using a polyethylene (PE), polypropylene (PP), syndiotactic 1,2-polybutadiene (PB), and styrene-ethylene (SE) copolymer elastomers were prepared using a single screw extruder. The four types of manufactured non-PVC (polyolefin) infusion tubes had good mechanical properties that were equivalent to PVC tube properties. The four types of prepared non-PVC (polyolefin) infusion tubes also prohibited drug absorption when compared to the commercialized PVC and PU tubes. Therefore, based on the results of this study, prepared non-PVC (polyolefin) tubes are good candidates for infusion because they prevent drug absorption and the release of DEHP.

Preparation of High Molecular Weight Atactic Poly(vinyl alcohol) by Photo-induced Bulk Polymerization of Vinyl Acetate

  • Lyoo, Won-Seok;Ha, Wan-Shik
    • Fibers and Polymers
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    • v.2 no.2
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    • pp.108-115
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    • 2001
  • Vinyl acetate was polymerized in ultraviolet-ray initiated bulk system at low temperatures using 2,2-azobis(2,4-dimethylvaleronitrile) (ADMVN) or 2,2-azobis(isobutyronitrile) (AIBN) as the photoinitiator, respectively. High molecular weight (HMW) poly(vinyl alcohol) (PVA) having number-average degree of polymerization ($P_n$) of 3,900-7,800 and syndiotactic diad (S-diad) content of 52.5-54.0% could be prepared by complete saponification of synthesized linear poly(vinyl acetate) (PVAc) having $P_n$ 5,900-9,400 obtained at conversion of below 30%. $P_n$ of PVA using ADMVN was larger than that of PVA using AIBN. On the other hand, conversion of the former was smaller than that of the latter, and it was found that the initiation rate of the ADMVN was lower than that of AIBN. This could be explained by a fact that the rate of photolysis of AIBN is faster than that of ADMVN due to the higher quantum yield or dissociation rate constant of AIBN than that of ADMVN. The $P_n$, syndiotacticity, and whiteness of PVA from PVAc polymerized at lower temperatures were superior to those of PVA from PVAc polymerized at higher temperatures.

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Crystallization Behavior of Polymers as Viewed from the Molecular Level

  • Tashiro, Kohji;Sasaki, Sono;Ueno, Yoko;Yoshioka, Akiko;Kobayashi, Masamichi
    • Macromolecular Research
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    • v.8 no.3
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    • pp.103-115
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    • 2000
  • The structural changes viewed from the molecular level have been investigated for the isothermal crystallization phenomena of polyethylene (PE) and the solvent-induced crystallization phenomenon of syndiotactic polystyrene (sPS) glassy sample. The data, which were collected by the time-resolved measurements of Fourier-transform infrared spectra, Raman spectra, synchrotron-sourced small-angle X-ray scattering, wide-angle X-ray scattering, and so on, were combined together to extract the detailed structural information in these phase transition phenomena. In the case of PE, the isothermal crystallization from the melt to the orthorhombic form was found to occur via the conformationally-disordered trans chain form, followed by the formation of the lamellar stacking structure of regular orthorhombic-type crystals. In the case of sPS, the amorphous chains in the glassy sample were found to enhance the mobility through the interaction with the injected solvent molecules, which act as a trigger to cause the conformational ordering from the random coil to the regular T$_2$G$_2$-type helical form. The thus created short helical segments were found to grow into longer helices, which gathered together to form the crystallites, as revealed by the organized coupling of the infrared, Raman and X-ray scattering data.

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Synthesis and Characterization of Poly(vinyl alcohol-b-styrene) via Atom Transfer Radical Polymerization and Saponification

  • Li, Guang-Hua;Cho, Chang-Gi
    • Macromolecular Research
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    • v.10 no.6
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    • pp.339-344
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    • 2002
  • Poly(vinyl alcohol-b-styrene) (poly(VA-b-St)) diblock copolymer containing high syndiotactic poly (vinyl alcohol) (PVA) was synthesized by the saponification of poly(vinyl pivalate-b-styrene) (poly(VPi-b-St)). For the block copolymer, poly(vinyl pivalate) (PVPi) with trichloromethyl end group was obtained via telomerization of vinyl pivalate with carbon tetrachloride as a telogen and 2,2-azobisisobutyronitrile (AIBN) as an initiator. Then resulting poly(vinyl pivalate) with trichloromethyl end group was used as an effient macroinitiator for the synthesis of poly(VPi-b-St) using atom transfer radical polymerization (ATRP) in the presence of CuCl/2,2'-bipyridine at 130 $^{\circ}C$. The poly(vinyl pivalate) macroinitiator, poly(VPi-b-St), poly(VA-b-St) were characterized by GPC, FT-IR and $^1$H-NMR. And the analysis showed that integrity of the block copolymer was maintained during saponification reaction.