• Title/Summary/Keyword: Syndiotacticity

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Suspension Polymerization Conditions of Vinyl Pivalate on Size Distribution of Poly(vinyl pivalate) Microspheres (폴리피발산비닐 구형입자의 크기 분포에 영향을 미치는 피발산비닐의 현탁중합 조건)

  • 류원석;박찬식;염정현;지병철
    • Proceedings of the Korean Fiber Society Conference
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    • 2001.10a
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    • pp.211-214
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    • 2001
  • 최근 입자를 이용한 색전술의 재료로서 광범위하게 사용되는 폴리비닐알코올(poly (vinyl alcohol) (PVA)) 입자는 전형적인 혼성배열(atactic)이다[1]. 제조된 PVA 입자가 고내구성 및 혈액내에서 안정성을 나타내기 위해서는 중합된 PVA 입자의 분자량 뿐만 아니라 교대배열성(syndiotacticity)도 커야 한다. 교대배열기(sydiotactic group)를 풍부하게 함유하고 있는 고분자량의 PVA를 제조하기 위해서는 고분자량의 교대배열성 전구체가 얻어지도록 입체장애를 일으키는 에스테르기를 보유하고 있는 단량체를 사용하거나 중합방법을 개선하는 것이 필요하다. (중략)

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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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Poly(vinyl alcohol)의 합성과 유변학적 성질

  • Lee, Jeong Kyung;Lee, Hyang Aee;Kim, Keyn Gyi
    • Journal of the Korean Chemical Society
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    • v.45 no.6
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    • pp.555-561
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    • 2001
  • Vinyl acetate usually used in PVA resin preparation was converted to PVAc by bulk polymerization using AIBN as a initiator and PVA was synthesized by changing the concentration of NaOH added for saponification subsequently. As a result of estimating molecular weight using GPC, molecular weight increased as the NaOH concentration increased to 2.5 N, 5.0 N, 7.5 N and 10.0 N and polydispersity had similar values of 2.1~2.3, however, showed slightly decreasing tendency. In addition, PVA saponificated by 10.0 N-NaOH showed high syndiotacticity in observation of tacticity using NMR spectroscopy. From this fact, the degree of tacticity was predicted to be high and it was in good agreement with the tendency of polydispersity by GPC. Also, from the result of FT-IR spectroscopy, it might be known that hydrolysis was more promoted in the PVA with 10.0 N-NaOH than other NaOH concentration. Intrinsic viscosity measured using Ubbelohde viscometer, which increased as the concentration of NaOH added for saponification increased. The change of shear strength with the change of shear rate was investigated using Brookfield viscometer, in consequence, viscosity of PVA synthesized decreased as shear rate increased. PVA solution confirmed to show the shear thining behavior by Casson plot and PVA with 10.0 N-NaOH had the largest yield value. DSC measurement was performed to know the thermal properties of PVA. Tp had nearly constant value of 214$^{\circ}C$ in all cases except for adding 2.5 N-NaOH and $\Delta$H was increased as the concentration of NaOH increased. From this properties, it was concluded that the degree of hydrogen bonding was proportional to the added concentration of NaOH and the increase of the degree of hydrogen bonding and hydrophobic interaction could affect the rheological and thermal properties of title compound.

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