ID | 115973 |
タイトル別表記 | Hydrogen-Bond-Assisted Stereocontrol in the Radical Polymerization of N-Isopropylacrylamide with Secondary Alkyl Phosphate : Effect of Bulkiness of Ester Group
HYDROGEN-BOND-ASSISTED STEREOCONTROL
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著者 |
Kitajima, Hiroko
Tokushima University
Ishii, Satoshi
Tokushima University
妹尾, 真紀子
Tokushima University
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キーワード | hydrogen bond
N-isopropylacrylamide
phosphate
radical polymerization
stereoregular polymers
stereospecific polymerization
syndiotactic
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資料タイプ |
学術雑誌論文
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抄録 | Radical polymerization of N-isopropylacrylamide (NIPAAm) in toluene at low temperatures was investigated in the presence of triisopropyl phosphate (TiPP). The addition of TiPP induced a syndiotactic-specificity that was enhanced by lowering polymerization temperature, whereas atactic polymers were obtained in the absence of TiPP regardless of temperature. Syndiotactic-rich poly(NIPAAm) with racemo diad = 65% was obtained at –60°C with a fourfold amount of TiPP, but almost atactic poly(NIPAAm)s were obtained by lowering temperature to –80°C. This result contrasted with the result in the presence of primary alkyl phosphates, such as tri-n-propyl phosphate, that stereospecificity varied from syndiotactic to isotactic by lowering polymerization temperature. NMR analysis at –80°C revealed that TiPP predominantly formed 1:1 complex with NIPAAm, although primary alkyl phosphates preferentially formed 1:2 complex with NIPAAm. Thus, it was concluded that a slight increase in bulkiness of the added phosphates influenced the stoichiometry of the NIPAAm-phosphate complex at lower temperatures and consequently a drastic change in the effect on stereospecificity of NIPAAm polymerization was observed.
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掲載誌名 |
Journal of Polymer Science Part A : Polymer Chemistry
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ISSN | 0887624X
10990518
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cat書誌ID | AA1068915X
AA11624127
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出版者 | Wiley
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巻 | 43
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号 | 17
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開始ページ | 3899
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終了ページ | 3908
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発行日 | 2005-07-18
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権利情報 | This is the peer reviewed version of the following article: Hirano, T., Kitajima, H., Ishii, S., Seno, M. and Sato, T. (2005), Hydrogen‐bond‐assisted stereocontrol in the radical polymerization of N‐isopropylacrylamide with secondary alkyl phosphate: The effect of the bulkiness of the ester group. J. Polym. Sci. A Polym. Chem., 43: 3899-3908., which has been published in final form at https://doi.org/10.1002/pola.20883. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
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言語 |
eng
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著者版フラグ |
著者版
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部局 |
理工学系
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