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ID 115976
タイトル別表記
HYDROGEN-BOND-ASSISTED STEREOCONTROL
Hydrogen-Bond-Assisted Stereocontrol in Radical Polymerization of N-Isopropylacrylamide by Using Primary Alkyl Phosphate : Effect of Chain Length of Straight Ester Group
Stereocontrol in NIPAAm polymerization
著者
Ishii, Satoshi Tokushima University
Kitajima, Hiroko Tokushima University
妹尾, 真紀子 Tokushima University
キーワード
hydrogen bond
N-isopropylacrylamide
phosphate
radical polymerization
stereospecific polymers
isotactic
syndiotactic
stereospecific polymerization
tacticity
資料タイプ
学術雑誌論文
抄録
Radical polymerizations of N-isopropylacrylamide (NIPAAm) were carried out in toluene at low temperatures in the presence of phosphoric acid esters such as trimethyl, triethyl (TEP), tri-n-propyl, and tri-n-butyl phosphates (TBP). Syndiotactic-rich poly(NIPAAm)s were obtained at the temperature range from –60°C to 0°C, and particularly TEP provided the highest syndiotacticity (racemo diad = 65%) at –40°C. On the other hand, lowering temperature reversed the stereoselectivity of the propagation reaction so that isotactic-rich poly(NIPAAm)s were obtained at –80°C. In particular, TBP exhibited the most isotactic-specificity (meso diad = 57%). Job's plots for NIPAAm-TBP mixtures revealed that NIPAAm and TBP formed 1:1 complex at 0°C and predominantly 1:2 complex at –80°C through a hydrogen-bonding interaction. Therefore, it is considered that the stereospecificity of NIPAAm polymerization should depend on the stoichiometry of the hydrogen-bond-assisted complex. Thus, the mechanism for the present polymerization system was discussed.
掲載誌名
Journal of Polymer Science Part A : Polymer Chemistry
ISSN
0887624X
10990518
cat書誌ID
AA1068915X
AA11624127
出版者
Wiley
43
1
開始ページ
50
終了ページ
62
発行日
2004-11-15
権利情報
This is the peer reviewed version of the following article: Hirano, T., Ishii, S., Kitajima, H., Seno, M. and Sato, T. (2005), Hydrogen‐bond‐assisted stereocontrol in the radical polymerization of N‐isopropylacrylamide with primary alkyl phosphate: The effect of the chain length of the straight ester group. J. Polym. Sci. A Polym. Chem., 43: 50-62., which has been published in final form at https://doi.org/10.1002/pola.20475. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
EDB ID
出版社版DOI
出版社版URL
フルテキストファイル
言語
eng
著者版フラグ
著者版
部局
理工学系