Hydrogen-bond-assisted stereocontrol in the radical polymerization of N-isopropylacrylamide with bidentate Lewis base

Hydrogen-bond-assisted stereocontrol in the radical polymerization of N-isopropylacrylamide with bidentate Lewis base
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N-异丙基丙烯酰胺双齿路易斯碱自由基聚合中的氢键辅助立体调控

DOI:
10.1016/j.polymer.2005.11.057
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发表时间:
2006
期刊:
影响因子:
4.6
通讯作者:
Tsuneyuki Sato
Tsuneyuki Sato
中科院分区:
化学2区
文献类型:
--
作者:
Tomohiro Hirano;H. Kitajima;M. Seno;Tsuneyuki Sato

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研究了二齿路易斯碱(例如二膦酸盐)存在下,甲苯中 N-异丙基丙烯酰胺 (NIPAAm) 的自由基聚合。所得聚(NIPAAm)的全同立构规整度在-80°C下略有增加,而富含间规立构的聚(NIPAAm)在-40–0°C下获得。该结果对应于伯烷基磷酸存在下观察到的结果。 NMR分析表明,NIPAAm单体和亚甲基二膦酸四异丙酯在0℃下形成单键氢键辅助复合物,但在-80℃下形成螯合复合物。因此,可以得出结论,NIPAAm 聚合反应中的立体定向性很大程度上取决于所添加的双齿路易斯碱的络合模式。
Radical polymerization of N-isopropylacrylamide (NIPAAm) in toluene was investigated in the presence of bidentate Lewis base such as diphosphonates. Isotacticity of the obtained poly(NIPAAm)s slightly increased at −80°C, whereas syndiotactic-rich poly(NIPAAm)s were obtained at −40–0°C. This result corresponded to the results observed in the presence of primary alkyl phosphates. NMR analysis revealed that NIPAAm monomer and tetraisopropyl methylenebisphosphonate formed mono-binding hydrogen-bond-assisted complex at 0°C, but a chelate complex at −80°C. Thus, it was concluded that the stereospecificity in NIPAAm polymerization strongly depended on the complexation mode of the added bidentate Lewis base.
DOI: 10.1163/156855504322890016
发表时间: 2004-01
影响因子: 1.6
作者:
Mana Ito;Takashi Ishizone
通讯作者: Mana Ito;Takashi Ishizone
水介质中聚(N-异丙基丙烯酰胺)(PNIPAm)的化学选择性阴离子聚合新方法
DOI: --
发表时间: 2004
期刊: Macromolecules 37
影响因子: --
作者:
Masanobu Uchiyama;et al.
通讯作者: et al.