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采用二维相关红外光谱法进一步研究基于[Bmim][BF4]的聚苯乙烯复合膜中的分子间相互作用和组分分布。

Further investigation of the intermolecular interactions and component distributions in a [Bmim][BF4]-based polystyrene composite membranes using two-dimensional correlation infrared spectroscopy.

机构信息

Key Laboratory of Molecular Engineering of Polymers (Ministry of Education) and Department of Macromolecular Science, Fudan University, Shanghai 200433, PR China.

出版信息

Langmuir. 2010 Jul 6;26(13):11427-34. doi: 10.1021/la1009225.

Abstract

The intermolecular interaction and distribution of components in [Bmim][BF(4)]-based polystyrene composite membrane which is composed of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]), poly(1-(2-methyl acryloyloxyundecyl)-3-methylimidazolium bromide) (poly(MAUM-Br)) and polystyrene is investigated by in situ Fourier transform infrared spectroscopy (FTIR) and two-dimensional correlation infrared spectroscopy (2DIR) in this study. A proposed model about the structure of this composite material is presented, and a sketch map about the local distributions of components is provided. In this model, alkyl chains in [Bmim][BF(4)], poly(MAUM-Br), and polystyrene in this system were supposed to form a polymeric network through aggregation or copolymerization. Cations of ionic liquids separate into the polymer network, while anions are kept mainly through the Coulomb force and partially by the hydrogen bonding between cations and anions. To support this model, FTIR has provided some hints on the pi-pi interaction existing in this complex material between the imidazole ring of ionic liquids and the benzene ring of polystyrene, based on the discovery of the shifts of IR absorption bands assigned to the C-C stretching vibrational mode. The sequential order of the responses from different chemical groups toward the variation of temperature is calculated by 2DIR, and the results suggest how different components distributed in this [Bmim][BF(4)]-based polystyrene composite membrane.

摘要

本文采用原位傅里叶变换红外光谱(FTIR)和二维相关红外光谱(2DIR)研究了由 1-丁基-3-甲基咪唑四氟硼酸盐([Bmim][BF4])、聚(1-(2-甲基丙烯酰氧基十一烷基)-3-甲基咪唑溴化物)(poly(MAUM-Br))和聚苯乙烯组成的[Bmim][BF4]基聚苯乙烯复合膜中分子间相互作用和各组分的分布。提出了一种关于该复合材料结构的模型,并提供了各组分局部分布的示意图。在该模型中,[Bmim][BF4]、poly(MAUM-Br)和聚苯乙烯中的烷基链被认为通过聚集或共聚形成聚合物网络。离子液体的阳离子分离到聚合物网络中,而阴离子主要通过库仑力保持,部分通过阳离子和阴离子之间的氢键保持。为了支持这个模型,FTIR 基于对 IR 吸收带归属的 C-C 伸缩振动模式的位移,提供了在这个复杂材料中离子液体的咪唑环和聚苯乙烯的苯环之间存在π-π相互作用的一些线索。通过 2DIR 计算了不同化学基团对温度变化的响应顺序,结果表明了不同组分在[Bmim][BF4]基聚苯乙烯复合膜中的分布情况。

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