Ionic liquid bonded polysiloxanes (PILs) are a class of polysiloxanes whose side chains contain ionic liquid (IL) moieties. Considering their excellent selectivity and thermo-stability, PILs have great potentials in the development of polar stationary phases for gas chromatography. In this paper, a novel synthesis strategy for PILs is proposed to diversify PIL stationary phases and also facilitate the study on relationships between stationary phase structure and separation performances. The polysiloxane with imidazole groups at the side chains was synthesized firstly, and then these imidazole groups further reacted with halogenated compounds to produce various IL groups. Upon this, fifteen PIL stationary phases differing in IL content, IL group or combination of different IL groups have been synthesized and used to prepare capillary columns through static coating method. These columns have quite different general polarity indexes (the average value of all Rohrschneider-McReynolds constants in this paper) falling in a broad range from 218 to 717, and most columns have column efficiency values over 3000 plates/m. In addition, IL content, structure of the IL and combination of different IL groups have noticeable influences on interaction features of the stationary phases. After that, the separation performances of these PIL stationary phases were demonstrated by separating various mixed samples of aliphatic esters, dichloro-anilines, alcohols, aromatic amines, substituted alkanes, and so on. In order to reveal the relationship of interaction characteristics and separation performances, a set of indexes of contribution rates (CRs) is proposed. Based on CRs, the separation selectivity of the PIL stationary phases has been discussed in detail. The results indicate that there are significant differences in the separation selectivity not only between PILs and conventional polar stationary phases, but also among different PILs. All of these imply a family of practical PILs with special selectivity could be constructed upon this synthesis strategy.
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