Citation: ZHAO Xue-Yan, CAO Yu-Rong, CAO Gui-Rong, XIAO Rui-Jie. Lamellar Liquid Crystalline Phase Formed by Triblock Copolymer L64 in 1-Butyl-3-methylimidazolium Tetrafluoroborate Ionic Liquid[J]. Acta Physico-Chimica Sinica, ;2012, 28(06): 1411-1417. doi: 10.3866/PKU.WHXB201203262 shu

Lamellar Liquid Crystalline Phase Formed by Triblock Copolymer L64 in 1-Butyl-3-methylimidazolium Tetrafluoroborate Ionic Liquid

1.
1. Department of Fundamental Courses, Institute of Disaster Prevention, Langfang 065201, Hebei Province, P. R. China;
2. Department of Information, China Cleaning Industry Association, Beijing 100044, P. R. China

Received Date: 7 February 2012
Available Online: 26 March 2012
Fund Project: 中国地震局教师科研基金(20110123) (20110123)中央高校基本科研业务费创新项目团队计划(ZY20110103)资助 (ZY20110103)

The aggregation behavior of the triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (L64, PEO₁₃PPO₃₀PEO₁₃) in the room-temperature ionic liquid 1-butyl-3- methylimidazolium tetrafluoroborate ([Bmim] [BF₄]) was investigated using polarized optical microscopy (POM), small-angle X-ray scattering (SAXS), and Fourier transform infrared (FTIR) spectroscopy. The phase diagram of the L64/[Bmim] [BF₄] system is described, where the micellar phase (L₁), a mixture of lamellar liquid crystalline (L_α) and L₁ phases, the L_α phase, a mixture of L_α and reverse micellar (L₂) phases, and the L₂ phase are sequentially mapped. Among these phases, the behavior of the L_α phase formed in the L64/[Bmim][BF₄] system in the L64 concentration region of 40%-65% (w, mass fraction) was focused on because it forms highly-ordered structures. The Maltese cross texture was found through POM characterization, and was typical for the L_α phase. The SAXS patterns further confirm the formation of the L_α phase. In addition, the lattice spacings of the L_α phase were obtained from the SAXS patterns. The effect of temperature on the microstructure of the L_α phase was also elucidated. As the temperature was increased, the lattice spacing and ordering of the L_α phase increased, while the interfacial area decreased for a certain temperature range. However, the birefringence of the L_α phase disappeared when the temperature reached a certain level, which was attributed to the breakdown of hydrogen bonding between [Bmim] [BF₄] and poly(ethylene oxide) chains, so the ordering of the L_α phase was decreased. The formation mechanism of the L_α phase is also discussed. Hydrogen bonding, electrostatic and solvophobic interactions are believed to be the main driving forces for the formation of L_α phase in the L64/[Bmim][BF₄] system.
- Ionic liquid,
- Block copolymer,
- Lamellar liquid crystalline,
- Aggregation behavior,
- Formation mechanism
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