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From Polymerizable Ionic Liquids to Poly(ionic liquid)s: Structure-Dependent Thermal, Crystalline, Conductivity, and Solution Thermoresponsive Behaviors
Macromolecules ( IF 5.1 ) Pub Date : 2019-01-22 00:00:00 , DOI: 10.1021/acs.macromol.8b02351 Yajnaseni Biswas 1 , Palash Banerjee 1 , Tarun K. Mandal 1
Macromolecules ( IF 5.1 ) Pub Date : 2019-01-22 00:00:00 , DOI: 10.1021/acs.macromol.8b02351 Yajnaseni Biswas 1 , Palash Banerjee 1 , Tarun K. Mandal 1
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This contribution describes the synthesis of 3-alkyl-1-vinylimidazolium bromide ionic liquid monomers (ILMs), ion exchange with bis(trifluoromethane)sulfonimide anion (NTf2–), and their radical polymerization to a homologous series of poly(ionic liquid)s (PILs) containing an imidazolium ion substituted with alkyl chains of different lengths (C2(n=7–11)). Owing to the presence of a long alkyl chain, all the ILMs show crystalline phases whose melting point and melting enthalpy increase sharply with increasing alkyl chain length, and those parameters decrease upon replacing Br– with a NTf2– anion. In addition to the solid crystalline phase, the ILMs with a Br– ion only show liquid crystalline mesophases above the melting of solid crystals. The corresponding PILs are semicrystalline in nature due to crystallizable alkyl side chain showing similar chain length and counteranion-dependent melting behaviors with poor crystallinity compared to those of ILMs. The formation of strong birefringent crystals of various morphologies including Maltese-cross and ring-banded spherulites is observed for ILMs. However, the corresponding PILs with a Br– ion show crystals with fibrillar morphology with weak birefringence, but surprisingly such fibrils are not observed for PILs with a NTf2– ion. The influence of structural modulations of ILMs and their corresponding PILs on their ionic conductivities is also investigated. Moreover, PILs with a Br– ion exhibit an upper critical solution temperature (UCST)-type turbid-to-transparent phase transition in CHCl3 with tunable cloud point as observed from turbidity and calorimetric measurements. Such a thermoresponsive solution phase behavior is totally absent for PILs when Br– is replaced with a NTf2– ion.
中文翻译：
从可聚合离子液体到聚离子液体：结构相关的热，结晶，电导率和溶液热响应行为
该文章描述了3-烷基-1-乙烯基咪唑鎓溴化离子液体单体（ILMs）的合成，与双（三氟甲烷）磺酰亚胺阴离子（NTf 2 –）的离子交换，以及它们的自由基聚合反应，形成了一系列同源的聚离子液体s（PILs）含有被不同长度的烷基链取代的咪唑鎓离子（C 2（n = 7-11））。由于一个长烷基链的存在，所有的的ILM显示结晶相的熔点，并随着烷基链长急剧熔化焓增加，并且这些参数减少在更换溴-与NTF 2 -阴离子。除固相外，带有Br –的ILM离子仅在固态晶体熔化后显示液晶中间相。相应的PIL本质上是半结晶的，这是由于可结晶的烷基侧链与ILM相比具有相似的链长和依赖于阴离子的熔融行为，且结晶度较差。对于ILM，观察到形成了各种形态的强双折射晶体，包括马耳他十字形和环带状球晶。然而，具有溴相应的Pils -离子显示晶体与弱双折射纤丝形态，但令人惊讶的这种原纤维不用于与NTF PILS观察2 -离子。还研究了ILM及其相应PIL的结构调制对其离子电导率的影响。此外，带有Br的PIL–从浊度和量热法测量中观察到，离子在CHCl 3中显示出较高的临界溶液温度（UCST）型混浊至透明相变，浊点可调。当溴这样的热反应溶液相行为是PILS完全不存在-被替换为NTF 2 -离子。
更新日期：2019-01-22
中文翻译：
从可聚合离子液体到聚离子液体：结构相关的热，结晶，电导率和溶液热响应行为
该文章描述了3-烷基-1-乙烯基咪唑鎓溴化离子液体单体（ILMs）的合成，与双（三氟甲烷）磺酰亚胺阴离子（NTf 2 –）的离子交换，以及它们的自由基聚合反应，形成了一系列同源的聚离子液体s（PILs）含有被不同长度的烷基链取代的咪唑鎓离子（C 2（n = 7-11））。由于一个长烷基链的存在，所有的的ILM显示结晶相的熔点，并随着烷基链长急剧熔化焓增加，并且这些参数减少在更换溴-与NTF 2 -阴离子。除固相外，带有Br –的ILM离子仅在固态晶体熔化后显示液晶中间相。相应的PIL本质上是半结晶的，这是由于可结晶的烷基侧链与ILM相比具有相似的链长和依赖于阴离子的熔融行为，且结晶度较差。对于ILM，观察到形成了各种形态的强双折射晶体，包括马耳他十字形和环带状球晶。然而，具有溴相应的Pils -离子显示晶体与弱双折射纤丝形态，但令人惊讶的这种原纤维不用于与NTF PILS观察2 -离子。还研究了ILM及其相应PIL的结构调制对其离子电导率的影响。此外，带有Br的PIL–从浊度和量热法测量中观察到，离子在CHCl 3中显示出较高的临界溶液温度（UCST）型混浊至透明相变，浊点可调。当溴这样的热反应溶液相行为是PILS完全不存在-被替换为NTF 2 -离子。
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