Tracy Clayton A, Adler Abagail M, Nguyen Anh, Johnson R Daniel, Miller Kevin M
Department of Chemistry, Murray State University, 1201 Jesse D. Jones Hall, Murray, Kentucky 42071, United States.
ACS Omega. 2018 Oct 18;3(10):13442-13453. doi: 10.1021/acsomega.8b01949. eCollection 2018 Oct 31.
Azide-alkyne "click" cyclization was used to prepare a series of polymerizable acetoacetate monomers containing a 1,2,3-trizolium ionic liquid group. The monomers were subsequently polymerized using base-catalyzed Michael addition chemistry, producing a series of covalently crosslinked 1,2,3-triazolium poly(ionic liquid) (TPIL) networks. Structure-activity relationships were conducted to gauge how synthetic variables, such as counteranion ([Br], [NO], [BF], [OTf], and [NTf]), and crosslink density (acrylate/acetoacetate ratio) effected thermal, mechanical, and conductive properties. TPIL networks were found to exhibit ionic conductivities in the range of 10-10 S/cm (30 °C, 30% relative humidity), as determined from dielectric relaxation spectroscopy, despite their highly crosslinked nature. Temperature-dependent conductivities demonstrate a dependence on polymer glass transition, with free-ion concentrations impacted by various ions' Lewis acidity/basicity and ion mobilities impacted by freely mobile anion size.
叠氮化物-炔烃“点击”环化反应被用于制备一系列含有1,2,3-三唑鎓离子液体基团的可聚合乙酰乙酸酯单体。随后，使用碱催化的迈克尔加成化学方法使这些单体聚合，生成一系列共价交联的1,2,3-三唑鎓聚（离子液体）（TPIL）网络。进行了结构-活性关系研究，以评估诸如抗衡阴离子（[Br]、[NO]、[BF]、[OTf]和[NTf]）以及交联密度（丙烯酸酯/乙酰乙酸酯比例）等合成变量如何影响热性能、机械性能和导电性能。尽管TPIL网络具有高度交联的性质，但通过介电弛豫光谱测定发现，它们在10⁻¹⁰ S/cm范围内表现出离子电导率（30°C，30%相对湿度）。温度依赖性电导率表明其依赖于聚合物玻璃化转变，自由离子浓度受各种离子的路易斯酸度/碱度影响，而离子迁移率受自由移动阴离子大小影响。
