Lewandowska Aneta, Gajewski Piotr, Szcześniak Katarzyna, Marcinkowska Agnieszka
Institute of Chemical Technology and Engineering, Poznan University of Technology, Berdychowo 4, 60-965 Poznan, Poland.
Gels. 2021 Nov 15;7(4):214. doi: 10.3390/gels7040214.
The influence of ene and thiol monomer structure on the mechanical and electrochemical properties of thiol-ene polymeric ionogels were investigated. Ionogels were obtained in situ by thiol-ene photopolymerization of 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATT), 2,4,6-triallyloxy-1,3,5-triazine (TAT), diallyl phthalate (DAP), and glyoxal bis(diallyl acetal) (GBDA) used as enes and trimethylolpropane tris(3-mercaptopropionate) (TMPTP), pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), and pentaerythritol tetrakis(3-mercaptobutyrate) (PETMB) used as thiols in 70 wt.% of ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImNTf). The mechanical strength of ionogels was studied by puncture resistance and ionic conductivity by electrochemical impedance spectroscopy. The course of photopolymerization by photo-DSC method (differential scanning calorimetry) as well as characterization of compositions and its components (by IR and UV spectroscopy-Kamlet-Taft parameters) were also studied. The resulting ionogels were opaque, with phase separation, which resulted from the dispersion mechanism of polymerization. The mechanical and conductive properties of the obtained materials were found to be largely dependent on the monomer structure. Ionogels based on triazine monomers TAT and TATT were characterized by higher mechanical strength, while those based on aliphatic GBDA had the highest conductivity. These parameters are strongly related to the structure of the polymer matrix, which is in the form of connected spheres. The conductivity of ionogels was high, in the range of 3.5-5.1 mS∙cm.
研究了烯类和硫醇类单体结构对硫醇-烯聚合物离子凝胶的力学和电化学性能的影响。通过1,3,5-三烯丙基-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮(TATT)、2,4,6-三烯丙氧基-1,3,5-三嗪(TAT)、邻苯二甲酸二烯丙酯(DAP)和乙二醛双(二烯丙基缩醛)(GBDA)作为烯类,以及三羟甲基丙烷三(3-巯基丙酸酯)(TMPTP)、季戊四醇四(3-巯基丙酸酯)(PETMP)和季戊四醇四(3-巯基丁酸酯)(PETMB)作为硫醇类,在70 wt.%的离子液体1-乙基-3-甲基咪唑双(三氟甲基磺酰)亚胺(EMImNTf)中进行硫醇-烯光聚合原位制备离子凝胶。通过抗穿刺性研究离子凝胶的机械强度,通过电化学阻抗谱研究离子电导率。还研究了光差示扫描量热法(photo-DSC)的光聚合过程以及组合物及其组分的表征(通过红外和紫外光谱 - 卡姆雷特 - 塔夫脱参数)。所得离子凝胶是不透明的,具有相分离,这是由聚合的分散机制导致的。发现所得材料的机械和导电性能在很大程度上取决于单体结构。基于三嗪单体TAT和TATT的离子凝胶具有较高的机械强度,而基于脂肪族GBDA的离子凝胶具有最高的电导率。这些参数与呈连接球体形式的聚合物基质的结构密切相关。离子凝胶的电导率很高,在3.5 - 5.1 mS∙cm范围内。