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用八（甲基丙烯酰氧基丙基）倍半硅氧烷对硫醇-烯离子凝胶进行改性。

Modification of Thiol-Ene Ionogels with Octakis(methacryloxypropyl) Silsesquioxane.

作者信息

Lewandowska Aneta, Gajewski Piotr, Szcześniak Katarzyna, Sadej Mariola, Patelski Piotr, Marcinkowska Agnieszka

机构信息

Department of Polymers, Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, Poznan University of Technology, Berdychowo 4, 60-965 Poznan, Poland.

出版信息

Polymers (Basel). 2021 Jan 26;13(3):385. doi: 10.3390/polym13030385.

DOI:10.3390/polym13030385
PMID:33530591
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7865288/
Abstract

The effect of polyhedral oligomeric silsesquioxane (POSS) on the synthesis and properties of hybrid organic-inorganic ionogels was investigated using octakis(methacryloxypropyl) silsesquioxane (methacryl-POSS). Ionogels were prepared in situ by thiol-ene photopolymerization of triallyl isocyanurate with pentaerythritol tetrakis(3-mercaptopropionate) in a mixture of imidazolium ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImNTf) and propylene carbonate (PC). Investigations included the kinetics of hybrid materials formation and selected physical and mechanical properties. The disadvantage of ionogels without the methacryl-POSS modifier is leakage and insufficient mechanical properties. Modifying the thiol-ene matrix by the addition of methacryl-POSS made it possible to obtain non-leaking ionogels with improved mechanical and conductive properties. The steric hindrance of POSS cages and high-density network formation played important roles in ionogel synthesis: decrease of polymerization rate (with almost no effect on conversion), as well as dimensions of the formed polymer spheres during dispersion polymerization (highly cross-linked polymer has poorer solubility in polymerizing medium at a similar conversion, and nucleation begins at lower conversion), an increase of glass transition temperature and puncture strength. Hybrid ionogels with high ionic conductivity in the range of 4.0-5.1 mS∙cm with the maximum parameter for 1.5 wt.% addition of the methacryl-POSS were obtained, which can be associated with ion-pair dissociations in ionic liquid clusters caused by methacryl-POSS.

摘要

使用八（甲基丙烯酰氧基丙基）倍半硅氧烷（甲基丙烯酰基-POSS）研究了多面体低聚倍半硅氧烷（POSS）对有机-无机杂化离子凝胶合成及性能的影响。离子凝胶通过三烯丙基异氰脲酸酯与季戊四醇四（3-巯基丙酸酯）在咪唑鎓离子液体1-乙基-3-甲基咪唑双（三氟甲基磺酰）亚胺（EMImNTf）和碳酸丙烯酯（PC）的混合物中进行硫醇-烯光聚合原位制备。研究包括杂化材料形成的动力学以及选定的物理和机械性能。未添加甲基丙烯酰基-POSS改性剂的离子凝胶的缺点是泄漏和机械性能不足。通过添加甲基丙烯酰基-POSS对硫醇-烯基质进行改性，使得能够获得具有改善的机械和导电性能的无泄漏离子凝胶。POSS笼的空间位阻和高密度网络的形成在离子凝胶合成中起重要作用：聚合速率降低（对转化率几乎无影响），以及分散聚合过程中形成的聚合物球的尺寸（高度交联的聚合物在相似转化率下在聚合介质中的溶解度较差，且成核在较低转化率时开始），玻璃化转变温度和穿刺强度增加。获得了离子电导率在4.0 - 5.1 mS∙cm范围内的杂化离子凝胶，添加1.5 wt.%甲基丙烯酰基-POSS时具有最大参数，这可能与甲基丙烯酰基-POSS引起的离子液体簇中的离子对解离有关。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/ebcc2239d28a/polymers-13-00385-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/36ab9f65e160/polymers-13-00385-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/f315de04a9ae/polymers-13-00385-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/ba5092632b8f/polymers-13-00385-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/3d9e49f821d9/polymers-13-00385-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/ccfbec549430/polymers-13-00385-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/5885049542b0/polymers-13-00385-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/6fdef8b9d4d6/polymers-13-00385-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/168d8f66caf8/polymers-13-00385-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/b23467615232/polymers-13-00385-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/ebcc2239d28a/polymers-13-00385-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/36ab9f65e160/polymers-13-00385-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/f315de04a9ae/polymers-13-00385-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/ba5092632b8f/polymers-13-00385-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/3d9e49f821d9/polymers-13-00385-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/ccfbec549430/polymers-13-00385-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/5885049542b0/polymers-13-00385-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/6fdef8b9d4d6/polymers-13-00385-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/168d8f66caf8/polymers-13-00385-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/b23467615232/polymers-13-00385-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6bd7/7865288/ebcc2239d28a/polymers-13-00385-g010.jpg

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