Facile synthesis of amine-substituted cyclosiloxanes via a photocatalytic thiol-ene reaction to generate ketoenamine-linked hybrid networks
Facile synthesis of amine-substituted cyclosiloxanes via a photocatalytic thiol-ene reaction to generate ketoenamine-linked hybrid networks
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DOI：
10.1038/s41428-022-00678-0
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发表时间：
2022-07
期刊：
影响因子：
2.8
通讯作者：
Huie Zhu;Yuhi Watanabe;N. Yoshida;Yuya Ishizaki;Mao Ohwada;R. Tang;M. Mitsuishi
中科院分区：
文献类型：
--
作者：
Huie Zhu;Yuhi Watanabe;N. Yoshida;Yuya Ishizaki;Mao Ohwada;R. Tang;M. Mitsuishi
1，3，5-三乙烯-1，3，5-三甲基环硅氧烷(D3V)、1，3，5，7-tetravinyl-1，3，5，7-tetramethylcyclosiloxane(D4V)和1，3，5，7，9-pentavinyl-1，3，5，7，9-pentamethylcyclosiloxane(D5V)与半胱胺盐酸盐在温和的条件下进行光催化硫醇-烯反应，合成了多臂功能环硅氧烷。然后与三乙胺进行脱盐反应，得到具有环状结构的胺基环硅氧烷(D4A和D5A)。其化学结构经核磁共振、傅里叶变换红外光谱、基质辅助激光解吸电离飞行时间质谱学确证。无论环硅氧烷环的数目多少，最终产物的区域选择性都是用高达93%的β加合物测定的。氨基官能化的环硅氧烷单体经过温和的席夫碱反应得到杂化网络。并对其形貌、热性能和孔隙率进行了研究。
Multiarmed functional cyclosiloxanes were obtained via a facile synthesis through the photocatalytic thiol-ene reaction of 1,3,5-trivinyl-1,3,5-trimethylcyclosiloxane (D3V), 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclosiloxane (D4V), and 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane (D5V) with cysteamine hydrochloride under mild conditions. A subsequent desalting reaction with triethylamine was conducted to obtain amine-functionalized cyclosiloxanes with ring structures (D4Aand D5A). The chemical structures were confirmed by nuclear magnetic resonance, Fourier transform infrared spectroscopy, and matrix-assisted laser desorption ionization time-of-flight mass spectra. The regioselectivities of the final products were determined withβ-adducts as high as 93% irrespective of the number of cyclosiloxane rings. The amino-functionalized cyclosiloxane monomers underwent a mild Schiff base reaction to obtain hybrid networks. Their morphologies, thermal properties, and porosities were also investigated.