Thiol–Trifluorovinyl Ether (TFVE) Photopolymerization: An On-Demand Synthetic Route to Semifluorinated Polymer Networks
Thiol–Trifluorovinyl Ether (TFVE) Photopolymerization: An On-Demand Synthetic Route to Semifluorinated Polymer Networks
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硫醇-三氟乙烯基醚 (TFVE) 光聚合：半氟化聚合物网络的按需合成途径
DOI：
10.1021/acs.macromol.6b01822
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发表时间：
2016
期刊：
影响因子：
5.5
通讯作者：
Patton, Derek L.
中科院分区：
文献类型：
--
作者：
Donovan, Brian R.;Ballenas, Jason E.;Patton, Derek L.
我们报道了第一个硫醇-三氟乙烯基醚(硫醇-TFVE)光聚合的例子，作为一种简单的、按需固化的合成路线来合成半氟化聚合物网络。用不同反应性的苯基三氟乙烯基醚与硫醇之间的小分子反应模型解释了硫醇-TFVE反应，它是通过在TFVE基团上反马氏加成而进行的。这些模型反应由19F-核磁共振、1H-核磁共振和FTIR表征，也提供了氧诱导降解途径的证据，可以通过在惰性气体气氛下进行反应来绕过该途径。用实时傅里叶变换红外光谱观察到双官能团TFVE单体与多官能团硫醇的光聚合反应动力学快、转化率高，用动态力学分析观察到具有窄玻璃化转变的均相半氟聚合物网络。与结构相似的氢化醚/硫醚键组成的硫醇-烯材料相比，加入到聚合物网络中的半氟醚/硫醚键产生的疏水材料具有更高和可调节的Tg，断裂应变增加2倍，断裂应力增加4倍，韧性增加5倍以上。Tg和机械韧性的提高归因于半氟醚/硫醚相对于氢化醚/硫醚具有更高的刚性、氢键能力和更强的碳-碳键。
We report a first example of thiol–trifluorovinyl ether (thiol–TFVE) photopolymerization as a facile, cure-on-demand synthetic route to semifluorinated polymer networks. The thiol–TFVE reactionwhich proceeds via anti-Markovnikov addition of a thiyl radial to the TFVE groupwas elucidated using model small molecule reactions between phenyl trifluorovinyl ether and thiols with varying reactivity. These model reactions, characterized by19F NMR,1H NMR, and FTIR, also provided evidence of an oxygen-induced degradation pathway that may be circumvented by performing the reactions under an inert gas atmosphere. Photopolymerization of difunctional TFVE monomers with multifunctional thiols occurred with rapid kinetics and high conversions as observed with real-time FTIR and provided homogeneous semifluorinated polymer networks with narrow glass transitions as observed with dynamic mechanical analysis. The semifluorinated ether/thioether linkage incorporated into the polymer network yielded hydrophobic materials with increased and tunableTg, a 2-fold increase in strain at break, 4-fold increase in stress at break, and more than 5-fold increase in toughness relative to a thiol–ene material composed of a structurally similar hydrogenated ether/thioether linkage. The increasedTgand mechanical toughness are attributed to the higher rigidity, hydrogen-bonding capacity, and stronger carbon–carbon bonds of the semifluorinated ether/thioether relative to the hydrogenated ether/thioether.
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影响因子：
4.6
作者：
Chiantore, O;Trossarelli, L;Lazzari, M
通讯作者：
Lazzari, M
DOI：
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发表时间：
1991
期刊：
影响因子：
--
作者：
T. Nguyen;C. Wakselman
通讯作者：
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由三氟乙烯基芳香族醚单体制成的半氟化聚合物
DOI：
--
发表时间：
2014
期刊：
影响因子：
--
作者：
Jianyong Jin;S. Iacono;Dennis W. Smith
通讯作者：
Dennis W. Smith
DOI：
--
发表时间：
1969
期刊：
影响因子：
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作者：
F. Ciampelli;M. Venturi;D. Sianesi
通讯作者：
D. Sianesi
氟烯烃化学：第 2 部分。硫醇与某些有毒 1,2-二氯多氟环烯烃的反应
DOI：
--
发表时间：
2004
期刊：
影响因子：
--
作者：
C. Timperley
通讯作者：
C. Timperley