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Enhanced Thermal Stability of Polystyrene by Interfacial Noncovalent Interactions
Macromolecules ( IF 5.1 ) Pub Date : 2018-07-18 00:00:00 , DOI: 10.1021/acs.macromol.8b01012 Yongming Hong 1 , Yawei Li 1 , Fengliang Wang 1 , Biao Zuo 1 , Xinping Wang 1 , Li Zhang 1 , Daisuke Kawaguchi , Keiji Tanaka
Macromolecules ( IF 5.1 ) Pub Date : 2018-07-18 00:00:00 , DOI: 10.1021/acs.macromol.8b01012 Yongming Hong 1 , Yawei Li 1 , Fengliang Wang 1 , Biao Zuo 1 , Xinping Wang 1 , Li Zhang 1 , Daisuke Kawaguchi , Keiji Tanaka
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The local conformation of polystyrene (PS) and deuterated PS at the interface with quartz substrates, which were covered with phenyl groups using phenyltrimethoxysilane (PTS) under various conditions, was examined by sum frequency generation spectroscopy. As evidenced by the red-shift of the wavenumber of the v2 vibration mode for phenyl groups, it was claimed that PTS phenyl groups standing vertically from the quartz surface induced the perpendicular orientation of PS phenyl rings by energetically favorable parallel-displaced π–π interactions at the interface. The local conformation of PS chains strongly anchored onto the substrate by the π–π interactions remained almost unchanged for 48 h even at a temperature 60 K higher than the bulk glass transition temperature. That is, the interfacial π–π interactions facilitated the adsorption of PS chains on the substrate to attain a large enthalpic gain, resulting in significantly slower dynamics of PS chains at the interface. Our results illustrate the importance of the interfacial noncovalent interactions in controlling the structure and dynamics of macromolecular chains at the interface as well as in the thin film geometry.
中文翻译：
界面非共价相互作用增强了聚苯乙烯的热稳定性
通过总频率产生光谱法检查了在与聚苯乙烯（PS）和氘代PS在石英基板的界面处的局部构象，所述石英基板在各种条件下使用苯基三甲氧基硅烷（PTS）被苯基覆盖。如v 2的波数的红移所证明的对于苯基的振动模式，据称从石英表面垂直竖立的PTS苯基通过界面处能量上有利的平行位移π-π相互作用诱导PS苯基环的垂直取向。即使在比本体玻璃化转变温度高60 K的温度下，通过π-π相互作用牢固锚定在基底上的PS链的局部构型在48小时内几乎保持不变。也就是说，界面π-π相互作用促进了PS链在基质上的吸附，从而获得较大的焓增，从而导致界面处PS链的动力学明显变慢。
更新日期：2018-07-18
中文翻译：
界面非共价相互作用增强了聚苯乙烯的热稳定性
通过总频率产生光谱法检查了在与聚苯乙烯（PS）和氘代PS在石英基板的界面处的局部构象，所述石英基板在各种条件下使用苯基三甲氧基硅烷（PTS）被苯基覆盖。如v 2的波数的红移所证明的对于苯基的振动模式，据称从石英表面垂直竖立的PTS苯基通过界面处能量上有利的平行位移π-π相互作用诱导PS苯基环的垂直取向。即使在比本体玻璃化转变温度高60 K的温度下，通过π-π相互作用牢固锚定在基底上的PS链的局部构型在48小时内几乎保持不变。也就是说，界面π-π相互作用促进了PS链在基质上的吸附，从而获得较大的焓增，从而导致界面处PS链的动力学明显变慢。
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