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硒化物功能化乙烯基单体的可控自由基聚合及其在氧化还原响应光子晶体中的应用。

Controllable Radical Polymerization of Selenide Functionalized Vinyl Monomers and Its Application in Redox Responsive Photonic Crystals.

机构信息

State Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Department of Polymer Science and Engineering, College of Chemistry Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P. R. China.

Department of Polymer Science and Engineering, College of Chemistry Chemical Engineering and RIRI Science, Soochow University, Suzhou, 215123, P. R. China.

出版信息

Macromol Rapid Commun. 2021 Sep;42(18):e2000764. doi: 10.1002/marc.202000764. Epub 2021 Feb 5.

Abstract

Selenium-containing monomer (p-phenylseleno) styrene (p-PhSeSt) is polymerized by reversible addition-fragmentation chain transfer polymerization. Polymer, (P(p-PhSeSt)), with controlled molecular weight and narrow molecular weight is obtained. The selenide moiety in obtained P(p-PhSeSt) can be selectively oxidized to selenoxide or selenone groups by H O or NaClO, respectively. These oxidized groups can be further reduced to selenide by Na S O . The structure changing of polymers during such redox cycle is characterized by nuclear magnetic resonance, X-ray photoelectron spectroscopy, and size exclusion chromatography. Properties, such as thermal performance, glass transition temperature, water contact angles, and refractive indices, of the resulting polymers are systematically investigated before and after oxidation. In addition, SiO inverse opal photonic crystal (IOPC) is fabricated by sacrificial polymer colloidal template method. Owing to changes of the RIs of P(p-PhSeSt) after selective oxidation, the predictable change of PC bandgap as a redox-responsive PC sensor is successfully realized, which provides new perspectives for modulating photonic crystals.

摘要

含硒单体(对苯硒基)苯乙烯(p-PhSeSt)通过可逆加成-断裂链转移聚合进行聚合。得到了具有可控分子量和较窄分子量分布的聚合物(P(p-PhSeSt))。通过 H2O2 或 NaClO,可分别将所得 P(p-PhSeSt)中的硒化物部分选择性氧化为硒氧化物或硒酮基团。这些氧化基团可以通过 Na2S2O8 进一步还原为硒化物。通过核磁共振、X 射线光电子能谱和凝胶渗透色谱对聚合物在这种氧化还原循环过程中的结构变化进行了表征。研究了氧化前后聚合物的热性能、玻璃化转变温度、水接触角和折射率等性能。此外,通过牺牲聚合物胶体模板法制备了 SiO2 反蛋白石光子晶体(IOPC)。由于 P(p-PhSeSt)选择性氧化后 RI 的变化,成功实现了作为氧化还原响应型 PC 传感器的 PC 带隙的可预测变化,为调控光子晶体提供了新的视角。

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