Thiol ligand capped quantum dot as an efficient and oxygen tolerance photoinitiator for aqueous phase radical polymerization and 3D printing under visible light,Polymer Chemistry

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Thiol ligand capped quantum dot as an efficient and oxygen tolerance photoinitiator for aqueous phase radical polymerization and 3D printing under visible light
Polymer Chemistry ( IF 4.1 ) Pub Date : 2021-08-17 , DOI: 10.1039/d1py00705j
Yifan Zhu ₁ , Emira Ramadani ₁ , Eilaf Egap _{1,

2}

Affiliation

We report here a rapid visible-light-induced radical polymerization in aqueous media photoinitiated by only ppm level thiol ligand capped cadmium selenide (CdSe) quantum dots (QDs). Simple ligand exchange procedures with various bifunctional thiol ligands facilitate the dispersion of CdSe QDs in water, thus expanding the scope of aqueous photocatalysts. The polymerization showcased excellent oxygen tolerance, giving a low dispersity (Đ) of 1.27. Additive thiol molecules were proposed to act as the coinitiating species, oxidized by photoexcited CdSe QDs to form thiyl radicals and further initiate the polymerization. More importantly, successful thiol–ene click reactions were achieved by scaling up the thiol to olefin ratio to 1, suggesting the thiol ligand coinitiating mechanism and meanwhile demonstrating the great potential of QD photocatalysts in organic transformations. Furthermore, the photoinitiation system using CdSe QDs could be readily employed for photo 3D printing of photocurable resin poly(ethylene glycol) diacrylates, opening up vast opportunities for fabricating advanced polymer–inorganic hybrid materials.

中文翻译：

硫醇配体封端的量子点作为一种高效的耐氧光引发剂，用于水相自由基聚合和可见光下的 3D 打印

我们在这里报告了在水性介质中由仅 ppm 级硫醇配体封端的硒化镉 (CdSe) 量子点 (QD) 光引发的快速可见光诱导的自由基聚合。与各种双功能硫醇配体的简单配体交换程序促进了 CdSe 量子点在水中的分散，从而扩大了水性光催化剂的范围。聚合表现出优异的耐氧性，提供低分散性（Đ) 的 1.27。提议添加硫醇分子作为共引发物质，被光激发的 CdSe QD 氧化以形成硫自由基并进一步引发聚合。更重要的是，成功的硫醇-烯点击反应是通过将硫醇与烯烃的比例扩大到 1 来实现的，这表明硫醇配体共引发机制，同时证明了 QD 光催化剂在有机转化中的巨大潜力。此外，使用 CdSe QD 的光引发系统可以很容易地用于光固化树脂聚（乙二醇）二丙烯酸酯的 3D 打印，为制造先进的聚合物 - 无机杂化材料开辟了广阔的机会。

更新日期：2021-08-25

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