Synthesis and Solution Self-Assembly of Poly(1,3-dioxolane)
Synthesis and Solution Self-Assembly of Poly(1,3-dioxolane)
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聚(1,3-二氧戊环)的合成及溶液自组装
DOI：
10.1021/acs.macromol.9b00302
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发表时间：
2019-05-14
期刊：
影响因子：
5.5
通讯作者：
Schacher, Felix H.
中科院分区：
文献类型：
--
作者：
Qiu, Huan;Yang, Zhening;Schacher, Felix H.
聚（1，3-二氧戊环）（PDO）是一种对pH和温度敏感的水溶性高分子，广泛应用于功能性水凝胶和纳米粒子中。在这方面的贡献，我们报告了一系列高效的稀土三氟甲磺酸盐催化剂的布朗斯台德酸无开环聚合的DO。PDO的重复单元包含完全交替的亲水性乙二醇和疏水性甲醛单元，导致在水溶液中氢键控制的自组装。在透射电子显微镜图像中观察到球形聚集体，其尺寸可以通过浓度和温度进行调节，进一步证实水合物是通过氢键从“封闭”的水分子中衍生出来的。聚集体的尺寸和形态不仅可以通过退火过程由于半结晶区域的重新排列来调制，而且可以通过金属盐产生棒状、蠕虫状或球形结构来调制。在这种情况下，PDO能够充当表面活性剂和还原剂，因为缩醛部分的酸解，其在一步中原位形成核-壳Cu修饰的杂化材料，从而为生成金属纳米颗粒提供了有前途的未来模板。
Poly(1,3-dioxolane) (PDO) is widely used as a pH- and temperature-sensitive water-soluble polymer applied in functional hydrogels and nanoparticles. In this contribution, we report a series of highly efficient rare-earth triflate catalysts for a Bronsted-acid-free ring-opening polymerization of DO. The repeat unit of PDO comprises perfectly alternating hydrophilic ethylene glycol and hydrophobic methyl aldehyde units leading to hydrogen-bonding-controlled self-assembly in aqueous solution. Spherical aggregates are observed in transmission electron microscopy images whose sizes can be tuned by concentration and temperature, further confirming that the hydrate is derived from "blocked" water molecules through hydrogen bonding. The size and morphology of the aggregates can be modulated not only by the annealing process owing to the realignment of semicrystalline regions but also by metal salts generating rodlike, wormlike, or spherical structures. In this case, PDO is able to act as both a surfactant and as a reductant on account of the acidolysis of acetal moieties, which form a core-shell Cu-decorated hybrid material in situ in one step, thus providing a promising future template for the generation of metal nanoparticles.