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Janus [3:5] Polystyrene–Polydimethylsiloxane Star Polymers with a Cubic Core
Macromolecules ( IF 5.5 ) Pub Date : 2018-01-11 00:00:00 , DOI: 10.1021/acs.macromol.7b02268
Peng-Fei Jin 1 , Yu Shao 1, 2 , Guang-Zhong Yin 1 , Shuguang Yang 2 , Jinlin He 3 , Peihong Ni 3 , Wen-Bin Zhang 1
Affiliation  

We describe the precision synthesis and self-assembly of a series of Janus star polymers with mixed [3:5] heteroarms of polystyrene (PS) and polydimethylsiloxane (PDMS) precisely arranged on a cubic scaffold of T8 polyhedral oligomeric silsesquioxane (POSS) in a spatially segregated fashion. The synthesis begins with a Janus POSS compound with three 2-hydroxylethyl groups on one face and five vinyl pendant groups on the rest vertexes. Facilitated by esterification and a “click” adaptor, two types of polymer arms are attached efficiently by sequential “click” reactions, which constitutes a general approach for modular synthesis of such Janus star polymers. The Janus feature is thoroughly characterized using NMR, FT-IR, SEC, and MALDI-TOF mass spectrometry, and the self-assembled structures are studied by small-angle X-ray scattering (SAXS) experiments. With increasing molecular weight of PS arm, the self-assembled phase transits from lamellae (LAM) to hexagonally packed cylinder (HEX) and further to inversed HEX structure, even though the molecular weight of each PDMS arm is as small as 1.4 kDa. Correspondingly, the feature sizes of these samples are very small. For example, the intercolumnar distance is only ∼6.4 nm in the HEX phase, and the column radius is as small as 1.8 nm. It is anticipated that diverse nanostructures can be created from the self-assembly of these Janus star polymers.

中文翻译:

Janus [3:5]具有立方核的聚苯乙烯-聚二甲基硅氧烷星形聚合物

我们描述了一系列Janus星形聚合物的精确合成和自组装,这些聚合物具有精确排列在T 8立方支架上的聚苯乙烯(PS)和聚二甲基硅氧烷(PDMS)的混合[3:5]杂支多面体低聚倍半硅氧烷(POSS)在空间上分开的方式。合成从Janus POSS化合物开始,该化合物在一个面上具有三个2-羟乙基,而在其余顶点具有五个乙烯基侧基。通过酯化和“点击”衔接子的促进,通过顺序的“点击”反应有效地连接了两种类型的聚合物臂,这构成了这种Janus星型聚合物模块化合成的一般方法。Janus特征使用NMR,FT-IR,SEC和MALDI-TOF质谱进行了彻底表征,并通过小角度X射线散射(SAXS)实验研究了自组装结构。随着PS臂分子量的增加,自组装相从薄片(LAM)转变为六方堆积圆柱体(HEX),然后进一步转变为逆HEX结构,即使每个PDMS臂的分子量小至1.4 kDa。相应地,这些样本的特征量很小。例如,在十六进制相中,柱间距离仅为〜6.4 nm,列半径小至1.8 nm。可以预料,这些Janus星型聚合物的自组装可以形成各种纳米结构。
更新日期:2018-01-11
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