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首页> 外文期刊>Journal of Polymer Science, Part A. Polymer Chemistry >Ordered Nanostructures at Two Different Length Scales Mediated by Temperature: A Triphenylene-Containing Mesogen-Jacketed Liquid Crystalline Polymer with a Long Spacer
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Ordered Nanostructures at Two Different Length Scales Mediated by Temperature: A Triphenylene-Containing Mesogen-Jacketed Liquid Crystalline Polymer with a Long Spacer

机译：温度介导的两个不同长度尺度上的有序纳米结构：带有长间隔基的含三亚苯基的介晶护套液晶聚合物

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摘要

A mesogen-jacketed liquid crystalline polymer (MJLCP) containing triphenylene (Tp) moieties in the side chains with 12 methylene units as spacers (denoted as PP12V) was synthesized. Its liquid crystalline (LC) phase behavior was studied with a combination of solution ~1H NMR, solid-state NMR, gel permeation chromatography, thermogravimetric analysis, polarized light microscopy, differential scanning calorimetry, and one- and two-dimensional wide-angle X-ray diffraction. By simply varying the temperature, two ordered nanostructures at sub-10-nm length scales originating from two LC building blocks were obtained in one polymer. The low-temperature phase of the polymer is a hexagonal columnar phase (Φ_H, a=2.06 nm) self-organized by Tp discotic mesogens. The high-temperature phase is a nematic columnar phase with a larger dimension (a'=4.07 nm) developed by the rod-like supramolecular mesogen-the MJLCP chain as a whole. A re-entrant isotropic phase is found in the medium temperature range. Partially homeotropic alignment of the polymer can be achieved when treated with an electric field, with the polymer in the Φ_H phase developed by the Tp moieties. The incorporation of Tp moieties through relatively long spacers (12 methylene units) disrupts the ordered packing of the MJLCP at low temperatures, which is the first case for main-chain/side-chain combined LC polymers with MJLCPs as the main-chain LC building block to the best of our knowledge. The relationship of the molecular structure and the novel phase behavior of PP12V has implications in the design of LC polymers containing nanobuilding blocks toward constructing ordered nanostructures at different length scales.
机译：合成了在侧链中含有三亚苯基（Tp）部分，以12个亚甲基单元为间隔基（表示为PP12V）的介晶夹层液晶聚合物（MJLCP）。通过溶液〜1H NMR，固态NMR，凝胶渗透色谱，热重分析，偏振光显微镜，差示扫描量热法和一维和二维广角X的组合研究了其液晶（LC）相行为射线衍射。通过简单地改变温度，在一种聚合物中获得了源自两个LC构件的亚十纳米以下的两个有序纳米结构。聚合物的低温相是由Tp盘状介晶元自组织的六方柱状相（Φ_H，a = 2.06 nm）。高温相是由棒状超分子介晶-MJLCP链整体形成的较大尺寸（a'＝ 4.07nm）的向列柱状相。在中等温度范围内发现凹状各向同性相。当用电场处理时，通过Tp部分形成的聚合物处于Φ_H相，可以实现聚合物的部分垂直排列。通过相对长的间隔基（12个亚甲基单元）引入Tp部分会破坏MJLCP在低温下的有序堆积，这是将MJLCPs作为主链LC结构的主链/侧链组合LC聚合物的第一种情况尽我们所能阻止。 PP12V的分子结构与新型相行为之间的关系对于包含纳米结构单元的LC聚合物的设计具有影响，以构造不同长度尺度的有序纳米结构。

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