Consequences of Molecular Architecture on the Supramolecular Assembly of Discrete Block Co-oligomers.
Consequences of Molecular Architecture on the Supramolecular Assembly of Discrete Block Co-oligomers.
复制标题
DOI：
10.1021/acs.macromol.0c02237
复制
发表时间：
2020-11-24
期刊：
影响因子：
5.5
通讯作者：
Vantomme G
中科院分区：
文献类型：
--
作者：
Lamers BAG;van der Tol JJB;Vonk KM;de Waal BFM;Palmans ARA;Meijer EW;Vantomme G
由离散嵌段组成的超分子嵌段共聚物具有将明确的形态与良好的本体材料性能相结合的能力，因此在纳米技术方面具有广阔的前景。在这里，我们展示了主链中明确的硅氧烷嵌段或作为侧接枝存在对超分子嵌段共聚物的性能的影响，该超分子嵌段共聚物形成具有亚 5 nm 域的有序纳米结构。为此，基于脲基嘧啶酮-氨基甲酸酯（UPy-UT）基序合成了两种类型的超分子嵌段共聚物。首先，离散长度的低聚二甲基硅氧烷 (oDMS) 用 UPy-UT 基序封端，提供主链 UPy-UT-Sin。在第二个中，UPy-UT基序与离散的oDMS接枝，提供接枝的UPy-UT-g-Si7。对于这两个系统，其组成是相似的；只是分子结构不同。在这两种情况下，UPy-UT 块的结晶与 oDMS 的相分离协同作用，导致层状形态的形成。接枝的 UPy-UT-g-Si7 可以形成长程有序片层，从而形成微米尺寸的二维超分子聚合物片，具有脆性。相比之下，UPy-UT-Sin 形成延展性材料。由于两种 BCO 的组成相似，形态和机械性能的差异是分子结构的直接结果。这些结果展示了能够形成嵌段共聚物的结构单元的分子设计如何由于相互作用的超分子性质而转化为受控的纳米结构和材料特性。
Supramolecular block copolymers composed of discrete blocks have promising properties for nanotechnology resulting from their ability to combine well-defined morphologies with good bulk material properties. Here, we present the impact of a well-defined siloxane block in either the main-chain or present as pendant grafts on the properties of supramolecular block copolymers that form ordered nanostructures with sub-5 nm domains. For this, two types of supramolecular block copolymers were synthesized based on the ureidopyrimidinone–urethane (UPy-UT) motif. In the first, oligodimethylsiloxanes (oDMS) of discrete length were end-capped with the UPy-UT motif, affording main-chain UPy-UT-Sin. In the second, the UPy-UT motif was grafted with discrete oDMS affording grafted UPy-UT-g-Si7. For the two systems, the compositions are similar; only the molecular architecture differs. In both cases, crystallization of the UPy-UT block is in synergy with phase segregation of the oDMS, resulting in the formation of lamellar morphologies. The grafted UPy-UT-g-Si7 can form long-range ordered lamellae, resulting in the formation of micrometer-sized 2D sheets of supramolecular polymers which show brittle properties. In contrast, UPy-UT-Sin forms a ductile material. As the compositions of both BCOs are similar, the differences in morphology and mechanical properties are a direct consequence of the molecular architecture. These results showcase how molecular design of the building block capable of forming block copolymers translates into controlled nanostructures and material properties as a result of the supramolecular nature of the interactions.
登录
查看更多内容
影响因子：
5.5
作者：
Lamers, Brigitte A. G.;van Genabeek, Bas;Meijer, E. W.
通讯作者：
Meijer, E. W.
影响因子：
5.5
作者：
Koo, CM;Wu, LF;Bates, FS
通讯作者：
Bates, FS
影响因子：
4.6
作者：
Pitet, Louis M.;Chamberlain, Bradley M.;Hillmyer, Marc A.
通讯作者：
Hillmyer, Marc A.
影响因子：
17.1
作者：
Berrocal JA;Zha RH;de Waal BFM;Lugger JAM;Lutz M;Meijer EW
通讯作者：
Meijer EW
影响因子：
5.5
作者：
Appel, Wilco P. J.;Portale, Giuseppe;Meijer, E. W.
通讯作者：
Meijer, E. W.