A new class of discrete-length block co-oligomers comprising oligodimethylsiloxane (oDMS) and oligomethylene (oM) is presented. For this, oM blocks containing up to 69 backbone carbons are synthesised via an iterative, Wittig reaction-based strategy. Ligation with oDMS hydrides permits the formation of a library of block co-oligomers (BCOs) in which the block configuration, MW, and composition can be tuned. Differential scanning calorimetry and small-angle X-ray scattering show that all BCOs exhibit microphase separation into well-ordered lamellar morphologies, driven by the crystallisation of the oM blocks. Pre-melting order–order transitions are present for a number of BCOs, resulting in an alteration of the oM crystal packing as well as in changes of the overall microphase-segregated structure. As a result of the discrete nature of the BCO chains, we propose models that describe the molecular organisation within the microphase-segregated structures by evaluating the changes in the lamellar thickness upon varying the BCO architecture.

中文翻译：

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离散的低聚二甲基硅氧烷-低聚二甲基和三嵌段共聚低聚物：合成，自组装和分子结构† •

提出了一种新的离散长度嵌段共聚低聚物，包括低聚二甲基硅氧烷（o DMS）和低聚亚甲基（o M）。对于这一点，ö含至多69个骨架碳M个块被合成通过迭代的，基于反应的Wittig策略。结扎ö DMS氢化物允许嵌段共低聚物（BCOS），其中所述块的配置，MW，和组合物可被调谐的文库的形成。差示扫描量热法和小角X射线散射表明，所有BCO都表现出微相分离，这是由o的结晶驱动的，形成了有序的层状形态M块。许多BCO均存在预熔化的阶跃转变，导致o M晶体堆积的变化以及整个微相分离结构的变化。由于BCO链的离散性，我们提出了一些模型，这些模型通过评估BCO结构改变时层状厚度的变化来描述微相分离结构内的分子组织。