Selection of monomer couples, ensuring reactivity ratios close to zero, is an effective strategy to induce spontaneous copolymerization into an alternating sequence. In addition, monomer design and customisation of the solvent–monomer interactions open the way to functional copolymers showing molecular self-assembly relevant to their regular amphipathic structure. In this work, we show that the design of comonomers with adequate reactivities and interactions can be used to direct copolymer self-assembly on a mesoscopic scale. We investigate spontaneous formation of nanoparticles through solvent/non-solvent interactions using the so-called “ouzo effect”. In this way, an ouzo diagram was built to determine the operation window for the self-assembly, in aqueous suspensions, of alternating copolymers consisting of vinyl phenol and maleimide units carrying long alkyl-pendant groups (C₁₂H₂₅ or C₁₈H₃₇). Also, investigations were pursued to account for the influence of the lateral lipophilic pendant units on the size and structure of the nanoaggregates formed during one-shot water addition. Structure characterisation by light scattering techniques (DLS and SLS), small-angle neutron scattering (SANS) and transmission electron microscopy (cryo-TEM and TEM) confirmed the self-assembly of copolymer chains into nanoparticles (size range: 60–300 nm), the size of which is affected by the lipophilicity of the alternating copolymers, solvent–water affinity and the solvent diffusion in water. Altogether, we present here the spontaneous ouzo effect as a simple method to produce stable alternating copolymer nanoparticles in water without the addition of stabilizing agents.

中文翻译：

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Ouzo 相的发生与交替的脂类/亲水共聚物在水中

单体对的选择，确保反应率接近于零，是诱导自发共聚成交替序列的有效策略。此外，单体设计和溶剂-单体相互作用的定制为功能共聚物开辟了道路，显示出与其规则两亲结构相关的分子自组装。在这项工作中，我们表明具有足够反应性和相互作用的共聚单体的设计可用于在介观尺度上指导共聚物自组装。我们使用所谓的“茴香酒效应”研究通过溶剂/非溶剂相互作用自发形成的纳米颗粒。通过这种方式，建立了一个茴香酒图来确定自组装的操作窗口，在水悬浮液中，₁₂ H ₂₅或 C ₁₈ H ₃₇）。此外，还进行了研究以解释横向亲脂性悬垂单元对一次性加水过程中形成的纳米聚集体的尺寸和结构的影响。通过光散射技术（DLS 和 SLS）、小角度中子散射（SANS）和透射电子显微镜（低温 TEM 和 TEM）进行的结构表征证实了共聚物链自组装成纳米颗粒（尺寸范围：60-300 nm） ，其大小受交替共聚物的亲油性、溶剂-水亲和力和溶剂在水中的扩散影响。总而言之，我们在此介绍了自发茴香酒效应，这是一种无需添加稳定剂即可在水中生产稳定的交替共聚物纳米颗粒的简单方法。