Centro de Física de Materiales (CSIC, UPV/EHU)-MPC Materials Physics Center, Paseo Manuel de Lardizabal 5, 20018, San Sebastian, Spain.
Donostia International Physics Center, Paseo Manuel de Lardizabal 4, 20018, San Sebastian, Spain.
Macromol Rapid Commun. 2019 May;40(9):e1900046. doi: 10.1002/marc.201900046. Epub 2019 Feb 25.
Access to completely deuterated single-chain nanoparticles (dSCNPs) has remained an unresolved issue. Herein, the first facile and efficient procedure to produce dSCNPs is reported, which comprises: i) the use of commercially available perdeuterated cyclic ether monomers as starting reagents, ii) a ring-opening copolymerization process performed in bulk to produce a neat dSCNP precursor, iii) a standard azidation reaction to decorate this precursor with azide moieties, and iv) a facile intramolecular azide photodecomposition step carried out under UV irradiation at high dilution providing with highly valuable, completely deuterated soft nano-objects from the precursor. dSCNPs are used to investigate by means of neutron-scattering measurements the form factor (radius of gyration, scaling exponent) of polyethylene oxide (PEO) chains in nanocomposites with different amounts of dSCNPs. Moreover, to illustrate the possibilities offered by the synthetic route disclosed in this communication for potential applications, the significant reduction in viscosity observed in a pure melt of polyether-based single-chain nanoparticles when compared to a melt of the corresponding linear polymer chains is shown.
完全氘代单链纳米颗粒（dSCNPs）的获得仍然是一个未解决的问题。在此，首次报道了一种生产 dSCNPs 的简便、高效的方法，包括：i）使用市售的全氘代环醚单体作为起始试剂，ii）在本体中进行开环共聚反应以制备纯的 dSCNP 前体，iii）通过标准的叠氮化反应在前体上修饰叠氮基团，以及 iv）在高稀释度下通过紫外光照射进行简单的分子内叠氮光解步骤，从前体中得到高价值的、完全氘代的软纳 米物体。使用中子散射测量研究了不同含量的 dSCNPs 纳米复合材料中聚环氧乙烷（PEO）链的构象因子（回转半径、标度指数）。此外，为了说明本通讯中所揭示的合成途径在潜在应用中提供的可能性，展示了与相应的线性聚合物链的熔体相比，在基于聚醚的单链纳米颗粒的纯熔体中观察到的粘度显著降低。
