Bolgova Yuliya I, Emel'yanov Artem I, Trofimova Olga M, Ivanova Anastasiya A, Albanov Alexander I, Kuznetsova Nadezhda P, Semenova Tatyana A, Pozdnyakov Alexander S
A.E. Favorsky Irkutsk Institute of Chemistry of the Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russia.
Polymers (Basel). 2024 Nov 21;16(23):3235. doi: 10.3390/polym16233235.
The requirement for the development of advanced technologies is the need to create new functional thermostable soluble polysilsesquioxanes. Combining the potential of organosilicon chemistry and the chemistry of heterocyclic compounds is a promising direction for the formation of novel organosilicon polymer systems with new properties and new possibilities for their practical application. Using the classical method of hydrolysis and polycondensation of previously unknown trifunctional (trimethoxysilylpropyl)glutarimide in the presence or absence of an acid or base catalyst, a universal approach to the formation of new thermostable soluble polysilsesquioxanes with glutarimide side-chain groups is proposed, which forms the basis for the synthesis of polysilsesquioxane polymers with different functionality. The weight average molecular weight of silsesquioxanes, determined by gel permeation chromatography, is practically independent of the reaction conditions and is 10-12 kDa; at the same time, the molecular weight distribution remains low and amounts to 1.38-1.47. According to thermogravimetric analysis, the resulting polysiloxanes have high thermal stability up to 335 °C. By the dynamic light scattering method, it was established that in an aqueous solution, silsesquioxane macromolecules are in an associated state, forming supramolecular structures due to the intermolecular interaction of individual macromolecules. The average hydrodynamic diameter of the particles was 46 nm. X-ray diffraction analysis showed the amorphous nature of the polymer. Polymer film coatings based on synthesized silsesquioxanes are characterized by 98% transmission in the visible spectrum and resistance to ultraviolet radiation, which is promising for the creation of functional transparent film coatings.
先进技术发展的需求在于创造新型功能性热稳定可溶性聚倍半硅氧烷。将有机硅化学的潜力与杂环化合物化学相结合,是形成具有新特性及实际应用新可能性的新型有机硅聚合物体系的一个有前景的方向。利用此前未知的三官能团(三甲氧基硅丙基)戊二酰亚胺在有或没有酸碱催化剂存在的情况下进行水解和缩聚的经典方法,提出了一种形成带有戊二酰亚胺侧链基团的新型热稳定可溶性聚倍半硅氧烷的通用方法,这为合成具有不同官能度的聚倍半硅氧烷聚合物奠定了基础。通过凝胶渗透色谱法测定的聚倍半硅氧烷的重均分子量实际上与反应条件无关,为10 - 12 kDa;同时,分子量分布仍然较低,为1.38 - 1.47。根据热重分析,所得聚硅氧烷在高达335℃时具有高的热稳定性。通过动态光散射法确定,在水溶液中,聚倍半硅氧烷大分子处于缔合状态,由于单个大分子之间的分子间相互作用形成超分子结构。颗粒的平均流体动力学直径为46 nm。X射线衍射分析表明该聚合物为无定形性质。基于合成的聚倍半硅氧烷的聚合物薄膜涂层在可见光谱中的透光率为98%,并且耐紫外线辐射,这对于制备功能性透明薄膜涂层很有前景。