Polyhedral oligomeric silsesquioxane (POSS) with a hollow rigid cage or semi cage structure is a new type of organic-inorganic hybrid nano-particles, which not only simultaneously combine the merits of inorganic and organic composition, but also obtains new properties by virtue of the synergistic effects, making it become the most potential choice in molecular structure design. When POSS is well dispersed in polymer matrix at molecular level or nano-scale aggregates, it can effectively improve the thermal properties, mechanical properties, magnetic properties, acoustic properties, surface properties and so on, therefore, POSS has developed rapidly in the field of biomedicine, catalyst, optical materials and dielectric materials. The preparation methods of POSS have vital impact on the structural properties of POSS/polymer nanocomposites. The early synthesis techno-logy of POSS/polymer nanocomposites mainly focused on the physical method which was immature. However, the nanoparticles in the compo-sites prepared by this method disperse unevenly, and are agglomeration-prone, which seriously affect the performances of the materials. Recently, researchers have paid close attention to the influence of structure on the properties of composite materials, in addition, they also have devoted much efforts on continuous innovation and research on synthetic technology. The technology of preparing the POSS/polymer nanocomposites via chemical method has made great progress with the precise control of the substituents and polymer chains on the Si atom in the POSS structure, significantly improving the compatibility between the POSS and the polymer matrix. Researchers have been capable of obtaining POSS/polymer nanocomposites with defined chemical structures and various functional groups through disparate chemical methods, and the structures are characterized by nuclear magnetic resonance hydrogen spectrum, time of flight mass spectrometry, silicon spectroscopy, fourier transform infrared spectroscopy, and wide angle X-ray diffraction. At the same time, POSS can be assembled into the polymer system in the form of main chain, side chain or end group to form POSS/polymer nanocomposites with diffe-rent topological structures such as graft structure, bead type structure or star type structure. The chemical method is benificial to give full play to the superior performance of POSS, greatly improve the synthesis efficiency of POSS/polymer nanocomposites, and provides a theoretical basis for further exploring the relationship between the structure of POSS/polymer and functional composite. In this paper, the molecular structure and properties of POSS and the structure and preparation methods of POSS/polymer nanocomposites were reviewed respectively. In which the preparation methods of POSS/polymer nanocomposites including blending method, atomic transfer free radical polymerization method, emulsion polymerization method, point strike chemistry method, electrospinning method were highlighted. Finally, the author proposes the further development direction of POSS/polymer nanocomposites, who believes that ensuring the good dispersion of POSS in diverse polymer matrix is still the primary problem, more characterization methods should be employed to acquire the related information of composite materials, and seek out the relationship between the degree of reaction of substituents and the properties of composite materials, which is of great significance for achieving potential the properties of composite materials. © 2019, Materials Review Magazine. All right reserved.
