Milenin Sergey A, Selezneva Elizaveta V, Tikhonov Pavel A, Vasil'ev Viktor G, Buzin Alexander I, Balabaev Nikolay K, Kurbatov Andrey O, Petoukhov Maxim V, Shtykova Eleonora V, Feigin Lev A, Tatarinova Elena A, Kramarenko Elena Yu, Chvalun Sergey N, Muzafarov Aziz M
Enikolopov Institute of Synthetic Polymeric Materials of Russian Academy of Sciences (ISPM RAS), 117393 Moscow, Russia.
A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), 119991 Moscow, Russia.
Polymers (Basel). 2021 Feb 17;13(4):606. doi: 10.3390/polym13040606.
A series of carbosilane dendrimers of the 4th, 6th, and 7th generations with a terminal trimethylsilylsiloxane layer was synthesized. Theoretical models of these dendrimers were developed, and equilibrium dendrimer conformations obtained via molecular dynamics simulations were in a good agreement with experimental small-angle X-ray scattering (SAXS) data demonstrating molecule monodispersity and an almost spherical shape. It was confirmed that the glass transition temperature is independent of the dendrimer generation, but is greatly affected by the chemical nature of the dendrimer terminal groups. A sharp increase in the zero-shear viscosity of dendrimer melts was found between the 5th and the 7th dendrimer generations, which was qualitatively identical to that previously reported for polycarbosilane dendrimers with butyl terminal groups. The viscoelastic properties of high-generation dendrimers seem to follow some general trends with an increase in the generation number, which are determined by the regular branching structure of dendrimers.
合成了一系列具有末端三甲基硅基硅氧烷层的第4、6和7代碳硅烷树枝状大分子。建立了这些树枝状大分子的理论模型,通过分子动力学模拟获得的平衡树枝状大分子构象与实验小角X射线散射(SAXS)数据吻合良好,证明了分子的单分散性和近乎球形的形状。证实了玻璃化转变温度与树枝状大分子的代数无关,但受树枝状大分子末端基团化学性质的显著影响。在第5代和第7代树枝状大分子之间发现树枝状大分子熔体的零剪切粘度急剧增加,这与先前报道的具有丁基末端基团的聚碳硅烷树枝状大分子的情况在定性上是相同的。高代树枝状大分子的粘弹性性质似乎随着代数的增加遵循一些一般趋势,这是由树枝状大分子的规则分支结构决定的。