Mikhailov I V, Darinskii A A, Zhulina E B, Borisov O V, Leermakers F A M
Institute of Macromolecular Compounds of the Russian Academy of Sciences, 199004, St. Petersburg, Russia.
Institute of Macromolecular Compounds of the Russian Academy of Sciences, 199004, St. Petersburg, Russia and St. Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101 St. Petersburg, Russia.
Soft Matter. 2015 Dec 28;11(48):9367-78. doi: 10.1039/c5sm01620g.
We present numerical results for the thermodynamic rigidity and induced persistence length of dendronized polymers with systematically varied topology of their grafts obtained by the Scheutjens-Fleer self-consistent field method. The results were compared to predictions of an analytical mean-field theory. The two approaches have marked different predictions. In particular, the analytical theory predicts that the induced persistence length and the effective segment aspect ratio of dendronized polymers are increasing functions of the degree of branching of their side chains, whereas numerical calculations provide evidence of the opposite dependences. This discrepancy is argued to be due to the ability of side chains to repartition from the compressed to the dilated regions of a curved bottle brush, which is accounted for by the numerical, but not by the analytical method. The difference is most crucial in the light of the expected ability of dendronized polymers to have a liquid crystalline ordering in semi-dilute solutions.
我们展示了通过Scheutjens-Fleer自洽场方法获得的具有系统变化接枝拓扑结构的树枝状聚合物的热力学刚性和诱导持久长度的数值结果。将结果与解析平均场理论的预测进行了比较。这两种方法有明显不同的预测。特别是，解析理论预测树枝状聚合物的诱导持久长度和有效链段长径比是其侧链支化度的增函数，而数值计算则提供了相反依赖性的证据。这种差异被认为是由于侧链能够从弯曲的瓶刷状聚合物的压缩区域重新分配到膨胀区域，这一点数值方法考虑到了，但解析方法没有考虑到。鉴于树枝状聚合物在半稀溶液中具有液晶有序排列的预期能力，这种差异最为关键。
