Well-defined dendronized polymers (denpols) bearing high-generation dendron are attractive nano-objects as high persistency provides distinct properties, contrast to the random coiled linear polymers However, their syntheses via graft-through approach have been very challenging due to their structural complexity and steric hindrance retarding polymerization. Here, we report the first example of the synthesis of poly(norbornene) (PNB) containing ester dendrons up to the sixth generation (G6) by ring-opening metathesis polymerization. This is the highest generation ever polymerized among dendronized polymers prepared by graft-through approach, producing denpols with molecular weight up to 1960 kg/mol. Combination of size-exclusion chromatography, light scattering, and neutron scattering allowed a thorough structural study of these large denpols in dilute solution. A semiflexible cylinder model was successfully applied to represent both the static and dynamic experimental quantities yielding persistent length (lp), cross-sectional radius (Rcs), and contour length (L). The denpol persistency seemed to increase with generation, with lp reaching 27 nm (Kuhn length 54 nm) for PNB-G6, demonstrating a rod-likeconformation. Poly(endo-tricycle[4.2.2.0]deca-3,9-diene) (PTD) denpolsexhibited larger persistency than the PNB analogues of the same generationpresumably due to the higher grafting density of the PTD denpols.As the dendritic side chains introduce shape anisotropy into the denpolbackbone, future work will entail a study of these systems in theconcentrated solutions and melts.
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机译:定义清晰的带有高密度树突的树状聚合物(denpols)是有吸引力的纳米物体,因为高持久性可提供独特的性能,与无规卷曲线性聚合物相反。然而,由于结构复杂,通过接枝法合成的树突状聚合物非常具有挑战性和位阻聚合。在这里,我们报道了通过开环复分解聚合合成直至第六代(G6)的含酯树突的聚降冰片烯(PNB)的第一个例子。这是通过接枝法制备的树枝状聚合物中聚合的最新一代,可生产分子量高达1960 kg / mol的树胶。尺寸排阻色谱,光散射和中子散射相结合,可以对稀溶液中的这些大树胶进行彻底的结构研究。半挠性圆柱模型已成功应用于表示静态和动态实验量,产生持续长度(lp),横截面半径(Rcs)和轮廓长度(L)。 denpol的持久性似乎随着世代的增加而增加,PNB-G6的lp达到27 nm(库恩长度为54 nm),表明呈棒状构象。聚(三环内[4.2.2.0] deca-3,9-二烯)(PTD)树胶表现出比同代PNB类似物更大的持久性大概是由于PTD牙粉的接枝密度更高。由于树突状侧链将形状各向异性引入到树突中骨干,未来的工作将需要对这些系统进行研究浓缩溶液并熔化。
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