Analysis of Surface Segregation of Bottlebrush Polymer Additives in Thin Film Blends with Attractive Intermolecular Interactions
Analysis of Surface Segregation of Bottlebrush Polymer Additives in Thin Film Blends with Attractive Intermolecular Interactions
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具有有吸引力的分子间相互作用的薄膜共混物中洗瓶刷聚合物添加剂的表面偏析分析
DOI：
10.1021/acs.macromol.0c00744
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发表时间：
2020
期刊：
影响因子：
5.5
通讯作者：
Verduzco, Rafael
中科院分区：
文献类型：
--
作者：
Miyagi, Kazuma;Mei, Hao;Terlier, Tanguy;Stein, Gila E.;Verduzco, Rafael
聚合物薄膜和涂层的表面化学具有广泛的应用，最近的研究表明，瓶刷聚合物可以用作改性薄膜界面和表面的添加剂。在与足够分子量的线性聚合物共混物中，瓶刷状聚合物将使界面丰富，部分是由熵效应驱动的。然而，先前的工作只研究了瓶刷和线性聚合物之间的中性或排斥相互作用的有限系统。在此，我们研究了具有吸引分子间相互作用的瓶刷聚合物和线性聚合物共混物的表面偏析。具体来说，我们研究了瓶刷式聚甲基丙烯酸环己基酯（BBPCHMA）和线性聚苯乙烯（PS）在BBPCHMA主链和线性PS长度范围内的共混物。飞行时间二次离子质谱测试表明，当瓶刷侧链比基体线性PS短时，瓶刷添加剂向膜表面强烈分离，热处理2天后，表面仍富集着瓶刷添加剂。与与线性PS具有中性或排斥性相互作用的瓶刷相比，铸态薄膜中BBPCHMA的表面偏析较弱，而热处理后的表面偏析更为明显。这一比较表明，在铸造过程中，结构效应可以驱动偏析，而在热退火过程中，聚合物与空气界面的相互作用更为显著。最后，我们证明了这些瓶刷添加剂可以在热退火过程中通过扩散到受损区域来自我修复受损表面。这项工作为了解瓶刷聚合物添加剂的偏析行为以及在铸造和热处理过程中驱动偏析的因素提供了新的见解。
The surface chemistry of polymer films and coatings is relevant to a wide range of applications, and recent work has shown that bottlebrush polymers can be used as additives to modify film interfaces and surfaces. In blends with linear polymers of a sufficient molecular weight, bottlebrush polymers will enrich interfaces driven, in part, by entropic effects. However, prior work has only studied a limited set of systems with either neutral or repulsive interactions between the bottlebrush and linear polymers. Herein, we investigated surface segregation in blends of bottlebrush and linear polymers with attractive intermolecular interactions. Specifically, we studied blends of bottlebrush poly(cyclohexyl methacrylate) (BBPCHMA) and linear polystyrene (PS) over a range of BBPCHMA backbone and linear PS lengths. Time-of-flight secondary ion mass spectroscopy measurements of the blends showed that bottlebrush additives strongly segregated to the film surface when the bottlebrush side chain was shorter than matrix linear PS, and the surface remained enriched with bottlebrush after 2 days of thermal annealing. In comparison to studies with bottlebrushes having neutral or repulsive interactions with linear PS, the surface segregation of BBPCHMA was weaker in the as-cast films but more significant after thermal annealing. This comparison suggests that architectural effects can drive segregation during casting and the interaction of the polymers with the air interface is more significant during thermal annealing. Finally, we demonstrated that these bottlebrush additives could self-heal a damaged surface by diffusing to a damaged region during thermal annealing. This work provides new insight into the segregation behavior of bottlebrush polymer additives and factors that drive segregation during casting and thermal annealing.
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