Tailoring the Wettability and Substrate Adherence of Thin Polymer Films with Surface-Segregating Bottlebrush Copolymer Additives
Tailoring the Wettability and Substrate Adherence of Thin Polymer Films with Surface-Segregating Bottlebrush Copolymer Additives
复制标题
使用表面隔离洗瓶刷共聚物添加剂调整聚合物薄膜的润湿性和基材粘附性
DOI：
10.1021/acs.langmuir.3c00703
复制
发表时间：
2023
期刊：
影响因子：
3.9
通讯作者：
Stein, Gila E.
中科院分区：
文献类型：
--
作者：
Laws, Travis S.;Mei, Hao;Terlier, Tanguy;Verduzco, Rafael;Stein, Gila E.
我们开发了基于苯乙烯(S)和丙烯酸丁酯（tBA）作为聚苯乙烯（PS）涂料添加剂的“反应性”瓶刷聚合物。瓶刷聚合物在溶液铸造过程中自发地向空气和基材界面绽放。整洁的PS薄膜是疏水性的，并且在干净的硅片上与天然氧化物的粘附性很差，而含有瓶刷的PS薄膜的亲水性和衬底粘附性可以通过热激活的tBA脱保护来定制，从而产生丙烯酸（AA）和丙烯酸酐（AH）。一个关键的设计参数是将tBA加入瓶刷中的方式：当瓶刷侧链是S和tBA的共聚物时，即使在高温下长时间热退火，脱保护程度也极低。然而，当瓶刷含有聚丙烯酸丁酯（PtBA）和PS侧链的混合物时，几乎所有的tBA都转化为AA和AH。因此，使用经过热处理和适当调理的“混合链”瓶刷设计，水接触角从未改性PS上的90°以上降低到含有瓶刷的PS膜上的75°，并且基材粘附程度与tBA脱保护程度成正比。
We developed “reactive” bottlebrush polymers based on styrene (S) andt-butyl acrylate (tBA) as additives for polystyrene (PS) coatings. The bottlebrush polymers spontaneously bloom to both the air and substrate interfaces during solution casting. While neat PS films are hydrophobic and poorly adhere to the native oxide on clean silicon wafers, the hydrophilicity and substrate adherence of bottlebrush-incorporating PS films can be tailored through the thermally activated deprotection of tBA to produce acrylic acid (AA) and acrylic anhydride (AH). A critical design parameter is the manner by which tBA is incorporated into the bottlebrush: When the bottlebrush side chains are copolymers of S and tBA, the extent of deprotection is extremely low, even after prolonged thermal annealing at elevated temperature. However, when the bottlebrush contains a mixture of poly(t-butyl acrylate) (PtBA) and PS side chains, nearly all tBA is converted to AA and AH. Consequently, using the “mixed-chain” bottlebrush design with thermal processing and appropriate conditioning, the water contact angle is reduced from over 90° on unmodified PS down to 75° on bottlebrush-incorporating PS films, and the substrate adherence is improved in proportion to the extent of tBA deprotection.