Synthesis of well‐defined chain‐end‐functionalized polystyrenes with four, eight, and sixteen perfluorooctyl groups and their surface characterization
Synthesis of well‐defined chain‐end‐functionalized polystyrenes with four, eight, and sixteen perfluorooctyl groups and their surface characterization
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DOI：
10.1002/pat.430
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发表时间：
2004
影响因子：
3.4
通讯作者：
A. Hirao;S. Sakai;K. Sugiyama
中科院分区：
文献类型：
--
作者：
A. Hirao;S. Sakai;K. Sugiyama
我们通过活性阴离子聚合，通过具有树枝状苄基溴部分的链端功能化聚苯乙烯与仲丁基锂和功能化1,1-二苯基烷基阴离子的偶联反应，成功合成了一系列具有一定数量的4、8和16个全氟辛基（C8F17）基团的新型链端功能化聚苯乙烯。 1,1-双(4-叔丁基二甲基硅氧基苯基)乙烯、脱保护以及与C8F17(CH2)3Br的Williamson反应。所得聚合物的分子量和分子量分布得到精确控制，并且链端官能度得到明确定义。由这种具有 C8F17 基团的链端官能化聚苯乙烯铸造的退火薄膜的表面结构已通过接触角和角度依赖性 X 射线光电子能谱 (XPS) 测量进行了表征。两次测量都清楚地观察到，C8F17 基团优先与其聚苯乙烯主链分离，并在表面显着富集。然而，通过将C8F17组的数量从4个、8个甚至16个增加，C8F17组的富集程度仅小幅增加。我们将目前的结果与之前使用具有 1、2、3 和 4 个 C8F17 基团的链端官能化聚苯乙烯以及结构类似的嵌段共聚物获得的结果进行了比较，并更详细地讨论了富集程度对 C8F17 基团数量的依赖性。版权所有 © 2004 约翰·威利父子有限公司
We have successfully synthesized a series of novel well-defined chain-end-functionalized polystyrenes with a definite number of four, eight, and sixteen perfluorooctyl (C8F17) groups, via living anionic polymerization, by the coupling reaction of chain-end-functionalized polystyrenes with dendritic benzyl bromide moieties with the functionalized 1,1-diphenylalkylanion prepared from sec-BuLi and 1,1-bis(4-tert-butyldimethylsilyloxyphenyl)ethylene, deprotection, and a Williamson reaction with C8F17(CH2)3Br. The resulting polymers were precisely controlled in molecular weight and molecular weight distribution as well as well-defined in chain-end-functionality. Surface structures of the annealed films cast from such chain-end-functionalized polystyrenes with C8F17 groups have been characterized by contact angle and angle-dependent X-ray photoelectron spectroscopy (XPS) measurements. It has been clearly observed by both measurements that the C8F17 groups are preferentially segregated from their polystyrene main chains and significantly enriched at the surfaces. However, the degree of enrichment of C8F17 group increased only to a small extent by increasing the C8F17 group from four, eight, and even sixteen in number. We have compared the present results with the previous ones obtained by using chain-end-functionalized polystyrenes with one, two, three, and four C8F17 groups and the structurally analogous block copolymers and discussed in more detail in terms of the dependence of enrichment degree on number of C8F17 group. Copyright © 2004 John Wiley & Sons, Ltd.