Anionic Grafting to Strategies for Functional Polymethacrylates: Convenient Preparation of Stimuli‐Responsive Block Copolymer Architectures
Anionic Grafting to Strategies for Functional Polymethacrylates: Convenient Preparation of Stimuli‐Responsive Block Copolymer Architectures
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DOI：
10.1002/macp.201800548
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发表时间：
2019-01
影响因子：
2.5
通讯作者：
Michael Appold;Jennifer Bareuther;M. Gallei
中科院分区：
文献类型：
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作者：
Michael Appold;Jennifer Bareuther;M. Gallei
功能性嵌段共聚物（BCP）在分离技术、药物传递或（纳米）光刻等领域有着重要的应用前景。在这里，描述了一种通用的策略，用于通过方便的后修饰策略制备聚苯乙烯-嵌段-聚异戊二烯（PS-B-PI）BCP的功能性聚（甲基丙烯酸酯）接枝（PMA）。B-PI通过硅氢加成方案引入氯硅烷部分而官能化。随后的阴离子接枝-聚合不同官能的PMA大阴离子导致接枝的BCP。将各种官能和非官能均聚物，即聚（二（乙二醇）甲基醚甲基丙烯酸酯）、聚（甲基丙烯酸）和聚（3-甲基丙烯酰氧基丙基）七异丁基-T8-倍半硅氧烷以及聚（甲基丙烯酸甲酯）、聚（甲基丙烯酸正丁酯）、聚（甲基丙烯酸异丙酯）、聚（甲基丙烯酸叔丁酯）和聚（甲基丙烯酸2-羟乙酯）嵌段选择性地掺入PI链段中。非功能性PMA衍生物的应用接枝策略，其特征在于不同大小的烷基取代基，揭示了对接枝效率的强烈影响。接枝BCP架构能够在本体状态下进行微相分离，而所得的形态显着影响的PMA段的引入所示的透射电子显微镜测量。此外，通过动态光散射研究了聚（甲基丙烯酸）接枝BCP的结构形成和pH切换能力，证明了本文研究的合成策略的可行性。
Functional block copolymers (BCP) are promising candidates for many important applications in fields of separations technologies, drug delivery, or (nano)lithography. Here, a universal strategy is described for the preparation of functional poly(methacrylate)s grafted (PMA) to polystyrene‐block‐polyisoprene (PS‐b‐PI) BCPs via a convenient postmodification strategy. PS‐b‐PIs are functionalized by means of hydrosilylation protocols for the introduction of chlorosilane moieties. Subsequent anionic grafting‐to polymerization of different functional PMA macro anions leads to grafted BCP. Various functional and non‐functional homopolymers, that is, poly(di(ethylene glycol) methyl ether methacrylate), poly(methacrylic acid), and poly(3‐methacryloxypropyl)heptaisobutyl‐T8‐silsesquioxane as well as poly(methyl methacrylate), poly(n‐butyl methacrylate), poly(iso‐propyl methacrylate), poly(tert‐butyl methacrylate), and poly(2‐hydroxy ethyl methacrylate) are block‐selectively incorporated into the PI segment. Applied grafting strategies for the non‐functional PMA derivatives, which feature different sizes of the alkyl substituent, reveal a strong influence on the grafting‐to efficiency. The grafted BCP architectures are capable of undergoing microphase separation in the bulk state, while the resulting morphology is significantly influenced by the introduction of PMA segments as shown by transmission electron microscopy measurements. Additionally, the structure formation and pH‐switching capability of the poly(methacrylic acid)‐grafted BCP is studied by dynamic light scattering, proving the feasibility for the herein investigated synthesis strategy.