Electrostatic Manipulation of Triblock Terpolymer Nanofilm Compartmentalization during Aqueous Photoinitiated Polymerization-Induced Self-Assembly,Macromolecules

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Electrostatic Manipulation of Triblock Terpolymer Nanofilm Compartmentalization during Aqueous Photoinitiated Polymerization-Induced Self-Assembly
Macromolecules ( IF 5.1 ) Pub Date : 2020-03-12 , DOI: 10.1021/acs.macromol.0c00024
Lei Cao ₁ , Qingqing Zhao ₁ , Qizhou Liu ₁ , Lei Ma ₁ , Chao Li ₁ , Xiyu Wang ₁ , Yuanli Cai ₁

Affiliation

Electrostatic manipulation of triblock terpolymer nanofilm compartmentalization has been achieved via visible light-initiated reversible addition–fragmentation chain transfer aqueous dispersion polymerization of diacetone acrylamide monomer using cationic–neutral diblock copolymer macro-chain transfer agent (macro-CTA) at 25 °C. This photoinitiated polymerization-induced self-assembly (photo-PISA) evolves into two modes depending on solution pH. At pH 2.5, this macro-CTA dissolves in water with a fully cationic block; electrostatic repulsion leads to conventional aqueous photo-PISA and the formation of monolayer colloidal nanofilms. At pH 7.3, the cationic block transforms to a hydrophobic ionomer block with 10% cationic repeat units, and the copolymer chains self-assemble into weakly cationic micelles, which leads to seeded photo-PISA via self-assembly into discrete nanoclusters within the hydrophobic lamellar framework to form multicompartmentalized monolayer nanofilms. The nanoscale phase-separated 2D-confined nanoclusters and the lamellar structure can be tuned by the ABC/BAC block sequence, the degree of polymerization of the growing block, and the copolymer concentration. This electrostatic manipulation sheds new light on the rational design and preparation of multicompartmentalized block copolymer 2D nanoobjects.

中文翻译：

三嵌段三元共聚物纳米膜在水引发的自组装过程中的自组装静电操纵

通过在25°C下使用阳离子-中性双嵌段共聚物大链转移剂（macro-CTA），通过可见光引发的可逆加成-断裂链转移双丙酮丙烯酰胺单体的水分散体聚合，实现了三嵌段三元共聚物纳米膜分隔的静电操作。这种光引发的聚合诱导的自组装（photo-PISA）取决于溶液的pH值演变为两种模式。在pH 2.5时，这种大分子CTA溶解在具有完全阳离子嵌段的水中。静电排斥导致常规的水性光-PISA和单层胶体纳米膜的形成。在pH 7.3下，阳离子嵌段转化为具有10％阳离子重复单元的疏水离聚物嵌段，并且共聚物链自组装成弱阳离子胶束，通过自组装成疏水的层状框架内的离散纳米簇，形成多隔室的单层纳米膜，从而产生种子状的光PISA。纳米级相分离的二维限制的纳米团簇和层状结构可以通过ABC / BAC嵌段序列，生长嵌段的聚合度和共聚物浓度进行调节。这种静电操作为多室嵌段共聚物二维纳米物体的合理设计和制备提供了新的思路。和共聚物浓度。这种静电操作为多室嵌段共聚物二维纳米物体的合理设计和制备提供了新的思路。和共聚物浓度。这种静电操作为多室嵌段共聚物二维纳米物体的合理设计和制备提供了新的思路。

更新日期：2020-03-12

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