Citation: CHENG Xiaomeng, JIAO Dongxia, LIANG Zhihao, WEI Jinjin, LI Hongping, YANG Junjiao. Self-Assembly Behavior of Amphiphilic Diblock Copolymer PS-b-P4VP in CO₂-Expanded Liquids[J]. Acta Physico-Chimica Sinica, ;2018, 34(8): 945-951. doi: 10.3866/PKU.WHXB201801292 shu

Self-Assembly Behavior of Amphiphilic Diblock Copolymer PS-b-P4VP in CO₂-Expanded Liquids

1.
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. China
2.
Beijing Key Laboratory of Environmentally Harmful Chemical Analysis, Beijing University of Chemical Technology, Beijing 100029, P. R. China

Corresponding author: LI Hongping, lihongping@zzu.edu.cn YANG Junjiao, yangjj@mail.buct.edu.cn
Received Date: 3 January 2018
Revised Date: 20 January 2018
Accepted Date: 25 January 2018
Available Online: 29 August 2018
Fund Project: This work was supported by the National Natural Science Foundation of China J1210060the Innovative Research Grant for Undergraduate Students of National/Zhengzhou University 201710459008This work was supported by the National Natural Science Foundation of China 21773215This work was supported by the National Natural Science Foundation of China (21773215, J1210060) and the Innovative Research Grant for Undergraduate Students of National/Zhengzhou University (201710459008)

The self-assembly behavior of block copolymers and their assembled micellar morphologies have attracted considerable attention because of their potential applications in biomedicine, drug delivery, and catalysis. Herein we report that CO₂-expanded liquids (CXLs) facilitate the morphology control of the self-assembled aggregates (SAAs) of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) formed in CO₂-expanded toluene. It is found that the anti-solvent effect of CXLs can successfully regulate the self-assembly behavior of the copolymer PS-b-P4VP. The difference in amphiphilicity between PS and P4VP block is reduced with increasing pressure of CO₂-expanded toluene owing to the anti-solvent effect of CO₂. In addition, this diminished difference may influence the interfacial tension at the P4VP core-PS corona interface, which triggers a morphological change of the aggregate. The SAA structures are dependent on both CXL pressure and copolymer composition under the experimental conditions implemented in this work. The morphological evolution of the SAAs in CXLs exhibits remarkable pressure dependence. As the pressure increases, the SAA structure of PS₁₆₈-b-P4VP₄₂₀ transits from primarily spheres (0.1 MPa) to mostly interconnected rods (6.35 MPa), the SAA of PS₇₉₀-b-P4VP₂₆₃ evolves from small vesicles (0.1 MPa) to large compound vesicles (LCVs, 6.35 MPa), whereas the PS₁₅₃-b-P4VP₁₅₃₀ counterpart switches from large compound micelles (LCMs, 0.1 MPa) to mainly large compound vesicles (LCVs, 6.35 MPa). Moreover, transmission electron microscopy (TEM) data on constant copolymer composition implies that the packing parameter p of the SAAs increases with the CXLs pressure. Especially, under the experimental conditions employed in this work, we find that the major factor controlling the SAA shape in conventional toluene is the copolymer composition, while in CO₂-expanded toluene, the dominant factor controlling the SAA morphology might be the varying contact area between shell-forming segment PS and the CXLs with increasing pressure. This work proves that the CXL method facilitates the modulation of morphology of the SAAs, and opens a green route for the development of new nano-functional materials.
- CO₂-expanded liquids,
- Colloidal aggregates,
- Morphology control,
- PS-b-P4VP,
- Self-assembly
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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Self-Assembly Behavior of Amphiphilic Diblock Copolymer PS-b-P4VP in CO2-Expanded Liquids

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通讯作者: 陈斌, bchen63@163.com

Self-Assembly Behavior of Amphiphilic Diblock Copolymer PS-b-P4VP in CO₂-Expanded Liquids