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Crystallization-driven self-assembly of Poly(methyl methacrylate)-b-Polyethylene-b-Poly(methyl methacrylate) triblock copolymers: aggregation behavior and effects of corona-forming block

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Abstract

Crystallization-driven self-assembly of poly(methyl methacrylate)-b-polyethylene-b-poly(methyl methacrylate) (PMMA-b-PE-b-PMMA) triblock copolymers in toluene and toluene-chloroform mixture solutions was carried out. It is found that the structure of amorphous corona-forming block, solvent selectivity and crystallization temperature play important roles in regulating the morphology of micelles. First of all, on cooling from a homogenous toluene solution, the linear-shaped PMMA100-b-PE572-b-PMMA100 (E1) and dumbbell-shaped (PMMA3)29-b-PE572-b-(PMMA3)29 (E3) are assembled into “striped disk-like” and “striped lozenge-shaped” micelles respectively, through a stepwise micellization/crystallization process. In the mixed solvent, both E1 and E3 can self-assemble into one-dimensional crystalline “cocoon silk” micelles at a higher crystallization temperature (60 °C and 70 °C, respectively) by the epitaxial crystallization of the unimers. At a lower temperature (30 °C and 50 °C, respectively), the “spindle-like” micelles were assembled due to the stronger crystallization driving force and weaker chain motion ability. In particular, E3 can be further transformed from “spindle-like” micelle to two-dimensional “lozenge-shaped” single crystals (at 30 °C), reflecting the regulatory role of corona-forming blocks.

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Acknowledgements

The Bio-ultrastructure Analysis Laboratory of the Key Laboratory of Applied Marine Biotechnology of the Ministry of Education, Ningbo University provides assistance with testing TEM.

Funding

The Project of the Natural Science Foundation of Ningbo (2019A610149), Natural Science Foundation of Zhejiang Province (LY18B040001) , National Natural Science Foundation of China (52007087).

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Authors and Affiliations

  1. Department of Polymer Science and Engineering, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, 315211, PR China

    Xin Han, Ning Gong, Xiaowen Si, Chenxi Jiang & Jingshan Mu

  2. Department of Physiology and Pharmacology, Health Science Center, Ningbo University, Zhejiang Province, Ningbo, 315211, PR China

    Jia Xu & Shimeng Sun

  3. Key Laboratory of Aquacultral Biotechnology Ministry of Education, Ningbo University, Ningbo, 315832, PR China

    PingPing Zhan

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  1. Xin Han
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Han, X., Gong, N., Si, X. et al. Crystallization-driven self-assembly of Poly(methyl methacrylate)-b-Polyethylene-b-Poly(methyl methacrylate) triblock copolymers: aggregation behavior and effects of corona-forming block. J Polym Res 30, 223 (2023). https://doi.org/10.1007/s10965-023-03608-7

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